CN110668463A - Method for preparing titanium-containing mordenite with high silicon-aluminum ratio - Google Patents
Method for preparing titanium-containing mordenite with high silicon-aluminum ratio Download PDFInfo
- Publication number
- CN110668463A CN110668463A CN201911078184.2A CN201911078184A CN110668463A CN 110668463 A CN110668463 A CN 110668463A CN 201911078184 A CN201911078184 A CN 201911078184A CN 110668463 A CN110668463 A CN 110668463A
- Authority
- CN
- China
- Prior art keywords
- titanium
- mordenite
- modified
- hydrogen
- silicon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/26—Mordenite type
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention provides a method for preparing titanium-containing mordenite with high silica-alumina ratio, which is to modify hydrogen-type mordenite to obtain the titanium-containing mordenite with high silica-alumina ratio. The invention introduces titanium into the mordenite molecular sieve framework through modification and simultaneously improves the silicon-aluminum ratio of the molecular sieve, and the obtained mordenite with high titanium-containing silicon-aluminum ratio has high crystallinity and purity, thereby being convenient for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis modification, and particularly relates to a preparation method of titanium-containing mordenite with a high silica-alumina ratio.
Background
Mordenite (MOR) is a molecular sieve with a twelve-ring super cage structure, and the mordenite molecular sieve shows excellent catalytic performance in reactions such as hydrocarbon cracking, hydrocracking, alkane isomerization, polycyclic aromatic compound alkylation and the like.
Titanium silicalite can be formed by incorporating the transition metal titanium into the molecular sieve framework. Because the titanium atom has a four-coordination structure, the titanium silicon mordenite has good high-selectivity catalytic activity for oxidation-reduction reaction and has excellent catalytic activity for ketoximation, epoxidation and other reactions. Compared with the titanium-silicon molecular sieves such as TS-1, Ti-MWW and the like, the synthesis of the titanium-silicon mordenite molecular sieve does not need an organic template agent, so that the titanium-silicon mordenite molecular sieve has lower production cost and good application prospect.
However, the use of titanium silicalite molecular sieves has presented a number of difficulties. For example, the formation of titanium tetrahedral structures on the silicon framework of mordenite is difficult, and the presence of aluminum atoms contained in the mordenite molecular sieve poisons the titanium active site, and the like. In contrast, effective means for forming tetradentate titanium are required, and deep dealumination of the mordenite molecular sieve is required.
In general, acidic substances such as hydrochloric acid and nitric acid are used for removing aluminum element in a molecular sieve, and the mechanism is that aluminum element is dissolved through the acidity of strong acid. However, strong acid has high requirements on equipment materials and high investment cost. The common method for supplementing titanium to mordenite is a gas phase method, in which a titanium-containing compound is gasified and then passes through a bed layer containing zeolite at a high temperature, so that titanium is deposited in a zeolite framework at a certain temperature. The method has complex process and difficult amplification, and is not suitable for industrial production.
Disclosure of Invention
In view of the above, the invention aims to provide a method for preparing mordenite with titanium-containing high silica-alumina ratio, so as to solve the problems of difficult dealumination, high cost, complex process, unsuitability for industrial production and the like of the existing mordenite, and simultaneously improve the titanium utilization rate and the titanium content of the product in the mordenite titanium modification process.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for preparing mordenite with titanium and high silicon-aluminum ratio comprises the following steps:
s1: dissolving a titanium source and oxalic acid in a solvent to prepare a modified solution;
s2: adding hydrogen mordenite into the modified liquid, and stirring to be uniform to obtain a modified liquid cement;
s3: placing the glue solution obtained in the step S2 into a reaction kettle, stirring and heating, slowly adding water into the reaction kettle while stirring, and continuing the reaction after the water is added until the modified mordenite glue solution is obtained;
s4: and (4) cleaning the modified mordenite glue solution obtained in the step (S3) to be neutral, drying by hot air, and then calcining to obtain the titanium modified mordenite with the high silica-alumina ratio.
The preparation method of the mordenite containing titanium and having high silica-alumina ratio uses a liquid phase deposition method to prepare a modified solution by placing a molecular sieve in a solution of oxalic acid and a titanium source, and the solvent of the modified solution selects an anhydrous organic solvent to ensure that the titanium source is not decomposed into titanium oxide in advance. Heating the modifying liquid to a certain temperature, adding water at a certain speed, slowly hydrolyzing the titanium-containing compound with the addition of the water to generate acidic substances such as hydrogen chloride and the like and titanium oxide, and under the hydrothermal condition, jointly acting the hydrogen chloride and oxalic acid on the aluminum in the mordenite molecular sieve to remove the aluminum from the molecular sieve framework. Meanwhile, titanium oxide generated by hydrolysis is deposited in the molecular sieve framework and gradually crystallized into titanium with a four-coordination framework. Through the treatments, the titanium-containing mordenite molecular sieve with high silica-alumina ratio is obtained. By adopting the preparation method, dealumination and titanium supplement are simultaneously carried out by a one-step method, not only can the mordenite be deeply dealuminated, but also the titanium utilization rate and the titanium content of the product can be obviously improved.
The invention adopts oxalic acid to dealuminate the mordenite, and the dealumination of the oxalic acid realizes the dissolution of aluminum through the combined action of the acidity and the complexing capacity of the oxalic acid.
Further, in the step S1, the titanium source is one of titanium fluorotitanate, titanium tetrachloride, isopropyl titanate, and titanium isooctanolate, and the titanium content in the titanium source is 0.1 to 1kg, preferably 0.2 to 0.5kg, in terms of equivalent of TiO 2.
Further, in the step S1, the amount of oxalic acid is 10 to 50 kg.
Further, in the step S1, the solvent is one or more of methanol, ethanol, tert-butyl alcohol, ethylene glycol, acetonitrile, toluene, and ethyl acetate, the total amount of the solvent is 20-80kg, and the amount of the hydrogen-type mordenite added is 5-15 kg.
Further, in step S1, the total amount of solvent is 50kg, and the amount of hydrogen-form mordenite added is 10 kg.
Further, in step S2, the particle size of the hydrogen-type mordenite is 50 to 1000nm, and the silica-alumina ratio is 5 to 10.
Further, in the step S3, the heating temperature is 100-.
Further, in the step S3, the reaction time is 24 hours, and the water adding rate is 0.05 kg/h.
Further, in the step S4, the calcination temperature is 550 ℃, and the calcination time is 4 h.
The preparation method of the mordenite containing titanium and having high silicon-aluminum ratio has the following advantages:
(1) the dealuminization titanium supplement modification method provided by the invention is simple and easy to realize large-scale industrial production;
(2) the dealuminization titanium supplementing modification method provided by the invention has the advantages of good titanium supplementing effect, high titanium content and no free titanium oxide;
(3) the dealuminizing titanium supplementing modification method provided by the invention has high titanium supplementing efficiency and high titanium utilization rate.
Detailed Description
The invention will be described in detail with reference to specific embodiments. The examples are intended to illustrate the invention, but are not intended to limit the scope of applicability of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
In the embodiment of the invention, a method for preparing titanium-containing mordenite with high silica-alumina ratio comprises the following specific steps:
(1) sieving hydrogen-type mordenite with the silicon-aluminum ratio of 10, and selecting the hydrogen-type mordenite with the particle size of 100-200nm for use;
(2) dissolving 1kg of titanium tetrachloride and 20kg of oxalic acid in 50kg of methanol, adding 10kg of hydrogen-type mordenite obtained by the sieve in the step (1), and stirring uniformly to obtain a mordenite molecular sieve modification solution;
(3) and (3) heating the modified liquid obtained in the step (2) in a reaction kettle to 150 ℃, adding water into the reaction kettle at a rate of 0.05kg/h after the temperature is stable, wherein the total water amount is 0.25kg, the total modification treatment time is 24h, cleaning the titanium modified molecular sieve product to be neutral after the modification is finished, drying, and calcining at 550 ℃ for 4h to obtain the titanium modified mordenite with the high silica-alumina ratio.
The test results of the silicon-aluminum ratio and silicon-titanium ratio of the product are shown in table 1.
Example 2
In the embodiment of the invention, a method for preparing titanium-containing mordenite with high silica-alumina ratio comprises the following specific steps:
(1) sieving hydrogen-type mordenite with the silicon-aluminum ratio of 20, and selecting the hydrogen-type mordenite with the particle size of 100-200nm for use;
(2) dissolving 0.8kg of fluotitanic acid and 30kg of oxalic acid in 50kg of ethyl acetate, adding 10kg of hydrogen-type mordenite obtained by the sieve in the step (1), and stirring the mixture uniformly to obtain a mordenite molecular sieve modified solution;
(3) and (3) heating the modified liquid obtained in the step (2) in a reaction kettle to 170 ℃, adding water into the reaction kettle at a rate of 0.05kg/h after the temperature is stable, wherein the total water amount is 0.5kg, the total modification treatment time is 24h, cleaning the titanium modified molecular sieve product to be neutral after the modification is finished, drying, and calcining at 550 ℃ for 4h to obtain the titanium modified mordenite with the high silica-alumina ratio.
The test results of the silicon-aluminum ratio and silicon-titanium ratio of the product are shown in table 1.
Example 3
In the embodiment of the invention, a method for preparing titanium-containing mordenite with high silica-alumina ratio comprises the following specific steps:
(1) sieving hydrogen-type mordenite with the silicon-aluminum ratio of 10, and selecting the hydrogen-type mordenite with the particle size of 100-200nm for use;
(2) dissolving 1kg of titanium isooctanolate and 25kg of oxalic acid in 50kg of toluene, adding 10kg of hydrogen-type mordenite obtained by the sieve in the step (1), and stirring the mixture uniformly to obtain a mordenite molecular sieve modification solution;
(3) and (3) heating the modified liquid obtained in the step (2) in a reaction kettle to 170 ℃, adding water into the reaction kettle at a rate of 0.05kg/h after the temperature is stable, wherein the total water amount is 0.5kg, the total modification treatment time is 24h, cleaning the titanium modified molecular sieve product to be neutral after the modification is finished, drying, and calcining at 550 ℃ for 4h to obtain the titanium modified mordenite with the high silica-alumina ratio.
The test results of the silicon-aluminum ratio and silicon-titanium ratio of the product are shown in table 1.
Comparative example 1
In a comparative example of the invention, a preparation method of modified mordenite comprises the following specific steps:
(1) sieving hydrogen-type mordenite with the silicon-aluminum ratio of 10, and selecting the hydrogen-type mordenite with the particle size of 100-200nm for use;
(2) dissolving 1kg of tetrabutyl titanate in 50kg of water, adding 10kg of the hydrogen-type mordenite obtained by the sieve in the step (1), and stirring uniformly to obtain a mordenite molecular sieve modification solution;
(3) and (3) heating the modified liquid obtained in the step (2) in a reaction kettle to 170 ℃, adding water into the reaction kettle at a rate of 0.05kg/h after the temperature is stable, wherein the total water amount is 0.5kg, the total modification treatment time is 24h, cleaning the titanium modified molecular sieve product to be neutral after the modification is finished, drying, and calcining at 550 ℃ for 4h to obtain the titanium modified mordenite with the high silica-alumina ratio.
The test results of the silicon-aluminum ratio and the silicon-titanium ratio of the product are shown in Table 1, and the final product contains no titanium.
Comparative example 2
In a comparative example of the invention, a preparation method of modified mordenite comprises the following specific steps:
(1) sieving hydrogen-type mordenite with the silicon-aluminum ratio of 10, and selecting the hydrogen-type mordenite with the particle size of 100-200nm for use;
(2) dissolving 1kg of tetrabutyl titanate in 50kg of water, adding 10kg of the hydrogen-type mordenite obtained by the sieve in the step (1), and stirring uniformly to obtain a mordenite molecular sieve modification solution;
(3) and (3) placing the modified liquid obtained in the step (2) into a reaction kettle, heating to 170 ℃ for hydrothermal treatment, keeping the temperature for 24 hours, after the modification is finished, cleaning the titanium modified molecular sieve to be neutral, drying, and calcining at 550 ℃ for 4 hours to obtain the titanium modified mordenite with the high silica-alumina ratio.
The test results of the silicon-aluminum ratio and the silicon-titanium ratio of the product are shown in Table 1, and the final product contains no titanium.
TABLE 1 comparison of test results for examples and comparative examples
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A method for preparing mordenite with titanium and high silicon-aluminum ratio is characterized in that the mordenite with titanium and high silicon-aluminum ratio is prepared by the following steps:
s1: dissolving a titanium source and oxalic acid in a solvent to prepare a modified solution;
s2: adding hydrogen mordenite into the modified liquid, and stirring to be uniform to obtain a modified liquid cement;
s3: placing the glue solution obtained in the step S2 into a reaction kettle, stirring and heating, slowly adding water into the reaction kettle while stirring, and continuing the reaction after the water is added until the modified mordenite glue solution is obtained;
s4: and (4) cleaning the modified mordenite glue solution obtained in the step (S3) to be neutral, drying by hot air, and then calcining to obtain the titanium modified mordenite with the high silica-alumina ratio.
2. The method of claim 1, wherein: in the step S1, the titanium source is one of fluotitanic acid, titanium tetrachloride, isopropyl titanate, and titanium isooctanolate, and the titanium content in the titanium source is 0.1 to 1kg in terms of equivalent of TiO 2.
3. The method of claim 1, wherein: in the step S1, the amount of oxalic acid is 10-50 kg.
4. The method of claim 1, wherein: in the step S1, the solvent is one or more of methanol, ethanol, tert-butyl alcohol, ethylene glycol, acetonitrile, toluene and ethyl acetate, the total amount of the solvent is 20-80kg, and the amount of the added hydrogen-type mordenite is 5-15 kg.
5. The method according to claim 1 or 4, characterized in that: in step S1, the total amount of solvent was 50kg, and the amount of hydrogen mordenite added was 10 kg.
6. The method of claim 1, wherein: in the step S2, the particle size of the hydrogen-type mordenite is 50-1000nm, and the silicon-aluminum ratio is 5-10.
7. The method of claim 1, wherein: in the step S3, the heating temperature is 100-180 ℃, the reaction time is 12-48h, the water addition amount is 0.1-5kg, and the water addition rate is 0.01-0.1 kg/h.
8. The method according to claim 1 or 7, characterized in that: in the step S3, the reaction time is 24h, and the water adding rate is 0.05 kg/h.
9. The method of claim 1, wherein: in the step S4, the calcining temperature is 550 ℃ and the calcining time is 4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911078184.2A CN110668463B (en) | 2019-11-06 | 2019-11-06 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911078184.2A CN110668463B (en) | 2019-11-06 | 2019-11-06 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110668463A true CN110668463A (en) | 2020-01-10 |
| CN110668463B CN110668463B (en) | 2021-04-02 |
Family
ID=69086243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911078184.2A Active CN110668463B (en) | 2019-11-06 | 2019-11-06 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110668463B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807243A (en) * | 2005-12-21 | 2006-07-26 | 大连理工大学 | Method for preparing heteroatom zeolite through solid phase isomorphous replacement |
| CN101182005A (en) * | 2007-11-09 | 2008-05-21 | 浙江大学 | Method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification |
| WO2009103549A1 (en) * | 2008-02-21 | 2009-08-27 | Süd-Chemie AG | Scr catalyst with ammonia accumulator function |
| CN101829593A (en) * | 2010-04-13 | 2010-09-15 | 中国地质大学（武汉） | Preparation method of titanium dioxide persulfate-loaded mordenite solid superacid catalyst |
| CN102101678A (en) * | 2010-12-07 | 2011-06-22 | 浙江大学 | Method for preparing titanium-silicon molecular sieve by virtue of liquid-solid phase replacement and modification of natural zeolite |
| CN102627289A (en) * | 2012-03-23 | 2012-08-08 | 岳阳昱泰化工科技发展有限公司 | Modification method of titanium-containing molecular sieve |
| CN102674389A (en) * | 2012-05-07 | 2012-09-19 | 华东师范大学 | Preparation method of titanium-containing nano-mordenite molecular sieve |
| CN105692649A (en) * | 2016-01-26 | 2016-06-22 | 中国天辰工程有限公司 | Preparation method of TS-1 titanium-silicon molecular sieve |
| CN107008493A (en) * | 2017-04-12 | 2017-08-04 | 中国天辰工程有限公司 | A kind of preparation method for alkene epoxidation or the titanium-containing catalyst of ketone oxamidinating |
| CN108264053A (en) * | 2012-02-07 | 2018-07-10 | 巴斯夫欧洲公司 | The preparation method of zeolitic material |
| CN110127717A (en) * | 2019-06-03 | 2019-08-16 | 福州大学 | A kind of upper titanium method of H-MOR molecular sieve |
-
2019
- 2019-11-06 CN CN201911078184.2A patent/CN110668463B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807243A (en) * | 2005-12-21 | 2006-07-26 | 大连理工大学 | Method for preparing heteroatom zeolite through solid phase isomorphous replacement |
| CN101182005A (en) * | 2007-11-09 | 2008-05-21 | 浙江大学 | Method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification |
| WO2009103549A1 (en) * | 2008-02-21 | 2009-08-27 | Süd-Chemie AG | Scr catalyst with ammonia accumulator function |
| CN101829593A (en) * | 2010-04-13 | 2010-09-15 | 中国地质大学（武汉） | Preparation method of titanium dioxide persulfate-loaded mordenite solid superacid catalyst |
| CN102101678A (en) * | 2010-12-07 | 2011-06-22 | 浙江大学 | Method for preparing titanium-silicon molecular sieve by virtue of liquid-solid phase replacement and modification of natural zeolite |
| CN108264053A (en) * | 2012-02-07 | 2018-07-10 | 巴斯夫欧洲公司 | The preparation method of zeolitic material |
| CN102627289A (en) * | 2012-03-23 | 2012-08-08 | 岳阳昱泰化工科技发展有限公司 | Modification method of titanium-containing molecular sieve |
| CN102674389A (en) * | 2012-05-07 | 2012-09-19 | 华东师范大学 | Preparation method of titanium-containing nano-mordenite molecular sieve |
| CN105692649A (en) * | 2016-01-26 | 2016-06-22 | 中国天辰工程有限公司 | Preparation method of TS-1 titanium-silicon molecular sieve |
| CN107008493A (en) * | 2017-04-12 | 2017-08-04 | 中国天辰工程有限公司 | A kind of preparation method for alkene epoxidation or the titanium-containing catalyst of ketone oxamidinating |
| CN110127717A (en) * | 2019-06-03 | 2019-08-16 | 福州大学 | A kind of upper titanium method of H-MOR molecular sieve |
Non-Patent Citations (3)
| Title |
|---|
| KUNYUE LENG ET AL: ""Ti-modified hierarchical mordenite as highly active catalyst for oxidative desulfurization of dibenzothiophene"", 《FUEL》 * |
| ZHANG FAZHI ET AL: ""Preparation of Titanium Containing Mordenits by Gas Solid Reaction"", 《分子催化》 * |
| 杨靖 等: ""天然沸石同晶取代制备钛丝光沸石"", 《浙江大学学报（理学版）》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110668463B (en) | 2021-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100699797B1 (en) | Mww type zeolite substance, precursor substance therefor, and process for producing these substances | |
| JP5752090B2 (en) | Titanium-silicon molecular sieve and method for producing the same, and method for producing cyclohexanone oxime using the molecular sieve | |
| TW200942326A (en) | Catalytic composition for producing olefins by catalytic cracking | |
| CN104709920A (en) | Tin-containing heteroatomic functional molecular sieve and synthesis and application thereof | |
| CN101327934A (en) | Preparation method of titanium-silicon molecular sieve with MFI structure | |
| CN104707648A (en) | Ionothermal post-synthesis for synthesis of functional heteroatomic molecular sieve | |
| CN102145300A (en) | Microsphere TS-1 catalyst and preparation method of microsphere TS-1 catalyst | |
| JP2021531162A (en) | Catalysts for producing ethylbenzene from ethanol and benzene, their production methods and applications | |
| CN110668463B (en) | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio | |
| CN1123390C (en) | Method for synthesizing titanium silicone molecular sieve | |
| TW202218987A (en) | Tin-titanium-silicon molecular sieve, preparation method therefor and use thereof | |
| CN108928832B (en) | Preparation method of germanium-free IWR zeolite molecular sieve | |
| CN104709919A (en) | Tin-containing molecular sieve with MWW topological structure and preparation and application thereof | |
| CN106082259A (en) | There is overlength catalytic life HTS and low cost preparation method thereof | |
| CN116425171A (en) | Preparation method of high-performance hydroisomerization catalyst mesoporous and microporous step structure ZSM 48 molecular sieve | |
| CN115518683B (en) | Supported catalyst, preparation method and application thereof, and method for synthesizing pyromellitic dianhydride by gas-phase oxidation of durene | |
| EP4253321A1 (en) | Super-macroporous zeo-1 molecular sieve, synthesis method therefor and use thereof | |
| JP5131624B2 (en) | Paraffin catalytic cracking process | |
| CN114931974A (en) | Composite titanium-aluminum silicate catalyst and preparation method and application thereof | |
| CN113019433B (en) | Preparation method of HZSM-5 zeolite catalyst | |
| CN100443408C (en) | Gas solid phase preparation method of high performance titanium silicon zeolite | |
| CN100553772C (en) | Be used to produce alkylbenzene Preparation of catalysts method | |
| CN1500728A (en) | Process for preparing titanium silicon molecular sieves | |
| CN108946755B (en) | Synthesis method of germanium-free IWR zeolite molecular sieve | |
| CN113443635A (en) | Titanium-containing Beta molecular sieve and synthesis method thereof |
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 |