CN104630309A - Method for extracting small granule starch from manioc waste - Google Patents
Method for extracting small granule starch from manioc waste Download PDFInfo
- Publication number
- CN104630309A CN104630309A CN201510048806.2A CN201510048806A CN104630309A CN 104630309 A CN104630309 A CN 104630309A CN 201510048806 A CN201510048806 A CN 201510048806A CN 104630309 A CN104630309 A CN 104630309A
- Authority
- CN
- China
- Prior art keywords
- starch
- manioc waste
- starch granule
- water
- granule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Non-Alcoholic Beverages (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for extracting small granule starch from manioc waste. The method comprises the following steps: pretreating the manioc waste to remove free starch, performing enzymatic hydrolysis on the filter residue, performing separation refining on the obtained starch emulsion to remove impurities, and dehydrating and drying the starch emulsion to obtain the small granule starch. The method is used for extracting the natural small granule starch from the cheap manioc waste without the processes of ball milling, modification and the like, and is low in energy consumption, low in cost and simple and convenient in process; the obtained small granule starch is even in grain size and the mean grain size is 5-6 microns; the problems of high production cost of the small granule starch and difficult dehydrating and drying and low comprehensive utilization rate of the manioc waste are effectively solved.
Description
Technical field
The invention belongs to manioc waste technical field of comprehensive utilization, specifically a kind of make manioc waste be easy to dry while extract the method for starch granule.
Background technology
Manioc waste produces waste material remained by tapioca (flour), and Guangxi is the main cassava producing region of China, and year produces tapioca (flour) about 500,000 tons, produces more than 100 ten thousand tons of manioc wastes simultaneously.Dry manioc waste contains the remaining starch of about 55%, and simultaneously containing higher lignocellulose, content is about about 23%, and a small amount of pectin, ash content, protein and fat etc.The composition of lignocellulose mainly contains Mierocrystalline cellulose, hemicellulose and xylogen, and hemicellulose and xylogen form network structure by covalent bond, and Mierocrystalline cellulose is embedded in wherein.Lignocellulose can fix the moisture of own wt 16 times, and because of the network structure that lignocellulose is stable, this part water is Bound moisture, and a large amount of moisture is wrapped constraint, and moisture is difficult to the release that dissociated.The usual water content of fresh manioc waste is about 85%, and it is technical barrier that manioc waste dehydrates always, is difficult to be removed with method moisture such as the drying of routine, oven dry.The manioc waste do not dewatered is unfavorable for storing, transporting, in stacking process, easy cooperating microorganisms causes moldy metamorphism, distribute sour taste, also prussic acid can be produced, environmental pollution is serious, thus constrain regenerative ratio and the deep processing and utilization of manioc waste, bring very hang-up and environmental protection pressure also to the cleaner production of cassava processing enterprise.
Cassava, generally containing the starch of 20-30%, is divided into free starch and in conjunction with starch.Tapioca (flour) extraction process domestic is at present more ripe, free starch in cassava almost all can be extracted, remaining is fettered by the lignocellulose parcel in manioc waste in conjunction with starch, be difficult to by free release in starch isolation process, a large amount of starch is dropped with manioc waste, causes the very large wasting of resources.
Starch granule, also known as very fine starch, refers to that grain diameter is less than a kind of starch of 10 μm.Due to starch granule have that particle is tiny, the feature such as molecular size narrow range and hypoallergenic, in making fat substitute, infant food, biodegradable material, solid support material, fabric sizing agent, developing out paper and makeup etc., have special effect.Current production starch granule is generally raw material with Commercial starch, and obtained by the acidolysis of physics ball milled and chemistry, enzymolysis or other method of modifying couplings, adding chemical agent can produce waste liquid on the one hand, adds the difficulty of separation and purification simultaneously; Ball-milling Time is long on the other hand, and energy consumption is high, and facility investment is large, and mechanical damage appears in starch particle surface, and uniform particle diameter is poor.Chinese patent ZL 201110090114.6 discloses a kind of method adopting Production by Enzymes Starch rice, and gained Starch rice particle diameter is 2 ~ 8 μm, but raw materials cost is high, is not suitable for suitability for industrialized production.Therefore by the restriction of quality product, production technique and cost, starch granule is not widely applied always.
In manioc waste, remnants' is starch granule in conjunction with starch, and be natural starch granule, price is about three times of tapioca (flour), but does not have the technology report extracting starch granule from manioc waste so far.From the manioc waste of cheapness, extract starch granule, not only cost is low, quality product is high, also can alleviate the pollution of manioc waste to environment, realize the clean recycling of manioc waste, create higher economic benefit and social benefit.
Summary of the invention
The object of the present invention is to provide a kind of method extracting starch granule from manioc waste.The method is without the need to the technique such as ball milling, modification, and production cost is low, energy consumption is low, technological operation is easy.
Another object of the present invention is to provide the starch granule obtained according to described method.This starch granule is natural extract, even particle size distribution, and median size is 5 ~ 6 μm.
The technical scheme that the present invention solves the problems of the technologies described above is:
From manioc waste, extract a method for starch granule, comprise following operation steps:
(1) pre-treatment: the water adding 2 ~ 4 times of weight in manioc waste, stirs 5 ~ 30min, filters with 100 eye mesh screens;
(2) filtrate in step (1), through vortex separation system purification and recover, obtains tapioca (flour);
(3) enzymolysis: the filter residue in step (1) adds the water of 1 ~ 4 times of weight, adjust ph 3.5 ~ 5.5 enters prozyme by 2/10000ths ~ thousand/slender acanthopanax of filter residue weight, and hydrolysis temperature is 25 ~ 55 DEG C, and enzymolysis time is 6 ~ 50h;
(4) separation and purification: the enzymolysis solution in step (3), after pipe line type high-shear dispersing emulsifying pump process, filters with 100 eye mesh screens, starch milk through sand separator desanding, then is concentrated by vortex separation system, is separated, refines;
(5) dehydrate: the starch milk that step (4) obtains through centrifuge dehydration, then obtains starch granule by air stream drying.
The median size of described starch granule is 5 ~ 6 μm.
Described prozyme is by following parts by weight preparation: cellulase 20 ~ 40%, beta-glucanase 10 ~ 20%, zytase 10 ~ 15%, pentosanase 6 ~ 10%, polygalacturonase 10 ~ 20%, proteolytic enzyme 5 ~ 10%, polyphenoloxidase 4 ~ 7%, lipase 2 ~ 4%, α-amylase 1 ~ 3%.
Polyphenoloxidase in described prozyme is laccase.
Above-mentioned (4) step, the manioc waste that screen filtration retains is softer, can be directly used in production feed or be processed into fibre product, the raw material of such as food fibre after drying.
Above-mentioned (4) and (5) step, starch milk contains the materials such as a small amount of soluble sugar, pectin through the water that eddy flow is separated after centrifugal, but these water can return tapioca (flour) and produce front operation as cleaning raw material cassava water, if organic concentration is comparatively large, anaerobism or aerobic treatment can be adopted to recycle.
The inventive method tool has the following advantages:
1. the present invention first carries out water-washing pre-treatment to manioc waste, the free starch of recyclable manioc waste fiber surface and tapioca (flour), and water lotion can be incorporated in tapioca (flour) production technique and carry out separating-purifying starch, and waste water can recycle aborning.
2. the present invention adopts prozyme to act synergistically on manioc waste, destroy the netted and chain-like structure of lignocellulose, reduce manioc waste viscosity, make to be wrapped constraint in conjunction with starch---starch granule is free out, the fibrous residue extracted after starch can rapid drying to moisture content be about 10%, enzymolysis efficiency is high, and working condition is gentle.
3. the present invention extracts natural starch granule from manioc waste, relative to the natural starch granule of other kinds, and the inventive method low in raw material price, source is concentrated, and production cost is low; With physics ball milling conventional at present compared with chemical modification method process commodity starch, the inventive method only need increase retort, all the other equipment all can share with tapioca (flour) production unit, investment of production is few, the starch granule centralized particle diameter obtained, starch particle surface is without breakage, and energy consumption is low, produces waste liquid few.
4. starch granule of the present invention may be used for raw materials for food industry, cosmetic material, papermaking stopping composition, plastic filler, coating or loading pigment etc., the starch granule that the present invention prepares is better than the common potato starch that uses at present or cereal starch as the performance of filler, because particle is tiny, its sticking power, water-soluble, fillibility etc. are all fine.
5. the inventive method efficiently solves the problem of the difficult application of manioc waste, not only recyclable tapioca (flour), the very high starch granule of added value can be obtained again, fiber simultaneously after process can be used for feedstuff industry or exploitation fibre product, alleviate the environmental protection pressure of tapioca (flour) enterprise, and can be enterprise and bring higher economic benefit.
Accompanying drawing explanation
Fig. 1 is the particle size analysis result of the starch granule extracted from manioc waste.
Embodiment
Below by embodiment, the present invention is described in further detail.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
embodiment 1
The method of starch granule is extracted from manioc waste:
In manioc waste, add the water of 2 times of weight, stir 30min, filter with 100 eye mesh screens, filtrate is delivered to vortex separation system and carries out purification and recover, obtains tapioca (flour).The water of 4 times of weight is added in filter residue, adjust ph 3.5, prozyme is entered by thousand/slender acanthopanax of filter residue weight, prozyme is formed by 20% cellulase, 15% beta-glucanase, 15% zytase, 6% pentosanase, 20% polygalacturonase, 10% proteolytic enzyme, 7% laccase, 4% lipase, 3% α-amylase mixed preparing, hydrolysis temperature is 55 DEG C, and enzymolysis time is 6h.After reaction terminates, by enzymolysis solution by pipe line type high-shear dispersing emulsifying pump process, then filter with 100 eye mesh screens, the starch milk that filtration obtains is after sand separator desanding, concentrate with vortex separation system, be separated, refine, then through centrifuge dehydration, obtain starch granule by air stream drying.This starch granule median size (meso-position radius) is 5.59 μm.
The manioc waste stayed after above-mentioned manioc waste enzymolysis can be directly used in the raw material of production feed or be processed into fibre product after drying.Starch milk returns tapioca (flour) through the water that eddy flow is separated after centrifugal and produces front operation as cleaning raw material cassava water, or recycles after adopting anaerobism or aerobic treatment.
embodiment 2
The method of starch granule is extracted from manioc waste:
In manioc waste, add the water of 3 times of weight, stir 20min, filter with 100 eye mesh screens, filtrate is delivered to vortex separation system and carries out purification and recover, obtains tapioca (flour).The water of 3 times of weight is added in filter residue, adjust ph 4.0, prozyme is added by the thousandth of filter residue weight, prozyme is formed by 30% cellulase, 10% beta-glucanase, 14% zytase, 10% pentosanase, 18% polygalacturonase, 8% proteolytic enzyme, 6% laccase, 3% lipase, 1% α-amylase mixed preparing, hydrolysis temperature is 45 DEG C, and enzymolysis time is 20h.After reaction terminates, by enzymolysis solution by pipe line type high-shear dispersing emulsifying pump process, then filter with 100 eye mesh screens, the starch milk that filtration obtains is after sand separator desanding, concentrate with vortex separation system, be separated, refine, then through centrifuge dehydration, obtain starch granule by air stream drying.This starch granule median size (meso-position radius) is 5.77 μm.
The manioc waste stayed after above-mentioned manioc waste enzymolysis can be directly used in the raw material of production feed or be processed into fibre product after drying.Starch milk returns tapioca (flour) through the water that eddy flow is separated after centrifugal and produces front operation as cleaning raw material cassava water, or recycles after adopting anaerobism or aerobic treatment.
embodiment 3
The method of starch granule is extracted from manioc waste:
In manioc waste, add the water of 4 times of weight, stir 5min, filter with 100 eye mesh screens, filtrate is delivered to vortex separation system and carries out purification and recover, obtains tapioca (flour).The water of 2 times of weight is added in filter residue, adjust ph 4.5, prozyme is entered by ten thousand/slender acanthopanax of filter residue weight, prozyme is formed by 40% cellulase, 13% beta-glucanase, 10% zytase, 8% pentosanase, 15% polygalacturonase, 5% proteolytic enzyme, 5% laccase, 2% lipase, 2% α-amylase mixed preparing, hydrolysis temperature is 35 DEG C, and enzymolysis time is 40h.After reaction terminates, by enzymolysis solution by pipe line type high-shear dispersing emulsifying pump process, then filter with 100 eye mesh screens, the starch milk that filtration obtains is after sand separator desanding, concentrate with vortex separation system, be separated, refine, then through centrifuge dehydration, obtain starch granule by air stream drying.This starch granule median size (meso-position radius) is 5.74 μm.
The manioc waste stayed after above-mentioned manioc waste enzymolysis can be directly used in the raw material of production feed or be processed into fibre product after drying.Starch milk returns tapioca (flour) through the water that eddy flow is separated after centrifugal and produces front operation as cleaning raw material cassava water, or recycles after adopting anaerobism or aerobic treatment.
embodiment 4
The method of starch granule is extracted from manioc waste:
In manioc waste, add the water of 2.5 times of weight, stir 15min, filter with 100 eye mesh screens, filtrate is delivered to vortex separation system and carries out purification and recover, obtains tapioca (flour).The water of 1 times of weight is added in filter residue, adjust ph 5.5, prozyme is added by 2/10000ths of filter residue weight, prozyme is formed by 35% cellulase, 20% beta-glucanase, 12% zytase, 10% pentosanase, 10% polygalacturonase, 6% proteolytic enzyme, 4% laccase, 2% lipase, 1% α-amylase mixed preparing, hydrolysis temperature is 25 DEG C, and enzymolysis time is 50h.After reaction terminates, by enzymolysis solution by pipe line type high-shear dispersing emulsifying pump process, then filter with 100 eye mesh screens, the starch milk that filtration obtains is after sand separator desanding, concentrate with vortex separation system, be separated, refine, then through centrifuge dehydration, obtain starch granule by air stream drying.This starch granule median size (meso-position radius) is 5.60 μm.
The manioc waste stayed after above-mentioned manioc waste enzymolysis can be directly used in the raw material of production feed or be processed into fibre product after drying.Starch milk returns tapioca (flour) through the water that eddy flow is separated after centrifugal and produces front operation as cleaning raw material cassava water, or recycles after adopting anaerobism or aerobic treatment.
experimental example 1 particle diameter ratio comparatively
Starch granule (embodiment 1) particle diameter that the inventive method obtains and several frequently seen starch particle diameter comparative result are in table 1:
Starch granule particle diameter prepared by visible the inventive method is significantly less than the particle diameter of common starch on the market.
The particle size analysis of the starch granule (embodiment 1) that the inventive method obtains the results are shown in Table 2.
experimental example 2
Starch granule prepared by the inventive method replaces other starch to prepare food, healthcare products or makeup.Its sticking power, water-soluble, fillibility etc., than existing common potato starch or cereal starch all good.
Claims (6)
1. from manioc waste, extract a method for starch granule, it is characterized in that, comprise following operation steps:
(1) pre-treatment: the water adding 2 ~ 4 times of weight in manioc waste, stirs 5 ~ 30min, filters with 100 eye mesh screens;
(2) filtrate in step (1), through vortex separation system purification and recover, obtains tapioca (flour);
(3) enzymolysis: the filter residue in step (1) adds the water of 1 ~ 4 times of weight, adjust ph 3.5 ~ 5.5 enters prozyme by 2/10000ths ~ thousand/slender acanthopanax of filter residue weight, and hydrolysis temperature is 25 ~ 55 DEG C, and enzymolysis time is 6 ~ 50h;
(4) separation and purification: the enzymolysis solution in step (3), after pipe line type high-shear dispersing emulsifying pump process, filters with 100 eye mesh screens, starch milk through sand separator desanding, then is concentrated by vortex separation system, is separated, refines;
(5) dehydrate: the starch milk that step (4) obtains through centrifuge dehydration, then obtains starch granule by air stream drying.
2. the method extracting starch granule from manioc waste according to claim 1, is characterized in that: described prozyme is prepared by following parts by weight: cellulase 20 ~ 40%, beta-glucanase 10 ~ 20%, zytase 10 ~ 15%, pentosanase 6 ~ 10%, polygalacturonase 10 ~ 20%, proteolytic enzyme 5 ~ 10%, polyphenoloxidase 4 ~ 7%, lipase 2 ~ 4%, α-amylase 1 ~ 3%.
3. the method extracting starch granule from manioc waste according to claim 2, is characterized in that: the polyphenoloxidase in described prozyme is laccase.
4. the method extracting starch granule from manioc waste according to claim 1, is characterized in that: the median size of described starch granule is 5 ~ 6 μm.
5. the method extracting starch granule from manioc waste according to claim 1, is characterized in that: step the (4) step, is directly used in the raw material of production feed or is processed into fibre product after the manioc waste drying that screen filtration retains.
6. the method extracting starch granule from manioc waste according to claim 1, it is characterized in that: above-mentioned steps (4) and (5) step, starch milk returns tapioca (flour) through the water that eddy flow is separated after centrifugal and produces front operation as cleaning raw material cassava water, or recycles after adopting anaerobism or aerobic treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510048806.2A CN104630309B (en) | 2015-01-30 | 2015-01-30 | The method that starch granule is extracted from manioc waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510048806.2A CN104630309B (en) | 2015-01-30 | 2015-01-30 | The method that starch granule is extracted from manioc waste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104630309A true CN104630309A (en) | 2015-05-20 |
| CN104630309B CN104630309B (en) | 2018-01-09 |
Family
ID=53209553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510048806.2A Active CN104630309B (en) | 2015-01-30 | 2015-01-30 | The method that starch granule is extracted from manioc waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104630309B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107922510A (en) * | 2015-08-07 | 2018-04-17 | 诺维信公司 | Starch isolation |
| CN109024035A (en) * | 2018-06-28 | 2018-12-18 | 广西驰胜农业科技有限公司 | A method of extracting cellulose from manioc waste |
| JPWO2021033742A1 (en) * | 2019-08-20 | 2021-11-25 | 日揮触媒化成株式会社 | Particles containing starch, their manufacturing methods, and cosmetics |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285058A (en) * | 2008-06-11 | 2008-10-15 | 吴鹏 | Compound enzyme preparation for manioc waste industry |
| CN201380054Y (en) * | 2009-03-31 | 2010-01-13 | 温州科瑞机械有限公司 | Pipe line type high-shear dispersing emulsifying pump |
| CN101990987A (en) * | 2009-08-14 | 2011-03-30 | 甘肃省农业科学院农产品贮藏加工研究所 | Method for recycling potato residue and waste water in production process of potato starch |
| CN102180980A (en) * | 2011-04-12 | 2011-09-14 | 江南大学 | Method for producing rice starch by adopting enzyme method and product obtained by using method |
| CN102286570A (en) * | 2011-05-26 | 2011-12-21 | 贵州华贵鹏博生物科技有限公司 | Method for independently separating and recycling starch resources from tuber residues |
-
2015
- 2015-01-30 CN CN201510048806.2A patent/CN104630309B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285058A (en) * | 2008-06-11 | 2008-10-15 | 吴鹏 | Compound enzyme preparation for manioc waste industry |
| CN201380054Y (en) * | 2009-03-31 | 2010-01-13 | 温州科瑞机械有限公司 | Pipe line type high-shear dispersing emulsifying pump |
| CN101990987A (en) * | 2009-08-14 | 2011-03-30 | 甘肃省农业科学院农产品贮藏加工研究所 | Method for recycling potato residue and waste water in production process of potato starch |
| CN102180980A (en) * | 2011-04-12 | 2011-09-14 | 江南大学 | Method for producing rice starch by adopting enzyme method and product obtained by using method |
| CN102286570A (en) * | 2011-05-26 | 2011-12-21 | 贵州华贵鹏博生物科技有限公司 | Method for independently separating and recycling starch resources from tuber residues |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107922510A (en) * | 2015-08-07 | 2018-04-17 | 诺维信公司 | Starch isolation |
| CN109024035A (en) * | 2018-06-28 | 2018-12-18 | 广西驰胜农业科技有限公司 | A method of extracting cellulose from manioc waste |
| JPWO2021033742A1 (en) * | 2019-08-20 | 2021-11-25 | 日揮触媒化成株式会社 | Particles containing starch, their manufacturing methods, and cosmetics |
| JP7026428B2 (en) | 2019-08-20 | 2022-02-28 | 日揮触媒化成株式会社 | Particles containing starch, their manufacturing methods, and cosmetics |
| KR20220050882A (en) * | 2019-08-20 | 2022-04-25 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Particles containing starch, manufacturing method thereof, and cosmetics |
| KR102582931B1 (en) | 2019-08-20 | 2023-09-26 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Particles containing starch, manufacturing method thereof, and cosmetics |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104630309B (en) | 2018-01-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2717097C2 (en) | Method and apparatus for forming lignin fraction, lignin composition and use thereof | |
| CN109577060B (en) | Method for preparing natural-color biomechanical pulp by treating wheat straw with hot water and alkaline biological enzyme | |
| CN101792495A (en) | Method for ultrasonically catalyzing and extracting hemicellulose, cellulose and lignin from plant straws | |
| CN107881842B (en) | Method for preparing high-strength corrugated base paper by using straws and waste paper pulp | |
| CN109676714A (en) | A method of bamboo extractive and bamboo pulp are prepared with bamboo | |
| CN103450362A (en) | Production technology of potato starch | |
| CN103696311A (en) | Office waste paper recycling method | |
| CN104630309A (en) | Method for extracting small granule starch from manioc waste | |
| CN103965365B (en) | A kind of preparation method of apple residue Microcrystalline Cellulose | |
| CN102154936B (en) | Method for preparing paper making wet end chemical addition agent by using cassava residue as raw material | |
| CN102242513A (en) | Method for independently separating and recovering plant cellulose from potato residues | |
| WO2021057159A1 (en) | Processing technology for removing adhesive substances from paper pulp | |
| CN102660885A (en) | Method for preparing high-performance long fiber by utilizing lignocelluloses biological method | |
| CN109629318B (en) | Method for preparing bio-mechanical pulp from wheat straw leaves | |
| CN103835179A (en) | Composite paper making pulp substrate and manufacturing method thereof | |
| CN111472186A (en) | Method for preparing high-quality crop straw dissolving pulp through hydrothermal pretreatment | |
| EP2297395B1 (en) | Methods and systems for feedstock production from sewage and product manufacturing therefrom | |
| CN108411689A (en) | A method of preparing waste paper reinforcing agent with agricultural stalk | |
| CN102250256A (en) | Preparation method of carboxymethyl cellulose | |
| CN107237192B (en) | A kind of regenerated newsprint and preparation method thereof | |
| CN106480129A (en) | A kind of preparation method of nano-cellulose | |
| CN106368032B (en) | Method that is a kind of while preparing cellulose fiber peacekeeping hemicellulose solution | |
| CN108753847A (en) | A kind of technique of stalk enzymatic hydrolysis and fermentation synchronous production ethyl alcohol, xylo-oligosaccharide, lignin, cellulose fiber slurry | |
| CN103496029A (en) | Method for manufacturing straw fiberboard | |
| CN103087204A (en) | Micro-powder cellulose preparation method |
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 |