CN109317092B - Modified zeolite molecular sieve and preparation method and application thereof - Google Patents
Modified zeolite molecular sieve and preparation method and application thereof Download PDFInfo
- Publication number
- CN109317092B CN109317092B CN201811108128.4A CN201811108128A CN109317092B CN 109317092 B CN109317092 B CN 109317092B CN 201811108128 A CN201811108128 A CN 201811108128A CN 109317092 B CN109317092 B CN 109317092B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- hopane
- organic acid
- zeolite molecular
- type molecular
- 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
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
Abstract
The invention provides a zeolite molecular sieve and a preparation method and application thereof. The zeolite molecular sieve is obtained by modifying an X-type molecular sieve; wherein the modification treatment is to modify the X-type molecular sieve in an organic acid alcohol solution. The zeolite molecular sieve can be used as an adsorbent of hopane in geological samples and is used for enriching the hopane in the geological samples. The zeolite molecular sieve of the invention can be effectively and controllably modified according to the needs.
Description
Technical Field
The invention relates to an enrichment method, in particular to an enrichment method of hopane in a geological sample, and belongs to the technical field of petroleum exploration.
Background
Molecular sieves are widely used as an important inorganic material as catalysts, adsorbents, ion exchangers and novel functional materials. The international association of pure and applied chemistry (IUPAC) classifies molecular sieves into 3 classes according to pore size: micropores (<2nm), mesopores (2-50nm) and macropores (>50 nm). The molecular sieve has shape selectivity and different pore diameters, so that different compounds and even molecules with different configurations of the same type of compounds have different behaviors in the molecular sieve, thereby realizing the separation of monomer compounds without generating significant isotope fractionation effect.
Microporous molecular sieves have been used for a long time for the separation and enrichment of specific components in geological samples. For example, Whitehead (V., W.E., The structure of petroleum pentacyclanes, in Advances in Organic Geochemistry, T.B.and B.F., Editors.1974, Technip: Paris.p.225-243.) pioneered enrichment of pentacyclic terpenoids in Nigeria crude oil with 0.8nm of 10X and NaX (FAU) molecular sieves found 22S to adsorb more than 22R isomers of hopane isomers. Dimmler and Strausz (Dimmler, A.and O.P.Strausz, entity of polycyclic specific oil, synthesized hydrocarbons from petroleum by adsorption on zeolite. journal of Chromatography A,1983.270(0): p.219-225.) utilization of 13X molecular sieves (NaX zeolite, pore size about 0.8nm) was used to separate the polycycloalkanes, hopane, tricyclotene, and drine from the branched and cyclic alkane fractions in Athabasca oil sands, but some of the hopane isomers were adsorbed on the molecular sieves for up to 36 hours. Armanios et al (armamios, C., R.Alexander, and R.Ian Kagi, Shape-selective sensing of petroleum hosts by ultrastable Y zeolite organic chemistry,1992.18(4): p.399-406.) utilize ultrastable Y molecular sieves (USY zeolites, FAU) to enrich different size and Shape hopane components in crude oil in Barrow subplants. The 17 α rearranged hopane elutes directly because it has a relatively large cross-section and is not adsorbed by the molecular sieve, whereas the 18 α C29Ts elutes relatively more slowly than the specific gravity hopane due to its adsorption by the molecular sieve. The 17 α hopane of 22R configuration has a longer retention time than the 22S 17 α hopane due to its easier access to the interior of the molecular sieve, and the 17 α hopane, norhopane and 17 β hopane lacking long chains are also relatively difficult to elute due to their hindrance in the molecular sieve, and they are not completely eluted with the 22R 17 α hopane by isooctane. The Armanios (Armanios, C., et al., Fractionation of discrete high molecular species using molecular devices, 1994.21(5): p.531-543) study found that the blocking of hopane in a molecular sieve depends on the size of the pore size of the molecular sieve and the effective cross-sectional diameter of conformational isomers of hopane molecules, and that when the effective cross-sectional diameter is larger, the effective cross-sectional diameter of 22S isomers such as C34 is greater than 0.9nm and thus cannot enter USY type molecular sieves having a pore size of only 0.74 nm. It can be known that the existing enriched biomarker compounds are all commercial microporous molecular sieves with relatively fixed types and pore sizes. The shape selectivity of a zeolitic molecular sieve is primarily due to the difference between its crystal pore size and the molecular size of the adsorbate or reactant, if chemical considerations are not taken into account. The microporous molecular sieve has a uniformly developed structure, and the enrichment effect on compounds with appropriate molecular sizes is relatively fixed. However, for the enriched target with a size larger than the pore diameter, on one hand, the target is difficult to enter the pore channel, and on the other hand, the target has a large diffusion resistance after being adsorbed in the pore channel and is difficult to escape, so that the enrichment effect of the specific type of commercial molecular sieve on certain specific compounds is poor (Zhang Yu, King Hongkong, and Song dynasty, the synthesis research progress of the microporous-mesoporous composite molecular sieve, chemical engineering, 2010(03), p.60-64.).
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a zeolite molecular sieve, which can be effectively and controllably modified according to actual needs.
In order to achieve the technical purpose, the invention firstly provides a zeolite molecular sieve, which is obtained by modifying an X-type molecular sieve; wherein the modification treatment is to modify the X-type molecular sieve in an organic acid alcohol solution.
In the zeolitic molecular sieves of the present invention, preferably the type X molecular sieve employed is a type 10X molecular sieve or a type 13X molecular sieve.
In the zeolite molecular sieve of the present invention, preferably, the alcohol solution of the organic acid is used in a concentration of 0.05mol/L to 0.5 mol/L. For example, the concentration of the alcohol solution of the organic acid used may be 0.2 mol/L.
In the zeolite molecular sieve of the present invention, preferably, the alcoholic solution of the organic acid used is a methanol or ethanol solution of the organic acid.
In the zeolitic molecular sieve of the present invention, preferably, the organic acid employed is oxalic acid, formic acid or citric acid.
In the zeolite molecular sieve of the present invention, preferably, the modification treatment is to add 5g of the type X molecular sieve to 30mL to 100mL of an alcoholic solution of an organic acid.
In order to achieve the above technical objects, the present invention further provides a method for preparing a zeolite molecular sieve, comprising the steps of:
adding 5g of X-type molecular sieve into 30-100 mL of organic acid alcohol solution;
stirring at 40-80 deg.C and 10-50 rpm for 1-10 h, vacuum filtering, washing to neutrality, and activating at 450 deg.C for 5-10 h to obtain zeolite molecular sieve.
According to the specific embodiment of the invention, the X-type molecular sieve is modified and then is placed in a dryer for cooling for standby.
The invention also aims to provide a method for effectively enriching the hopane, and the purity and the content of the hopane enriched by the method meet the requirements of the monomer hydrocarbon isotope analysis.
In order to achieve the technical purpose, the invention provides an adsorbent for hopane in geological samples, and the adsorbent adopts the zeolite molecular sieve.
In order to achieve the technical purpose, the invention also provides an enrichment method of the hopane in the geological sample, and the enrichment method adopts the adsorbent.
Preferably, the enrichment process of the present invention may comprise the steps of:
dissolving saturated hydrocarbon components in n-pentane or n-hexane, mixing with the hopane adsorbent in the geological sample, and carrying out chromatographic column adsorption to obtain a molecular sieve for adsorbing hopane; wherein the mass ratio of the molecular sieve to the saturated hydrocarbon component is 30:1-200: 1;
desorbing and enriching the hopane to finish the enrichment of the hopane in the geological sample.
In the enrichment process of the present invention, the saturated hydrocarbon component employed can be obtained by:
extracting a rock sample to obtain an asphalt A sample; or the like, or, alternatively,
and (3) carrying out chromatographic separation on the petroleum sample by using a silica gel column or a silica gel/alumina column to obtain a saturated hydrocarbon component.
In the enrichment method of the present invention, 0.2mg to 5mg of the saturated hydrocarbon component is dissolved in 0.2mL to 1.0mL of n-pentane or n-hexane. Further, the saturated hydrocarbon component obtained by the above steps is subjected to nitrogen purging at room temperature until dry for use.
More specifically, the chromatography column adsorption step may be performed in a glass column having an inner diameter of 5mm to 10 mm. The lower end of the glass column was sealed with extracted absorbent cotton. The specific adsorption steps are as follows:
dissolving saturated hydrocarbon components in n-pentane or n-hexane, and then filling the mixture into a glass column to ensure that no liquid flows out from the lower end of the glass column;
standing at room temperature for 0.5-2 h to allow hopane molecules to be effectively adsorbed, and eluting normal saturated hydrocarbon and other isomeric saturated hydrocarbon components with 10-30 mL of n-pentane or n-hexane.
In the enrichment method of the invention, isooctane can be used as a desorption agent during desorption. Specifically, the desorption means is a direct leaching or solvent extraction manner. Wherein, the direct leaching step is as follows:
the glass column was rinsed directly with isooctane and the eluted solution was collected.
Wherein, the solvent extraction can be carried out in a rapid solvent extraction Apparatus (ASE), and the specific steps are as follows:
transferring the molecular sieve in the glass column into a sample chamber of a rapid solvent extraction instrument, adopting isooctane as an extraction solvent, extracting at the temperature of 100 ℃ and 150 ℃, extracting for 2-4 times, wherein the volume of the extraction liquid is 10-50% of the volume of the sample chamber, and collecting and combining the solution extracted for multiple times.
In the enrichment method of the invention, the desorbed product is purged with nitrogen at 60-80 ℃ after enrichment.
The method for enriching the hopane in the geological sample is simple, easy to operate, quick and effective; the enriched hopane has high purity and meets the determination requirement of the isotope analysis of the monomer hydrocarbon.
The zeolite molecular sieve of the invention keeps the original structural characteristics of the molecular sieve, and can effectively and controllably reform the aperture of the molecular sieve.
The adsorbent for hopane in geological samples is used for increasing the sizes of micropores appropriately on the premise of reducing damage to a molecular sieve macrostructure as much as possible, so that enrichment of molecules with the sizes larger than the original pore diameters is realized.
Drawings
Fig. 1 is a process flow diagram of the method for enriching hopane in a geological sample according to example 1.
FIG. 2 is a chromatogram of the enriched hopane product before and after modification of the molecular sieve in example 1.
FIG. 3a is a scanning electron micrograph of an unmodified 13X molecular sieve of example 2.
FIG. 3b is a scanning electron micrograph of the unmodified 13X molecular sieve of example 2.
FIG. 3c is a scanning electron micrograph of the unmodified 13X molecular sieve of example 2.
FIG. 4a is a scanning electron micrograph of the modified 13X molecular sieve of example 2.
FIG. 4b is a scanning electron micrograph of the modified 13X molecular sieve of example 2.
Fig. 4c is a scanning electron micrograph of the modified 13X molecular sieve of example 2.
FIG. 5a is a scanning electron micrograph of the modified 13X molecular sieve of example 2.
FIG. 5b is a scanning electron micrograph of the modified 13X molecular sieve of example 2.
FIG. 5c is a scanning electron micrograph of the modified 13X molecular sieve of example 2.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The hopane compounds belong to triterpenoids, and are widely distributed biomarkers due to the fact that the hopane compounds contain 5 benzene rings and are also named as pentacyclic triterpenoids.
Example 1
This example first provides a zeolitic molecular sieve, which is prepared by the following steps:
adding 5g of 13X type molecular sieve into 80mL of oxalic acid ethanol solution with the concentration of 0.1mol/L, stirring at the rotating speed of 20rpm at 50 ℃ for 2h, carrying out suction filtration, washing to be neutral, activating at 450 ℃ for 8h, and placing in a dryer for cooling while the solution is hot for later use.
The embodiment also provides a method for enriching hopane in a geological sample, which specifically comprises the following steps as shown in fig. 1:
preparation of saturated hydrocarbon component
Separating an asphalt A sample or a petroleum sample obtained by extracting a rock sample by using a silica gel column or a silica gel/alumina column chromatography to obtain a saturated hydrocarbon component; the saturated hydrocarbon components were blown dry at room temperature with nitrogen and weighed.
Adsorption of hopane compound on molecular sieve chromatographic column
Weighing a modified 13X-type molecular sieve, placing the molecular sieve in a glass column with the lower end sealed by extracted absorbent cotton and the inner diameter of 6mm, dissolving saturated hydrocarbon components by using 0.5mL of n-pentane, and transferring the dissolved saturated hydrocarbon components to the glass column to ensure that liquid does not flow out; wherein the mass ratio of the modified 13X type molecular sieve to the saturated hydrocarbon component is 100: 1; the glass column is placed at room temperature for 0.5h until hopane molecules are effectively adsorbed, and then 20mL of n-pentane is used for eluting normal saturated hydrocarbon and other isomeric saturated hydrocarbon components.
Molecular sieve desorption of hopane compounds
The molecular sieve column was rinsed directly with 9mL of isooctane and the rinsed solution was collected.
Enrichment product concentration and subsequent analysis
And (3) carrying out nitrogen blowing concentration on the enriched product solution obtained in the previous step at 70 ℃ to a proper volume, and filling the concentrated product solution into a 2mL sample bottle for subsequent analysis.
As can be seen from FIG. 2, the recovery rates of the modified molecular sieve (0.1 mol/L oxalic acid ethanol solution) for the C29 hopane (C29H), C30 hopane (C30H) and C31(22S) hopane (C31H (22S)) are obviously improved, and the product has good purity after chromatographic separation, and can meet the requirement of subsequent monomer hydrocarbon isotope analysis. The recovery rates of the three compounds are respectively improved from 5%, 4% and 5.7% of unmodified compounds to 93.9%, 62.2% and 93.4% of modified compounds, and the enrichment effect is remarkably improved (effectiveness); wherein the recovery rate of the hopane product is continuously increased along with the prolonging of the modification time, and the controllability of the hopane product is also shown.
The difference of carbon isotope ratios of all the hopane monomers before and after enrichment is less than 0.3 per thousand, and the isotope analysis precision requirement is met.
The recovery rates of the enriched hopane products before and after modification of the molecular sieve are shown in table 1.
TABLE 1
Example 2
In this example, isothermal adsorption tests were performed on an unmodified 13X molecular sieve, an oxalic acid-modified 13X molecular sieve for 2 hours, and an oxalic acid-modified 13X molecular sieve for 8 hours, and the average pore size of the molecular sieves was increased from 0.6685nm, which is unmodified, to 0.9200nm, which is modified for 8 hours. As can be seen from fig. 3a, 3b, 3c, 4a, 4b, 4c, 5a, 5b, and 5c, the modified molecular sieve retains the original structural features of the molecular sieve, and the pores of the modified molecular sieve can be increased as desired.
Claims (5)
1. A zeolite molecular sieve is characterized in that the zeolite molecular sieve is obtained by modifying an X-type molecular sieve; wherein the modification treatment is to modify the X-type molecular sieve in an alcoholic solution of organic acid, and the modification comprises the following steps:
adding 5g of X-type molecular sieve into 30-100 mL of organic acid alcohol solution;
stirring at 40-80 ℃ and at the rotating speed of 10-50 rpm for 1-10 h, then performing suction filtration and washing to be neutral, and activating at 450 ℃ for 5-10 h to obtain the zeolite molecular sieve;
wherein the X-type molecular sieve is a 10X-type molecular sieve or a 13X-type molecular sieve;
the organic acid alcohol solution is organic acid methanol or organic acid ethanol solution, the concentration of the organic acid alcohol solution is 0.05mol/L-0.5mol/L, and the organic acid is oxalic acid, formic acid or citric acid.
2. A method of preparing a zeolitic molecular sieve according to claim 1, characterized in that it comprises the following steps:
adding 5g of X-type molecular sieve into 30-100 mL of organic acid alcohol solution;
stirring at 40-80 deg.C and 10-50 rpm for 1-10 h, vacuum filtering, washing to neutrality, and activating at 450 deg.C for 5-10 h to obtain the zeolite molecular sieve.
3. An adsorbent for hopane in a geological sample, which is the zeolite molecular sieve of claim 1.
4. A method for enriching hopane in a geological sample, which is characterized in that the adsorbent adopted in the method is the adsorbent for hopane in the geological sample as claimed in claim 3.
5. The enrichment method according to claim 4, characterized in that the enrichment method comprises the following steps:
dissolving saturated hydrocarbon components in n-pentane or n-hexane, mixing with the hopane adsorbent in the geological sample according to claim 3, and performing chromatographic column adsorption to obtain a molecular sieve for adsorbing hopane; wherein the mass ratio of the molecular sieve to the saturated hydrocarbon component is 30:1-200: 1;
desorbing and enriching the hopane to finish the enrichment of the hopane in the geological sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811108128.4A CN109317092B (en) | 2018-09-21 | 2018-09-21 | Modified zeolite molecular sieve and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811108128.4A CN109317092B (en) | 2018-09-21 | 2018-09-21 | Modified zeolite molecular sieve and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109317092A CN109317092A (en) | 2019-02-12 |
| CN109317092B true CN109317092B (en) | 2021-11-30 |
Family
ID=65265756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811108128.4A Active CN109317092B (en) | 2018-09-21 | 2018-09-21 | Modified zeolite molecular sieve and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109317092B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625082B (en) * | 2020-12-14 | 2022-05-24 | 长江大学 | Method for separating and purifying hopane by neutral alumina |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289492A (en) * | 2007-04-17 | 2008-10-22 | 中国石油天然气股份有限公司 | Process for separating sterane and hopane form mother oil or rock extract by 13X molecular sieve |
| CN102101877A (en) * | 2009-12-16 | 2011-06-22 | 中国石油天然气股份有限公司 | Method for separating gonane and hopane from crude oil or rock extract |
| CN103031140A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for adsorbing and separating normal paraffin in naphtha |
| CN103732537A (en) * | 2011-04-08 | 2014-04-16 | 瑞弗科技有限公司 | Mesoporous framework-modified zeolites |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6906233B2 (en) * | 2002-12-12 | 2005-06-14 | Exxon Mobil Chemical Patents Inc. | Modified metalloaluminophosphate molecular sieves |
| US20070297975A1 (en) * | 2006-06-23 | 2007-12-27 | Janssen Marcel J | Metal loading of molecular sieves using organic carriers with limited water content |
-
2018
- 2018-09-21 CN CN201811108128.4A patent/CN109317092B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289492A (en) * | 2007-04-17 | 2008-10-22 | 中国石油天然气股份有限公司 | Process for separating sterane and hopane form mother oil or rock extract by 13X molecular sieve |
| CN102101877A (en) * | 2009-12-16 | 2011-06-22 | 中国石油天然气股份有限公司 | Method for separating gonane and hopane from crude oil or rock extract |
| CN103732537A (en) * | 2011-04-08 | 2014-04-16 | 瑞弗科技有限公司 | Mesoporous framework-modified zeolites |
| CN103031140A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for adsorbing and separating normal paraffin in naphtha |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109317092A (en) | 2019-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR930006400B1 (en) | Selective adsorption of carbon dioxide on zeolite | |
| CN104492383B (en) | A kind of metal organic frame adsorbent and its preparation method and application | |
| Cao et al. | Metal-organic framework UiO-66 for rapid dispersive solid phase extraction of neonicotinoid insecticides in water samples | |
| Ji et al. | Porous layer open-tubular capillary columns: preparations, applications and future directions | |
| JP6293794B2 (en) | Method for separating xylene in simulated moving bed using zeolite adsorbent solid having a particle size between 150 microns and 500 microns | |
| US7468468B2 (en) | Process for separating meta-xylene from a feed of aromatic hydrocarbons by liquid phase adsorption | |
| CN103908955B (en) | The preparation method of the superhigh cross-linking type polymeric adsorbent that a kind of acetamido is modified and application thereof | |
| JPH0570112A (en) | Process of collecting nf3 purified from mixture of nf3 and cf4 | |
| CN109317092B (en) | Modified zeolite molecular sieve and preparation method and application thereof | |
| US7780763B2 (en) | Method of desorbing a volatile component from a spent adsorbent with rotating packed bed and method of recovering 2,2,3,3-tetrafluro-1-propanol from a gas stream by adsorption | |
| CN113461513B (en) | Porous cobalt formate material, preparation method and application thereof, and separation method of alkane isomer mixture | |
| MXPA06015023A (en) | Use of adsorbent microporous carbon material, for reducing benzene content in hydrocarbon flows. | |
| CN1939883B (en) | Process for separating meta-xylene from a feed of aromatic hydrocarbons | |
| Hoering et al. | Shape-selective sorption of monomethylalkanes by silicalite, a zeolitic form of silica | |
| Macko et al. | Adsorption of polypropylene from dilute solutions on a zeolite column packing | |
| JP2023027092A (en) | Method of decarbonating gaseous flows | |
| CN113680172A (en) | Trapping agent for hydrocarbon gas and separation method of near-boiling point gas | |
| CN115090000B (en) | Purifying and separating method for dioxin | |
| Baronskaya et al. | Ethylene recovery from the gas product of methane oxidative coupling by temperature swing adsorption | |
| CN112625082B (en) | Method for separating and purifying hopane by neutral alumina | |
| Shi et al. | Controllable Preparation of Macroporous Molecularly Imprinted Monolithic Hplc Columns for On-Line Concentration, Purification, and Determination of Trace Fluoroquinolones Veterinary Drug Residues in Milk | |
| RU2302372C2 (en) | Method for chromatographic separation of fullerenes | |
| KR20090058376A (en) | The recovery method of alcohols or ethers from waste water by activated carbon fiber adsorption towers | |
| CN117467468A (en) | Column chromatography method for rapidly separating stan in crude oil | |
| US3546256A (en) | Process for separating organic mixtures containing nf2 groups |
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 |