CN105622353A - Method for extracting Cakile Maritima phenolic substance from supercritical carbon dioxide - Google Patents
Method for extracting Cakile Maritima phenolic substance from supercritical carbon dioxide Download PDFInfo
- Publication number
- CN105622353A CN105622353A CN201510980163.5A CN201510980163A CN105622353A CN 105622353 A CN105622353 A CN 105622353A CN 201510980163 A CN201510980163 A CN 201510980163A CN 105622353 A CN105622353 A CN 105622353A
- Authority
- CN
- China
- Prior art keywords
- extraction
- carbon dioxide
- kele
- strand
- supercritical carbon
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/004—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by obtaining phenols from plant material or from animal material
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Botany (AREA)
- Extraction Or Liquid Replacement (AREA)
- Medicines Containing Plant Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for extracting a Cakile Maritima phenolic substance from supercritical carbon dioxide. The method comprises the following steps: putting Cakile Maritima leaf powder into a supercritical extraction kettle and adopting supercritical carbon dioxide fluid to extract and separate, wherein the extraction temperature is 35-75 DEG C, the extraction pressure is 20-60 MPa, the extraction time is 0.5-5 hours, the flow rate of the carbon dioxide is 1-30 L/hour, and the flow rate of an entrainer is 1-10 ml/min; decompressing, analyzing and separating the obtained supercritical carbon dioxide fluid containing an extract to obtain an extraction product, namely the phenolic substance, wherein the separation temperature is 25-75 DEG C, and the separation pressure is 1-20 MPa. The method disclosed by the invention is short in extraction time, higher in separation efficiency and product yield, and environmentally friendly. Therefore, the invention provides the ideal extraction method of the Cakile Maritima phenolic substance.
Description
Technical field
The invention belongs to the extraction process field of effective ingredients in plant, particularly to the method for a kind of supercritical carbon dioxide extraction strand Ka Kele aldehydes matter.
Background technology
Strand Ka Kele (CAKILEMARITIMA) is one of common halophytes in three kinds of big West Coasts, is generally grown in Sha Shanshang, is widely used in ethnic drug. Strand Ka Kele has diuresis, and Vitamin C is sick, digestion promoting, relieving constipation, eliminating jaundice edema, regulates the multiple efficacies such as lymphoid tuberculosis and lymph disorder. Strand Ka Kele blade there is substantial amounts of aldehydes matter to accumulate, such as flavonoid, sinapic acid etc. These aldehydes matters have in-vitro antibacterial, scavenging free radicals and antioxidant activity, have the potential as the Natural antioxidant, preservative.
At present, the method extracting strand Ka Kele aldehydes matter main is organic solvent extractionprocess. This extracting method does not need special instrument, and application is comparatively general, but there is the shortcomings such as Product Safety is low, extract length consuming time, extraction ratio is low. By a large amount of solvent extractions, re-evaporation concentrates, and this separation method extract is impure too much, easily causes chemical solvent and metal residual, and organic solvent makes consumption big, and pollutant are many, and cost is high.
Supercritical liquid extraction technique is using supercritical fluid as extractant, utilizes it to have the feature of liquids and gases double properties concurrently and carries out the new technique of options extract and separate by controlling temperature and pressure. Extractant conventional at present is carbon dioxide. In the supercritical state, supercritical carbon dioxide is contacted with material to be separated so that it is selectively polarity size, the boiling point height composition different with molecular size range are extracted successively. Then the method by decompression, intensification makes supercritical fluid become common gases, is extracted material and then wholly or substantially precipitates out, thus reaching the purpose of separating-purifying. According to literature search, up to the present there is no and adopt the method for supercritical carbon dioxide extraction strand Ka Kele blade aldehydes matter to come out.
Summary of the invention
It is an object of the invention to the shortcoming overcoming prior art with not enough, it is provided that the method for a kind of supercritical carbon dioxide extraction strand Ka Kele aldehydes matter.
The purpose of the present invention is achieved through the following technical solutions: the method for a kind of supercritical carbon dioxide extraction strand Ka Kele aldehydes matter, comprises the steps:
(1) strand Ka Kele blade powder is loaded in supercritical extraction reactor, employing co_2 supercritical fluid extraction separates: extraction temperature is 35��75 DEG C, extracting pressure 20��60MPa, extraction time is 0.5��5 hour, carbon dioxide flow rate is 1��30L/ hour, entrainer flow velocity 1��10ml/min;
(2) supercritical carbon dioxide fluid containing extract that will obtain, is separated by decantation to extraction product, separation temperature 25��75 DEG C through decompression solution, and separating pressure is 1��20MPa, and the extraction product collecting gained is aldehydes matter.
Strand Ka Kele blade powder described in step (1) obtains preferably by following steps: by strand Ka Kele blade through pre-freeze, then carries out vacuum lyophilization process, then pulverizes.
The condition of described pre-freeze is preferably-70��-20 DEG C and processes 8��18 hours.
The time of described vacuum lyophilization is preferably 20��36 hours.
The specification of described pulverizing is preferably 20��60 orders.
Extraction temperature described in step (1) is preferably 40��50 DEG C.
Extracting pressure described in step (1) is preferably 25��40MPa.
Extraction time described in step (1) is preferably 2��4 hours.
Carbon dioxide flow rate described in step (1) is preferably 10��20L/ hour.
Entrainer flow velocity described in step (1) is preferably 4��8ml/min.
Entrainer described in step (1) is the one in alcohol, ketone and ether or at least two, or the mixed liquor that a kind of or at least two in alcohol, ketone and ether and water are formed.
Described alcohol is preferably the one in ethanol, propanol and methanol or at least two.
Described ketone is preferably acetone.
Described ether is preferably petroleum ether.
Entrainer described in step (1) is preferably the ethanol water of percent by volume 60%.
Extract and separate described in step (1) is preferably and takes cycling extraction mode.
The time of described cycling extraction is preferably 30min.
Separation temperature described in step (2) is preferably 35��40 DEG C.
Separating pressure described in step (2) is preferably 2��10MPa.
The present invention has such advantages as relative to prior art and effect:
(1) the invention provides a kind of strand Ka Kele aldehydes matter extraction separating method, the method is that solvent method is separated the novel technique combined with carbon dioxide supercritical fluid extraction, take full advantage of the excellent properties of organic solvent extraction polarity similar substance and play the feature of the efficient extract and separate of supercritical carbon dioxide fluid, thus obtaining higher separation efficiency and higher product yield.
(2) present invention adopts the aldehydes matter that supercritical carbon dioxide fluid can extract in the Ka Kele of strand under gentle cryogenic conditions, in the whole carbon dioxide inert environments being operated in closing, it is possible to effectively prevent oxidation and the decomposition of aldehydes matter.
(3) for same raw material, organic solvent extracts needs 7 hours repeatedly, and the yield that blade lyophilized powder extracts is less than for 2.0%, and supercritical carbon dioxide extraction is typically in 0.5��5 hour, yield can reach more than 6.5%, and extraction time reduces, and extraction ratio substantially increases.
(4) it is the gas that colorless and odorless is nontoxic under the supercritical carbon dioxide fluid normality that the present invention adopts, after separating with extraction component, entirely without the residual of solvent, it is possible to be effectively prevented under conventional solvent extraction conditions the residual of solvent toxicity. Also prevent the murder by poisoning to human body of the extraction process and the pollution to environment simultaneously, be a kind of natural and environmental protection abstraction technique.
(5) the method treasury of the present invention takes, separates, and is absent from the phase transition process of material, does not need recycling design, easy to operate, simplifies technological process; Extraction efficiency is high, and power consumption is few, reduces cost, and green non-pollution, is the method for a kind of desirable strand Ka Kele aldehydes matter extract and separate.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
The fresh blade of strand Ka Kele, pre-freeze 10 hours at-40 DEG C, put into vacuum freeze drier, lyophilizing 20 hours. Lyophilizing blade pulverized 20 mesh sieves. Taking blade dry powder to load in supercritical extraction reactor for 1kg time, carry out extract and separate, extracting pressure 30Mpa, extraction temperature is 40 DEG C, CO2Flow velocity is 10L/ hour, and entrainer (percent by volume 60% ethanol) flow velocity is 5ml/min; After 4 hours extract, obtained the supercritical CO containing extract2Fluid, is separated by decantation to extraction product through decompression solution, and separating pressure is 10Mpa, separation temperature 35 DEG C, and the extraction product collecting gained is aldehydes matter, is 75.3mg/g by Forint phenol method detection level, and recovery rate is 7.53%.
Embodiment 2
The fresh blade of strand Ka Kele, pre-freeze 18 hours at-20 DEG C, put into vacuum freeze drier, lyophilizing 20 hours. Lyophilizing blade pulverized 60 mesh sieves. Taking blade dry powder to load in supercritical extraction reactor for 1kg time, carry out extract and separate, extracting pressure 35Mpa, extraction temperature is 45 DEG C, CO2Flow velocity is 15L/ hour, and entrainer (percent by volume 60% ethanol) flow velocity is 4ml/min; After 3 hours extract, obtained the supercritical CO containing extract2Fluid, is separated by decantation to extraction product through decompression solution, and separating pressure is 10Mpa, separation temperature 35 DEG C, and the extraction product collecting gained is aldehydes matter, is 83.2mg/g by Forint phenol method detection level, and recovery rate is 8.32%.
Embodiment 3
The fresh blade of strand Ka Kele, pre-freeze 10 hours at-40 DEG C, put into vacuum freeze drier, lyophilizing 24 hours. Lyophilizing blade pulverized 40 mesh sieves. Taking blade dry powder to load in supercritical extraction reactor for 1kg time, carry out extract and separate, extracting pressure 30Mpa, extraction temperature is 45 DEG C, CO2Flow velocity is 20L/ hour, and entrainer (percent by volume 60% ethanol) flow velocity is 8ml/min; After 3.5 hours extract, obtained the supercritical CO containing extract2Fluid, is separated by decantation to extraction product through decompression solution, and separating pressure is 8Mpa, separation temperature 40 DEG C, and the extraction product collecting gained is aldehydes matter, is 85.9mg/g by Forint phenol method detection level, and recovery rate is 8.59%.
Embodiment 4
The fresh blade of strand Ka Kele, pre-freeze 18 hours at-20 DEG C, put into vacuum freeze drier, lyophilizing 30 hours. Lyophilizing blade pulverized 20 mesh sieves. Taking blade dry powder to load in supercritical extraction reactor for 1kg time, carry out extract and separate, extracting pressure 25Mpa, extraction temperature is 40 DEG C, CO2Flow velocity is 10L/ hour, and entrainer (percent by volume 60% ethanol) flow velocity is 8ml/min; After 2 hours extract, obtained the supercritical CO containing extract2Fluid, is separated by decantation to extraction product through decompression solution, and separating pressure is 2Mpa, separation temperature 35 DEG C, and the extraction product collecting gained is aldehydes matter, is 65.8mg/g by Forint phenol method detection level, and recovery rate is 6.58%.
Embodiment 5
The fresh blade of strand Ka Kele, pre-freeze 8 hours at-70 DEG C, put into vacuum freeze drier, lyophilizing 36 hours. Lyophilizing blade pulverized 60 mesh sieves. Taking blade dry powder to load in supercritical extraction reactor for 1kg time, carry out extract and separate, extracting pressure 40Mpa, extraction temperature is 50 DEG C, CO2Flow velocity is 20L/ hour, and entrainer (percent by volume 60% ethanol) flow velocity is 4ml/min; After 3 hours extract, obtained the supercritical CO containing extract2Fluid, is separated by decantation to extraction product through decompression solution, and separating pressure is 10Mpa, separation temperature 40 DEG C, and the extraction product collecting gained is aldehydes matter, is 78.4mg/g by Forint phenol method detection level, and recovery rate is 7.84%.
Comparative example 1
The fresh blade of strand Ka Kele, dries at 65 DEG C to constant weight, dries blade and pulverized 40 mesh sieves. Taking blade dry powder to load in supercritical extraction reactor for 1kg time, carry out extract and separate, extracting pressure 30Mpa, extraction temperature is 40 DEG C, CO2Flow velocity is 10L/ hour, and entrainer (percent by volume 60% ethanol) flow velocity is 5ml/min; After 4 hours extract, obtained the supercritical CO containing extract2Fluid, is separated by decantation to extraction product through decompression solution, and separating pressure is 10Mpa, separation temperature 35 DEG C, and the extraction product collecting gained is aldehydes matter, is 30.1mg/g by Forint phenol method detection level, and recovery rate is 3.01%.
Comparative example 2
The fresh blade of strand Ka Kele, pre-freeze 10 hours at-40 DEG C, put into vacuum freeze drier, lyophilizing 24 hours. Lyophilizing blade pulverized 40 mesh sieves. Taking blade dry powder 1kg and add percent by volume 60% ethanol of 5 times of volumes, 50 DEG C extract 3 times repeatedly, each 3 hours. Extract mixes, and rotary evaporation concentrates, and detecting gained aldehydes matter content by Forint phenol method is 18.9mg/g, recovery rate 1.89%.
Comparative example 3
The fresh blade of strand Ka Kele, dries at 65 DEG C to constant weight, dries blade and pulverized 40 mesh sieves. Taking blade dry powder 1kg and add percent by volume 60% ethanol of 5 times of volumes, 50 DEG C extract 3 times repeatedly, each 3 hours. Extract mixes, and rotary evaporation concentrates, and detecting gained aldehydes matter content by Forint phenol method is 7.15mg/g, recovery rate 0.715%.
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the method for a supercritical carbon dioxide extraction strand Ka Kele aldehydes matter, it is characterised in that comprise the steps:
(1) strand Ka Kele blade powder is loaded in supercritical extraction reactor, employing co_2 supercritical fluid extraction separates: extraction temperature is 35��75 DEG C, extracting pressure 20��60MPa, extraction time is 0.5��5 hour, carbon dioxide flow rate is 1��30L/ hour, entrainer flow velocity 1��10ml/min;
(2) supercritical carbon dioxide fluid containing extract that will obtain, is separated by decantation to extraction product, separation temperature 25��75 DEG C through decompression solution, and separating pressure is 1��20MPa, and the extraction product collecting gained is aldehydes matter.
2. the method for supercritical carbon dioxide extraction strand Ka Kele aldehydes matter according to claim 1, it is characterized in that: the strand Ka Kele blade powder described in step (1) is for obtain as follows: by strand Ka Kele blade through pre-freeze, then carry out vacuum lyophilization process, then pulverize.
3. the method for supercritical carbon dioxide extraction strand Ka Kele aldehydes matter according to claim 2, it is characterised in that: the condition of described pre-freeze is-70��-20 DEG C and processes 8��18 hours;
The time of described vacuum lyophilization is 20��36 hours;
The specification of described pulverizing is 20��60 orders.
4. the method for supercritical carbon dioxide extraction strand Ka Kele aldehydes matter according to claim 1, it is characterised in that: the extraction temperature described in step (1) is 40��50 DEG C;
Extracting pressure described in step (1) is 25��40MPa;
Extraction time described in step (1) is 2��4 hours.
5. the method for supercritical carbon dioxide extraction strand Ka Kele aldehydes matter according to claim 1, it is characterised in that: the carbon dioxide flow rate described in step (1) is 10��20L/ hour;
Entrainer flow velocity described in step (1) is 4��8ml/min.
6. the method for supercritical carbon dioxide extraction strand Ka Kele aldehydes matter according to claim 1, it is characterized in that: the entrainer described in step (1) is the one in alcohol, ketone and ether or at least two, or the mixed liquor that a kind of or at least two in alcohol, ketone and ether and water are formed.
7. the method for supercritical carbon dioxide extraction strand Ka Kele aldehydes matter according to claim 6, it is characterised in that: described alcohol is the one in ethanol, propanol and methanol or at least two;
Described ketone is acetone;
Described ether is petroleum ether.
8. the method for supercritical carbon dioxide extraction strand Ka Kele aldehydes matter according to claim 1, it is characterised in that: the extract and separate described in step (1) is for taking cycling extraction mode.
9. the method for supercritical carbon dioxide extraction strand Ka Kele aldehydes matter according to claim 8, it is characterised in that: the time of described cycling extraction is 30min.
10. the method for supercritical carbon dioxide extraction strand Ka Kele aldehydes matter according to claim 1, it is characterised in that: the separation temperature described in step (2) is 35��40 DEG C;
Separating pressure described in step (2) is 2��10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510980163.5A CN105622353B (en) | 2015-12-22 | 2015-12-22 | The method of supercritical carbon dioxide extracting strand Ka Kele aldehydes matters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510980163.5A CN105622353B (en) | 2015-12-22 | 2015-12-22 | The method of supercritical carbon dioxide extracting strand Ka Kele aldehydes matters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105622353A true CN105622353A (en) | 2016-06-01 |
| CN105622353B CN105622353B (en) | 2017-11-21 |
Family
ID=56037746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510980163.5A Active CN105622353B (en) | 2015-12-22 | 2015-12-22 | The method of supercritical carbon dioxide extracting strand Ka Kele aldehydes matters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105622353B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106307019A (en) * | 2016-09-12 | 2017-01-11 | 惠安县科联农业科技有限公司 | Special food formulation for atherosclerotic patients to consume and production method thereof |
| CN106473068A (en) * | 2016-09-12 | 2017-03-08 | 惠安华晨贸易有限公司 | A kind of food formula for strengthening body anti-fatigue ability and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6332052A (en) * | 1986-07-24 | 1988-02-10 | 株式会社ブリヂストン | Sheet waterproof structure with rooftop external heat insuration |
| CN101544543A (en) * | 2008-03-28 | 2009-09-30 | 广州合诚三先生物科技有限公司 | Method for purifying and separating phenolic compounds in magnolia medicament |
| CN102232994A (en) * | 2011-05-06 | 2011-11-09 | 南京泽朗医药科技有限公司 | Method for preparing total phenols of Lignum Sappan |
-
2015
- 2015-12-22 CN CN201510980163.5A patent/CN105622353B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6332052A (en) * | 1986-07-24 | 1988-02-10 | 株式会社ブリヂストン | Sheet waterproof structure with rooftop external heat insuration |
| CN101544543A (en) * | 2008-03-28 | 2009-09-30 | 广州合诚三先生物科技有限公司 | Method for purifying and separating phenolic compounds in magnolia medicament |
| CN102232994A (en) * | 2011-05-06 | 2011-11-09 | 南京泽朗医药科技有限公司 | Method for preparing total phenols of Lignum Sappan |
Non-Patent Citations (2)
| Title |
|---|
| RIADH KSOURI等: "Salinity effects on polyphenol content and antioxidant activities in leaves of the halophyte Cakile maritima", 《PLANT PHYSIOLOGY AND BIOCHEMISTRY》 * |
| S, BEER等: "Salt-stimulated Phosphoenolpyruvate Carboxylase in Cakile maritima", 《PHYSIOL. PLANT.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106307019A (en) * | 2016-09-12 | 2017-01-11 | 惠安县科联农业科技有限公司 | Special food formulation for atherosclerotic patients to consume and production method thereof |
| CN106473068A (en) * | 2016-09-12 | 2017-03-08 | 惠安华晨贸易有限公司 | A kind of food formula for strengthening body anti-fatigue ability and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105622353B (en) | 2017-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110304994B (en) | Method for extracting high-purity cannabidiol from industrial cannabis sativa | |
| CN103981018B (en) | A kind of preparation method of Ganoderma spore oil | |
| CN101721452B (en) | New process for improving utilization ratio of lithospermum | |
| CN111909006B (en) | Green high-efficiency conversion extraction method of resveratrol in giant knotweed rhizome | |
| CN103087828B (en) | A kind of Yunnan black tea essential oil and preparation method thereof | |
| CN102965198A (en) | Method for extracting and processing lavender essential oil | |
| CN110575679A (en) | Natural animal and plant extraction system and method | |
| CN105622353A (en) | Method for extracting Cakile Maritima phenolic substance from supercritical carbon dioxide | |
| CN103393787B (en) | The method of supercritical continuous carbon dioxide extraction oriental cherry effective ingredient | |
| CN107803049A (en) | The method for preparing papper oil and pepper oleoresin using ultrasonic subcritical fluid extraction technology | |
| CN101485814B (en) | Supercritical CO2 extraction method for saponin component in Paris polyphylla var. yunnanensis | |
| CN110862315B (en) | By using supercritical CO 2 Method for extracting carnosic acid from rosemary leaves | |
| CN101838178A (en) | Preparation method of lycopene | |
| CN102558104A (en) | Method for purifying lipstatin | |
| CN111187244B (en) | Novel method for extracting apigenin from celery | |
| CN101906254A (en) | Method for extracting capsaicin ointment from dimethyl ether | |
| CN105131841A (en) | Extraction method of pepper oleoresin | |
| CN105061211A (en) | Lignocellulosic biomass direct pressurized liquefaction and ethyl levulinate directional preparation method | |
| CN101074257B (en) | Method for extracting cholesterine in lanosterol by supercritical CO2 | |
| CN102813686B (en) | Method for extracting active ingredients from hibiscus sabdariffa calyx | |
| CN112707878A (en) | Extraction method of phthalide compounds | |
| CN1245826A (en) | Supercritical CO2 extraction method for extracting camplotheca acuminata seed vegetable oil | |
| CN111848363A (en) | Preparation method of high-purity cannabidiol | |
| CN103980326A (en) | Preparation method of salidroside by supercritical CO2 reverse micelles extraction | |
| CN102302693A (en) | Method for extracting imperata cylindrical root extract |
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 |