CN103769078B - A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation method and application - Google Patents
A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation method and application Download PDFInfo
- Publication number
- CN103769078B CN103769078B CN201210408472.1A CN201210408472A CN103769078B CN 103769078 B CN103769078 B CN 103769078B CN 201210408472 A CN201210408472 A CN 201210408472A CN 103769078 B CN103769078 B CN 103769078B
- Authority
- CN
- China
- Prior art keywords
- chromium
- catalyst
- alkali metal
- active component
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention discloses a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation method and application.This catalyst is with Al
2o
3for carrier, take chromium as active component, take alkali metal as co catalysis component, be benchmark by the weight of final catalyst, the content of chromium oxide is 10.0% ~ 30.0%, alkali metal oxide content is 0.5% ~ 3.0%, and surplus is aluminium oxide, described active component chromium before dipping alkali metal co catalysis component and after dipping alkali metal co catalysis component step impregnation on alumina support.The application of above-mentioned catalyst for manufacturing olefin by low-carbon alkane dehydrogenation in preparing propylene by dehydrogenating propane.This catalyst for manufacturing olefin by low-carbon alkane dehydrogenation has high activity stability and Propylene Selectivity, and preparation method is simple, is suitable for commercial Application.
Description
Technical field
The present invention relates to a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation method and application, relate in particular to a kind of C3 ~ C4 dehydrating alkanes alkene catalyst and its preparation method and application.
Background technology
In recent years, along with the fast development of Global Oil chemical industry, also growing to the demand of low-carbon alkene.Low-carbon alkanes catalytic dehydrogenation technology is the effective way of volume increase C3 ~ C4 alkene.At present, dehydrogenating low-carbon alkane technology comprises in the world: the Oleflex technique of Uop Inc., the Catofin technique of ABB Lu Musi company, the Star technique of Kang Fei (Uhde) company, the FBD-4 technique of Snamprogetti/Yarsintz company, the PDH technique etc. of Lin De/BASF AG.In the device built, former Soviet Union's great majority adopt FBD-4 technique, and Catofin and Oleflex technique has become the leading technique adopted in new device.Oleflex technique is mainly catalyst based based on Pt, and Catofin technique is mainly with Cr
2o
3/ Al
2o
3be main.
CN86104031A discloses the method that one prepares C3 ~ C5 paraffin hydrocarbon dehydrogenation catalyst, the method adopts surface area and the pore volume of high-temperature roasting method (higher than 1000 DEG C) adjustment alumina support, then with the compound solution oxide impregnation alumina supporter containing chromium and potassium, and it is dry, then by products obtained therefrom siliceous compound solution dipping, finally drying and roasting is carried out.CN1668555A discloses a kind of dehydrogenation catalyst complex containing aluminium oxide, chromium oxide, lithia and sodium oxide molybdena.This catalyst is mixed in Woelm Alumina matrix chromium oxide, lithia and sodium oxide molybdena, or be prepared from matrix chromium oxide and sodium oxide molybdena being mixed into Woelm Alumina and lithia.Active component chromium is adopted that infusion process is disposable loads in Woelm Alumina matrix by said method, and prepared catalyst exists shortcoming and the deficiency such as selective low of activity stability difference and product.
For the deficiency of above preparation method, CN200910012450.1 discloses a kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof.Prepared catalyst take chromium as active metal component, take alkali metal as co catalysis component, to contain chromium aluminium oxide for carrier, wherein content meter by weight, chromium oxide content is in the carrier 2.0% ~ 15.0%, total content is in the final catalyst 10.0% ~ 45.0%, alkali-metal content with oxide basis for 1.0% ~ 5.0%.In the method, active metal component chromium introduces the method in alumina support is that part adopts kneading method, and part adopts infusion process, and adopts three one-step baking methods and hydro-thermal method process to be mixed into the boehmite of chromium.Said method improves the load capacity of chromium and the activity of catalyst and stability, enhances the anti-carbon deposition ability of catalyst, extends the service life of catalyst.But the preparation process more complicated of the method, active component chromic oxide content is higher, and the activity stability of catalyst and the option demand of product improve further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation method and application.This catalyst has high activity stability and target product selectivity, and preparation method is simple, is suitable for commercial Application.
A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, with Al
2o
3for carrier, take chromium as active component, take alkali metal as co catalysis component, be benchmark by the weight of final catalyst, the content of chromium oxide is 10.0% ~ 30.0%, alkali metal oxide content is 0.5% ~ 3.0%, and surplus is aluminium oxide, described active component chromium before dipping alkali metal co catalysis component and after dipping alkali metal co catalysis component step impregnation on alumina support.
Before dipping alkali metal co catalysis component, flood the active component chromium of 60% ~ 80% in the present invention, after dipping alkali metal co catalysis component, flood the active component chromium of surplus.
Co catalysis component alkali metal described in the present invention is the one in potassium, sodium and lithium.
A preparation method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, comprises the steps:
(1) to Al
2o
3carrier carries out flooding appropriate active component chromium, then drying, roasting;
(2) by step (1) gained containing chromium alumina load alkali metal, then drying, roasting;
(3) by the remaining active component chromium of alumina load containing chromium, alkali metal containing of step (2) gained, then drying, roasting obtain catalyst for manufacturing olefin by low-carbon alkane dehydrogenation of the present invention.
The presoma of the chromium described in the inventive method can be chromic nitrate, chromic acid or chromium acetate.The alkali metal of described load can be the one in lithium, sodium or potassium, preferred potassium, and the mass percentage that the potassium oxide of load accounts for catalyst is 0.1 ~ 3.0%, preferably 0.5 ~ 1.5%.
Dip time described in said method is 1 ~ 24 hour, preferably 1 ~ 12 hour.Described drying and roasting carry out in air atmosphere, and drying is 60 DEG C ~ 150 DEG C dryings 1 ~ 8 hour, and roasting is roasting 2 ~ 8 hours at 500 ~ 650 DEG C.
The total amount of the chromium flooded in the inventive method step (1) and (3) is 10.0% ~ 30.0% by oxide basis weight content in the final catalyst, the amount of the active component chromium flooded in step (1) is the 60%-80% of active component chromium total amount in final catalyst, preferred 65%-75%.
The application of above-mentioned catalyst for dehydrogenation of low-carbon paraffin in preparing propylene by dehydrogenating propane.
In the present invention, active component chromium oxide divides secondary to introduce in the front and back of dipping alkali metal promoter, the content of the active component chromium that the content of the active component chromium of introducing is introduced after being obviously greater than dipping alkali metal promoter before dipping alkali metal promoter.The active component chromium of graded impregnation and alkali metal promoter produce synergy, reduce the strong interaction between active component chromium and metal promoter and catalyst carrier, active component and alkali metal promoter can be made to be dispersed in carrier surface, improve decentralization and the load capacity of active component, more activated centre is contacted with reactant, avoid the formation of alpha-oxidation chromium, improve alkali metal as the effective adjustment of co catalysis component to Surface Acidity of Alumina Support, reduce the generation of the side reaction such as cracking, thus improve the activity of catalyst and selective.
Detailed description of the invention
Below in conjunction with embodiment to catalyst for manufacturing olefin by low-carbon alkane dehydrogenation of the present invention and preparation method thereof
Functions and effects be described further.
Example 1
Choose the ball-type γ-Al that diameter is 1.5 ~ 3mm
2o
3the presoma of the chromium that supported chromium oxide is chosen is chromic acid.Normal temperature dipping chromic acid solution was dried 5 hours in 120 DEG C after 5 hours, 600 DEG C of roastings 4 hours.The content of the active component chromium oxide of institute's load is 70% of chromium total content in final catalyst.By the carrier loaded potassium oxide of load active component chromium, normal temperature dipping was dried 2 hours in 120 DEG C after 5 hours, 540 DEG C of roastings 3 hours.Carrier after load potassium oxide is continued load active component chromium, and normal temperature dipping chromic acid solution was dried 5 hours in 120 DEG C after 5 hours, and the obtained catalyst of 600 DEG C of roastings 4 hours is denoted as A.In obtained catalyst, chromium oxide quality accounts for 15% of catalyst gross mass, and potassium oxide quality accounts for 1% of catalyst gross mass.
Comparative example 1
Adopt conventional dipping method, active component chromium single-steeping before load potassium oxide is introduced, and all the other conditions are with embodiment 1, and obtained catalyst is denoted as B.In obtained catalyst, chromium oxide quality accounts for 15% of catalyst gross mass, and potassium oxide quality accounts for 1% of catalyst gross mass.
Example 2
Choose the ball-type γ-Al that diameter is 1.5 ~ 3mm
2o
3the presoma of the chromium that supported chromium oxide is chosen is chromic nitrate.Normal temperature dipping chromium nitrate solution was dried 5 hours in 120 DEG C after 5 hours, 600 DEG C of roastings 4 hours.The content of the active component chromium oxide of institute's load is 65% of chromium total content in final catalyst.By the carrier loaded sodium oxide molybdena of load active component chromium, normal temperature dipping was dried 2 hours in 120 DEG C after 5 hours, 540 DEG C of roastings 3 hours.Carrier after load sodium oxide molybdena is continued load active component chromium, and normal temperature dipping chromium nitrate solution was dried 5 hours in 120 DEG C after 5 hours, and the obtained catalyst of 600 DEG C of roastings 4 hours is denoted as C.In obtained catalyst, chromium oxide quality accounts for 21% of catalyst gross mass, and sodium oxide molybdena quality accounts for 1.5% of catalyst gross mass.
Example 3
Choose the ball-type γ-Al that diameter is 1.5 ~ 3mm
2o
3the presoma of the chromium that supported chromium oxide is chosen is chromium acetate.Normal temperature dipping chromium acetate solution was dried 5 hours in 120 DEG C after 5 hours, 600 DEG C of roastings 4 hours.The content of the active component chromium oxide of institute's load is 80% of chromium total content in final catalyst.By the carrier loaded lithia of load active component chromium, normal temperature dipping was dried 2 hours in 120 DEG C after 5 hours, 540 DEG C of roastings 3 hours.Carrier after load lithia is continued load active component chromium, and normal temperature dipping chromium acetate solution was dried 5 hours in 120 DEG C after 5 hours, and the obtained catalyst of 600 DEG C of roastings 4 hours is denoted as D.In obtained catalyst, chromium oxide quality accounts for 27% of catalyst gross mass, and lithia quality accounts for 0.5% of catalyst gross mass.
The catalyst got prepared by above each embodiment is evaluated in micro-reactor, and its appreciation condition is: propane volume space velocity 1000h
-1, reaction temperature 620 DEG C, reaction pressure is normal pressure.It initially lists in table 1 with propane one way molar yield when 30 minutes and Propylene Selectivity.
Table 1
| Catalyst | C 0/% | C 30/% | S 0/% | S 30/% |
| A | 55.58 | 42.34 | 85.92 | 88.48 |
| B | 48.72 | 35.87 | 80.94 | 86.97 |
| C | 56.33 | 43.16 | 85.78 | 89.62 |
| D | 56.82 | 42.27 | 84.56 | 86.95 |
Claims (10)
1. a catalyst for manufacturing olefin by low-carbon alkane dehydrogenation, with Al
2o
3for carrier, take chromium as active component, take alkali metal as co catalysis component, be benchmark by the weight of final catalyst, the content of chromium oxide is 10.0% ~ 30.0%, alkali metal oxide content is 0.5% ~ 3.0%, and surplus is aluminium oxide, it is characterized in that: described active component chromium before dipping alkali metal co catalysis component and after dipping alkali metal co catalysis component step impregnation on alumina support.
2. catalyst according to claim 1, is characterized in that: the active component chromium of described dipping 60% ~ 80% before dipping alkali metal co catalysis component, floods the active component chromium of surplus after dipping alkali metal co catalysis component.
3. catalyst according to claim 1, is characterized in that: described co catalysis component alkali metal is the one in potassium, sodium and lithium.
4. a preparation method for catalyst for manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1, comprises the steps:
(1) to Al
2o
3carrier carries out flooding appropriate active component chromium, then drying, roasting;
(2) by step (1) gained containing chromium alumina load alkali metal, then drying, roasting;
(3) by the remaining active component chromium of alumina load containing chromium, alkali metal containing of step (2) gained, then drying, roasting obtain catalyst for manufacturing olefin by low-carbon alkane dehydrogenation of the present invention.
5. method according to claim 4, is characterized in that: the presoma of described chromium is chromic nitrate, chromic acid or chromium acetate.
6. method according to claim 4, is characterized in that: the alkali metal of described load is the one in lithium, sodium or potassium.
7. method according to claim 6, is characterized in that: the alkali metal of described load is potassium, and the mass percentage that the potassium oxide of load accounts for catalyst is 0.5 ~ 3.0%.
8. method according to claim 4, is characterized in that: described dip time is 1 ~ 24 hour; Described drying all 60 DEG C ~ 150 DEG C dryings 1 ~ 8 hour, roasting all roastings 2 ~ 8 hours at 500 ~ 650 DEG C.
9. method according to claim 4, it is characterized in that: the total amount of the chromium flooded in step (1) and (3) is 10.0% ~ 30.0% by oxide basis weight content in the final catalyst, and the amount of the active component chromium flooded in step (1) is the 60%-80% of active component chromium total amount in final catalyst.
10. the application of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation according to claim 1 in preparing propylene by dehydrogenating propane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210408472.1A CN103769078B (en) | 2012-10-24 | 2012-10-24 | A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210408472.1A CN103769078B (en) | 2012-10-24 | 2012-10-24 | A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769078A CN103769078A (en) | 2014-05-07 |
| CN103769078B true CN103769078B (en) | 2015-12-02 |
Family
ID=50562112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210408472.1A Active CN103769078B (en) | 2012-10-24 | 2012-10-24 | A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103769078B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104148070B (en) * | 2014-08-11 | 2016-06-15 | 中国海洋石油总公司 | A kind of catalyst for dehydrogenation of low-carbon paraffin containing skeleton silver and its preparation method |
| CN104174396B (en) * | 2014-08-11 | 2017-07-28 | 中海油天津化工研究设计院有限公司 | A kind of catalyst for dehydrogenation of low-carbon paraffin of argentiferous and preparation method thereof |
| CN106669648B (en) * | 2015-11-05 | 2018-12-04 | 中国石油化工股份有限公司大连石油化工研究院 | A kind of preparation method of silica modified mesoporous material |
| CN106669703B (en) * | 2015-11-05 | 2018-12-04 | 中国石油化工股份有限公司大连石油化工研究院 | A kind of SiO2Modified catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof |
| CN105749986B (en) * | 2016-02-15 | 2019-03-05 | 中国石油大学(北京) | A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and the preparation method and application thereof |
| CN107398267A (en) * | 2016-05-20 | 2017-11-28 | 青岛科技大学 | A kind of catalyst for dehydrogenation of low-carbon paraffin and its preparation method and application |
| CN106040271B (en) * | 2016-05-30 | 2018-07-17 | 天津科技大学 | A kind of preparing propylene by dehydrogenating propane catalyst and preparation method thereof |
| CN106563440A (en) * | 2016-11-14 | 2017-04-19 | 中海油天津化工研究设计院有限公司 | Crystal-grain-distribution-controlled light alkane dehydrogenation catalyst and preparation method thereof |
| KR102234966B1 (en) * | 2017-06-07 | 2021-03-31 | 에스케이가스 주식회사 | Catalyst having enhanced stability, conversion ratio and selectivity for manufacturing olefin, and A method thereof |
| WO2019180518A1 (en) * | 2018-03-19 | 2019-09-26 | Sabic Global Technologies B.V. | Method of preparation of dehydrogenation catalyst with high chromium content |
| CN110560060B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for propane dehydrogenation and preparation method |
| CN110560041B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for producing propylene by propane dehydrogenation |
| CN110560037B (en) * | 2018-06-05 | 2022-07-12 | 中国石油化工股份有限公司 | Method for preparing propylene by propane dehydrogenation |
| CN110560061B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Process for the dehydrogenation of propane |
| CN110560043B (en) * | 2018-06-05 | 2021-10-01 | 中国石油化工股份有限公司 | Method for producing propylene by propane dehydrogenation |
| CN109331811A (en) * | 2018-11-06 | 2019-02-15 | 中国科学院兰州化学物理研究所苏州研究院 | Mesoporous chromium aluminium composite oxide catalyst and the preparation method and application thereof |
| CN110180530B (en) * | 2019-07-02 | 2023-05-05 | 大庆斯凡达新材料有限公司 | Catalyst for preparing olefin by dehydrogenating low-carbon alkane and preparation method thereof |
| CN110508317A (en) * | 2019-08-23 | 2019-11-29 | 上海绿强新材料有限公司 | A kind of integral catalyzer preparation method of manufacturing olefin by low-carbon alkane dehydrogenation |
| CN115430457A (en) * | 2021-06-03 | 2022-12-06 | 中国科学院大连化学物理研究所 | Single-layer dispersed low-Cr-load propane dehydrogenation propylene preparation catalyst and preparation method thereof |
| CN115779886B (en) * | 2021-09-10 | 2024-03-26 | 中国石油化工股份有限公司 | Sulfur-resistant alkane dehydrogenation catalyst and preparation method and application thereof |
| CN115970673A (en) * | 2022-12-23 | 2023-04-18 | 西南化工研究设计院有限公司 | Chromium-based alkane dehydrogenation catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940922A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN102019178A (en) * | 2009-09-14 | 2011-04-20 | 卓润生 | Propane dehydrogenation to propylene catalyst and preparation and applications thereof |
| CN102123790A (en) * | 2008-07-14 | 2011-07-13 | 苏德-化学公司 | Catalyst for dehydrogenation of hydrocarbons |
-
2012
- 2012-10-24 CN CN201210408472.1A patent/CN103769078B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102123790A (en) * | 2008-07-14 | 2011-07-13 | 苏德-化学公司 | Catalyst for dehydrogenation of hydrocarbons |
| CN101940922A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN102019178A (en) * | 2009-09-14 | 2011-04-20 | 卓润生 | Propane dehydrogenation to propylene catalyst and preparation and applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103769078A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103769078B (en) | A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and its preparation method and application | |
| CN103769156B (en) | A kind of dehydrogenation and its preparation method and application | |
| CN104174396B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin of argentiferous and preparation method thereof | |
| CN100464849C (en) | Catalyst propane using aluminium oxide modified mesonore molecular sieve as carrier for dehydrogenation producing propylene | |
| CN101898131B (en) | Dehydrogenation catalyst taking Sn-containing alumina as carrier and preparation method thereof | |
| CN105792934B (en) | Utilize the hydrocarbon dehydrogenation manufacture method of sponge-type carrier | |
| CN102441444B (en) | A kind of preparation method of dehydrogenation | |
| CN104588011B (en) | Alkane dehydrogenation catalyst and preparation method thereof | |
| CN101147871A (en) | Nickel catalyst for selective hydrogenation | |
| CN106607023B (en) | For catalyst for preparing isobutene through dehydrogenation of iso-butane and preparation method thereof | |
| CN104971717A (en) | Pt-modified ZnO/Al2O3 catalyst and preparation method and application thereof | |
| CN102553632B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof and application | |
| CN111408370A (en) | Supported PtZn intermetallic alloy catalyst and preparation method and application thereof | |
| CN103420769A (en) | Method for preparing low-carbon olefin from low-carbon alkane through dehydrogenation | |
| CN102911000B (en) | Dehydrogenation method for light alkanes | |
| CN102389831A (en) | Catalyst for preparing propylene through propane catalytic dehydrogenation and preparation method thereof | |
| CN104107712A (en) | Mixed C3/C4 alkane dehydrogenation catalyst and preparation method thereof | |
| CN108435221A (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin and its preparation method and application | |
| CN110237849A (en) | A kind of platinum based catalyst and preparation method thereof for preparing propylene by dehydrogenating propane | |
| CN101191078B (en) | Nickel catalyst with composite pore structure used for selective hydrogenation | |
| CN101844081B (en) | Selective hydrogenation catalyst and application thereof | |
| CN112934230A (en) | Low-Pt long paraffin dehydrogenation catalyst, and preparation method and application thereof | |
| CN104549260B (en) | Catalyst for preparing olefin through dehydrogenation of isobutene and preparation method of catalyst | |
| CN101850250A (en) | selective hydrogenation catalyst for removing alkadiene in mixed C4 and preparation method thereof | |
| CN103787810B (en) | Dehydrogenation method of mixed light alkane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |