CN101475972A - Method for producing L-arabinose from corncob - Google Patents
Method for producing L-arabinose from corncob Download PDFInfo
- Publication number
- CN101475972A CN101475972A CNA2009100779433A CN200910077943A CN101475972A CN 101475972 A CN101475972 A CN 101475972A CN A2009100779433 A CNA2009100779433 A CN A2009100779433A CN 200910077943 A CN200910077943 A CN 200910077943A CN 101475972 A CN101475972 A CN 101475972A
- Authority
- CN
- China
- Prior art keywords
- arabinose
- corn cob
- production method
- acid
- treatment
- 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
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention provides a method of using corn core to produce L-arabinose, including the following steps: processing the corn cob to get the raw materials containing L-arabinose, inoculating microorganism to improve the purity of the L-arabinose component and simultaneously produce other byproducts, and then isolating the byproducts and L-arabinose, respectively extracting, refining, to get the high-purity L-arabinose and byproducts. The method has advantages of low production cost, high productivity, a wide array of raw material sources, and capability of adjusting the byproduct kinds at any time in accordance with market conditions, etc.
Description
Technical field
The present invention relates to a kind of production method of L-arabinose, specifically, relate to a kind of method of utilizing corn cob to produce L-arabinose, belong to medicine, food chemical field.
Background technology
L-arabinose is a kind of function sugar of using industries such as food and medicine, has special physiological properties.Physiologist and nutritionist with regard to L-arabinose in enteron aisle to being used as of sugar metabolism the series of studies discovery: L-arabinose has remarkable blocking effect to the metabolic conversion of sucrose, makes its good in fat-reducing, application prospect aspect the control of diabetes.It is reported that the L-arabinose that needs only interpolation 2% in common sucrose just can suppress the absorption of sucrose, has suppressed blood glucose value simultaneously and has raise about 50% less.If the L-arabinose addition reaches 4%, blood glucose value is not raise fully, Regular Insulin is secreted hardly.
According to estimates, China has 4,000 ten thousand above diabeticss at least, has become the third-largest state of world diabetics, and other has 6,000 ten thousand pre-diabetes crowds.Therefore, L-arabinose for ordinary people influence bigly may add iodine with salt, soy sauce adds iron and mentions in the same breath.
CN1299420A has proposed a kind of method of producing L-arabinose by acid hydrolysis, this method weak point is the simple degrade plant material such as hydrochloric acid or sulfuric acid of using in the whole process, the product of preparation is the mixed sugar liquid that contains L-arabinose, wood sugar, semi-lactosi and glucose etc., its raw material treatment capacity is 500 grams to the maximum, how not show in the technological process and to obtain L-arabinose xln product by purifying.
CN1373135A propose to use the acid hydrolysis gum arabic, separates the method for L-arabinose then by column chromatography, and weak point is that production cost height, efficient are low.
CN1966665A, CN101100685A propose to produce L-arabinose with sulfuric acid and amylase degrading maize wheat bran, and its weak point is the corn bran feedstock quantity not sufficient to satisfy the demands, and output is restricted, and the corn bran price is higher than corn cob far away.
Existing in a word L-arabinose production technology is sayed from large-scale production, all exists certain problem on its economy and the production efficiency.
Summary of the invention
The purpose of this invention is to provide that a kind of production cost is low, production efficiency is high, raw material sources L-arabinose production method widely.
In order to realize the object of the invention, a kind of method of utilizing corn cob to produce L-arabinose of the present invention comprises the steps:
1) earlier corn cob is carried out acid treatment, obtain corn cob liquid glucose and corn cob slag, again corn cob liquid glucose purifying treatment is obtained containing the raw material of L-arabinose;
2) raw material that will contain L-arabinose then ferments by microbe inoculation, fermented liquid;
3) again to fermented liquid handle byproduct and L-arabinose;
4) respectively byproduct and L-arabinose are made with extra care at last, obtained byproduct and crystallization L-arabinose.
Wherein, the acid that the described corn cob acid treatment of step 1) is used is sulfuric acid, hydrochloric acid, phosphoric acid etc. or their mixture, and acid concentration is 0.01N-0.5N, and temperature is 80-150 ℃, and the treatment time is 10-300 minute.
Corn cob can obtain corn cob liquid glucose and corn cob slag through peracid treatment.
Described corn cob liquid glucose can further be handled and obtain L-arabinose, can mainly contain the fermention medium or the fuel of glucose as preparation for the corn cob slag.
Steps such as described corn cob liquid glucose purifying treatment comprises decolouring, desalination, concentrate, specifically, the general gac that adopts of decolouring carries out, and desalination adopts ion exchange resin to carry out, and concentrates to adopt reverse osmosis membrane to carry out.
Step 2) described microorganism is a yeast, specifically comprises candiyeast, bread yeast, cereuisiae fermentum or pichia spp etc.
The present invention inoculates different types of yeast will utilize wood sugar or the different product of glucose generation in the corn cob liquid glucose, just can produce alcohol as the inoculation pichia spp, and the inoculation candida tropicalis just can produce Xylitol, but L-arabinose can not be utilized.
Microbial fermentation of the present invention can adopt this area strain inclined plane commonly used to cultivate and the seed enlarged culturing.
The gained fermented liquid need carry out degerming, removal of impurities, decolouring, desalination step process behind the microbial fermentation.Can obtain byproduct and the material that is rich in L-arabinose respectively.
The material that is rich in L-arabinose through concentrating, crystallization, centrifugal highly purified crystallization L-arabinose.
Described concentrating adopts reverse osmosis membrane-systems and/or vaporizers to carry out more.
By the processing of the present invention, except obtaining also can to obtain different byproducts the L-arabinose, such as changing into Xylitol or ethanol by glucose, wood sugar to corn cob.
The production method of L-arabinose of the present invention, use the corn cob raw material of wide material sources,, obtain containing the raw material of L-arabinose by the acid treatment method and the liquid glucose purifying method of routine, by microbe inoculation, produce other products when having improved in the material purity of L-arabinose.Its advantage is:
1. use the corn cob raw material, production cost is low;
2. L-arabinose content is higher in the corn cob, the production efficiency height, and also the yield of L-arabinose generally can reach about 85%, and the L-arabinose product purity can reach 99.5%;
3. raw material sources is extensive;
4. by microbe inoculation, make that glucose, wood sugar are converted into easily and the isolating component of L-arabinose in the corn cob liquid glucose, and the kind of the byproduct that is changed into by glucose, wood sugar can adjust also, such as changing into Xylitol or ethanol.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The method of corn cob pre-treatment and corn cob liquid glucose purifying treatment comprises the steps:
1. the weight of will giving money as a gift earlier is 1000 kilograms, and putting into volume through the corn cob of washing after the removal of impurities is in the 5 cubical acidolysis pots, after adding water and being settled to 4.5 cubes temperature is heated to 110 ℃ and add 40 kilograms of vitriol oils, is incubated 60 minutes.
2. above-mentioned material is separated by sheet frame, and the washing solid phase, 4.5 cubes of corn cob liquid glucoses and corncob acid hydrolysis slag obtained.
In the corn cob liquid glucose by volume 1 ‰ add Powdered Activated Carbons, insulation is 30 minutes under 55 ℃ of conditions, removes gac with candle filter then, obtains the liquid glucose that decolours.
4. the decolouring liquid glucose enters cationic exchange coloum that loads 001 * 7 Zeo-karb and the anion-exchange column that loads 201 * 7 anionite-exchange resin, removes foreign ion in the liquid glucose, obtains from handing over liquid glucose;
5. after handing over liquid glucose to enter the reverse osmosis membrane concentrating unit to concentrate, obtain total sugar concentration and be 15% corn cob liquid glucose (for containing the raw material of L-arabinose).
Following table 1 is a corn cob liquid glucose main component.
The main component of table 1 corn cob liquid glucose
| Project | Content (%) |
| The DNS total reducing sugar | 15 |
| Glucose | 0.57 |
| Wood sugar | 12.65 |
| L-arabinose | 1.80 |
Embodiment 2
Produce L-arabinose, the production method of by-product Xylitol, the Xylitol preparation comprises the steps:
1. Xylitol seed preparation: from the strain inclined plane to the shake-flask culture, insert seeding tank then, the seed tank culture base consist of embodiment 1 preparation corn cob concentrate liquid glucose, yeast powder, corn steep liquor, feed sterile air and cultivate.
Bacterial classification: candida tropicalis (G.tropicalis)
Slant medium: glucose 1%, wood sugar 1%, yeast powder 0.3%, peptone 0.5%, corn cob liquid glucose 3%, agar 2%.
Shake-flask culture base: glucose 1%, wood sugar 2%, yeast powder 0.5%, peptone 0.8%.
Seed tank culture base: corn cob liquid glucose 3%, yeast powder 0.5%, corn steep liquor 0.8%, glucose 1%.
Seed tank culture condition: ventilating ratio: 1:0.5;
Culture temperature: 29～31 ℃
Cultivate pH:6.0～6.5
2. fermentative preparation Xylitol
The corn cob of embodiment 1 preparation is concentrated liquid glucose, add in the fermentor tank, add the corn steep liquor of 0.1% ammonium sulfate and 0.3%, steam heating to 121 ℃ was kept 30 minutes, was cooled to 32 ℃, insert the seed liquor that step 1 is cultivated, inoculum size is 10% of a fermention medium volume.
Technological condition for fermentation: initial pH6.0; Ventilating ratio adopts two sections control methods: preceding 10 hours 1:0.4, reduce to 1:0.15, then up to fermentation ends.30～32 ℃ of leavening temperatures, fermentation period was less than 72 hours.
The fermenting-ripening mash is seen: brown liquid, proportion 1.06, wet amount of yeast 5%; Xylitol concentration 9.5%; Xylitol is to wood sugar transformation efficiency 75%.
3. xylitol fermentation liquor is handled
Fermented liquid degerming, removal of impurities
Fermented liquid is the board-like membrane filtration of 50KD through molecular weight cut-off, obtains clarifying fermentation clear liquid and yeast, and yeast oven dry back is as feed.
The decolouring of powder carbon
Under 75～80 ℃ of conditions, add Powdered Activated Carbon, dosage is 3 ‰ of a volume of material, is incubated after 30 minutes to filter with plate-and-frame filter press, obtains the Xylitol destainer.
The ion-exchange desalination
Destainer enters the cationic exchange coloum of filling 001 * 7 strongly acidic cation-exchange, the anion-exchange column of filling 201 * 7 strong basic type anion-exchange resins, and input speed is controlled at 5BVS/h, obtains Xylitol from handing over liquid.
Concentrate: the material solid content is brought up to 90% with plate-type evaporator.
Crystallization: the material after will concentrating is put into horizontal crystallizer, is cooled to 50～60 ℃, presses 10% of Xylitol amount and adds xylitol seed crystals, and growing the grain by the cooling of 1 ℃/h cooling rate, cooled to below 25 ℃ after 10 hours.
Separate:, obtain xylitol crystal and Xylitol mother liquor with whizzer fractional crystallization material.
Embodiment 3
Produce L-arabinose, the production method of by-product Xylitol, the L-arabinose preparation comprises the steps:
1. L-arabinose separates in the Xylitol mother liquor
The Xylitol mother liquor that embodiment 2 is produced pumps into the simulated moving bed system of loading PCR642,60 ℃ of system operation temperature, and washing water quantity is 8 times of inlet amount, collects wood sugar phase, L-arabinose phase, Xylitol phase respectively.
2.L-pectinose concentrates
The L-arabinose that simulated moving bed system is collected enters RO system (reverse osmosis system) mutually, and material is concentrated into solid content 15%, with plate-type evaporator the material solid content is brought up to 75% then.
3.L-pectinose crystallization
L-arabinose after concentrating is put into horizontal crystallizer, is cooled to the crystal seed that adds L-arabinose amount 2% after 45 ℃, and growing the grain by the cooling of 1 ℃/h cooling rate, cooled to below 25 ℃ after 10 hours.
4.L-pectinose is centrifugal
With whizzer fractional crystallization material, and, obtain L-arabinose crystal and L-arabinose mother liquor with 10 ℃ of cold water washing crystal.
Embodiment 4
Produce L-arabinose, by-product alcoholic acid production method, ethanol preparation comprises the steps:
1. ethanol fermentation seed preparation
Substratum consists of corn cob and concentrates liquid glucose 5 ± 1%, yeast extract paste 0.2%, corn steep liquor 1%, dipotassium hydrogen phosphate 0.15%, ammonium sulfate 0.05%, Secondary ammonium phosphate 0.2%.
With substratum by 110 ℃ of sterilizations 20 minutes, be cooled to 31 ℃ after, by 10% inoculum size inoculation yeast CGMCC No.1859 (preservation date: on November 08th, 2006, and open in CN101186943), culture condition: 31 ℃, cultivated 36 hours.
2. fermentation culture
Substratum consists of corn cob and concentrates liquid glucose 14 ± 1%, yeast extract paste 0.2%, corn steep liquor 1%, dipotassium hydrogen phosphate 0.05%, ammonium sulfate 0.05%, Secondary ammonium phosphate 0.15%.
Substratum is by 121 ℃ of sterilizations 30 minutes, be cooled to 36 ℃ after, insert to cultivate sophisticated seed liquor by 10% inoculum size, fermentation condition: 36 ℃ of leavening temperatures, fermentation pH4.8 ± 0.2, preceding 4 hours ventilating ratio 1:0.2, stop after 4 hours ventilating fermentation period 58 hours.
3. the degerming of ethanol fermentation liquid, removal of impurities
Fermentation liquid is obtained yeast and fermentation clear liquid after by the disk plate centrifuge separated yeast, and yeast oven dry back is as feed.
4. ethanol distillation
By distillation tower, cat head is gathered ethanol with the fermentation clear liquid after degerming, the removal of impurities, and tower bottoms is the component that is rich in L-arabinose.
Embodiment 5
Produce L-arabinose, by-product alcoholic acid production method, the L-arabinose preparation comprises the steps:
1. tower bottoms decolouring
Under 75 ℃ of conditions, add Powdered Activated Carbon, dosage is 2 ‰ of a volume of material, is incubated after 30 minutes to filter with plate-and-frame filter press, obtains the tower bottoms destainer.
2. ion-exchange desalination
Destainer enters the cationic exchange coloum of filling 001 * 7 strongly acidic cation-exchange, the anion-exchange column of filling 201 * 7 strong basic type anion-exchange resins, and input speed is controlled at 5BVS/h, obtains tower bottoms from handing over liquid.
3. concentrate: the material solid content is brought up to 15% with the RO film.
4.L-pectinose separates
RO membrane concentration liquid enters the simulated moving bed system of filling PCR642,60 ℃ of system operation temperature, and washing water quantity is 4 times of inlet amount, collects wood sugar phase, L-arabinose phase, fusel phase respectively.
5.L-pectinose concentrates
The L-arabinose that simulated moving bed system is collected enters the RO system mutually, and material is concentrated into solid content 15%, with plate-type evaporator the material solid content is brought up to 75% then.
6.L-pectinose crystallization
L-arabinose after concentrating is put into horizontal crystallizer, is cooled to the crystal seed that adds L-arabinose amount 2% after 45 ℃, and growing the grain by the cooling of 1 ℃/h cooling rate, cooled to below 25 ℃ after 10 hours.
7.L-pectinose is centrifugal
With whizzer fractional crystallization material, and, obtain the L-arabinose crystal with 10 ℃ of cold water washing crystal.Product purity reaches 99.5%.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (8)
1. a method of utilizing corn cob to produce L-arabinose is characterized in that, comprises the steps:
1) earlier corn cob is carried out acid treatment, obtain corn cob liquid glucose and corn cob slag, again corn cob liquid glucose purifying treatment is obtained containing the raw material of L-arabinose;
2) raw material that will contain L-arabinose then ferments by microbe inoculation, fermented liquid;
3) again to fermented liquid handle byproduct and L-arabinose;
4) respectively byproduct and L-arabinose are made with extra care at last, obtained byproduct and crystallization L-arabinose.
2. according to the described L-arabinose production method of claim 1, it is characterized in that the acid that the acid treatment of corn cob described in the step 1) is used is 0.01N-0.5N as sulfuric acid, hydrochloric acid, phosphoric acid or their mixture, acid concentration, temperature is 80-150 ℃, and the treatment time is 10-300 minute.
3. according to claim 1 or 2 described L-arabinose production methods, it is characterized in that described corn cob liquid glucose purifying treatment comprises decolouring, desalination, enrichment step.
4. according to the described L-arabinose production method of claim 3, it is characterized in that described decolouring adopts gac to handle, described desalination adopts ion exchange resin or electrodialytic membranes to handle, and described concentrated employing reverse osmosis membrane or vaporizer are handled.
5. according to the described L-arabinose production method of claim 1, it is characterized in that step 2) described in microorganism be yeast.
6. according to the described L-arabinose production method of claim 5, it is characterized in that described yeast is candiyeast, bread yeast, cereuisiae fermentum or pichia spp.
7. according to any described L-arabinose production method of claim 1-6, it is characterized in that fermentation liquor treatment described in the step 3) comprises degerming, removal of impurities, decolouring, desalination step.
8. according to any described L-arabinose production method of claim 1-7, it is characterized in that refining concentrated, crystallization, the centrifugation step of comprising described in the step 4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100779433A CN101475972B (en) | 2009-02-04 | 2009-02-04 | Method for producing L-arabinose from corncob |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100779433A CN101475972B (en) | 2009-02-04 | 2009-02-04 | Method for producing L-arabinose from corncob |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101475972A true CN101475972A (en) | 2009-07-08 |
| CN101475972B CN101475972B (en) | 2012-04-04 |
Family
ID=40836751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100779433A Active CN101475972B (en) | 2009-02-04 | 2009-02-04 | Method for producing L-arabinose from corncob |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101475972B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101818216A (en) * | 2010-04-26 | 2010-09-01 | 安徽丰原发酵技术工程研究有限公司 | Method for refining corncob acid hydrolysis solution |
| CN101824055B (en) * | 2009-12-30 | 2012-07-25 | 山东福田药业有限公司 | Method for preparing L-arabinose by taking corn bran as material |
| CN102659854A (en) * | 2012-03-15 | 2012-09-12 | 济南圣泉唐和唐生物科技有限公司 | Purification method for L-arabinose |
| CN103274404A (en) * | 2013-06-19 | 2013-09-04 | 济南圣泉集团股份有限公司 | Method for preparing active carbon adsorption material by plant acidolysis residues |
| CN101665523B (en) * | 2009-09-30 | 2015-09-30 | 济南圣泉唐和唐生物科技有限公司 | The production method of L-arabinose and D-xylose pref |
| CN114032256A (en) * | 2021-10-15 | 2022-02-11 | 山东寿光巨能金玉米开发有限公司 | Method for co-producing ethanol and L-arabinose by using corn bran |
| CN117069776A (en) * | 2023-08-01 | 2023-11-17 | 北京澳特舒尔保健品开发有限公司 | Method for preparing L-arabinose from liquid xylitol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3834152B2 (en) * | 1998-05-01 | 2006-10-18 | 三和興産株式会社 | Method for producing L-arabinose by acid hydrolysis method |
| CN101100685B (en) * | 2007-08-01 | 2010-06-09 | 李萍 | Method for preparing L-arabinose |
-
2009
- 2009-02-04 CN CN2009100779433A patent/CN101475972B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665523B (en) * | 2009-09-30 | 2015-09-30 | 济南圣泉唐和唐生物科技有限公司 | The production method of L-arabinose and D-xylose pref |
| CN101824055B (en) * | 2009-12-30 | 2012-07-25 | 山东福田药业有限公司 | Method for preparing L-arabinose by taking corn bran as material |
| CN101818216A (en) * | 2010-04-26 | 2010-09-01 | 安徽丰原发酵技术工程研究有限公司 | Method for refining corncob acid hydrolysis solution |
| CN101818216B (en) * | 2010-04-26 | 2012-07-04 | 安徽丰原发酵技术工程研究有限公司 | Method for refining corncob acid hydrolysis solution |
| CN102659854A (en) * | 2012-03-15 | 2012-09-12 | 济南圣泉唐和唐生物科技有限公司 | Purification method for L-arabinose |
| CN102659854B (en) * | 2012-03-15 | 2014-08-13 | 济南圣泉唐和唐生物科技有限公司 | Purification method for L-arabinose |
| CN103274404A (en) * | 2013-06-19 | 2013-09-04 | 济南圣泉集团股份有限公司 | Method for preparing active carbon adsorption material by plant acidolysis residues |
| CN114032256A (en) * | 2021-10-15 | 2022-02-11 | 山东寿光巨能金玉米开发有限公司 | Method for co-producing ethanol and L-arabinose by using corn bran |
| CN117069776A (en) * | 2023-08-01 | 2023-11-17 | 北京澳特舒尔保健品开发有限公司 | Method for preparing L-arabinose from liquid xylitol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101475972B (en) | 2012-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101475972B (en) | Method for producing L-arabinose from corncob | |
| Cheng et al. | Optimization of pH and acetic acid concentration for bioconversion of hemicellulose from corncobs to xylitol by Candida tropicalis | |
| CN102268490B (en) | Clean technique for co-producing xylose, xylitol and arabinose from agricultural waste and forest waste | |
| CN100572543C (en) | Utilize corn cob or agriculture and forestry organic waste material to prepare the method for Xylitol | |
| CN101538589A (en) | New clean method for producing xylitol and arabinose | |
| CN101775413B (en) | Technique for producing xylitol and dulcitol simultaneously | |
| CN102399826A (en) | Comprehensive utilizing method of sweet sorghum stalks | |
| CN101857523A (en) | Method for producing xylitol and arabitol simultaneously by utilizing xylose mother liquid | |
| CN109486876A (en) | A method of threonine is extracted and is purified in fermentation | |
| CN100390271C (en) | Method of producing xylosic alcohol and its special baterial strain | |
| CN102399837B (en) | Method for synthesizing acarbose through microbial fermentation | |
| CN101736058A (en) | Method for producing mannitol by taking jerusalem artichoke as raw materials through biotransformation | |
| CN103173340A (en) | Method for producing organic acid seasoning liquid for wine through utilizing white wine brewage byproduct | |
| CN101705253A (en) | Method for treating xylose mother solution | |
| CN102352396A (en) | Method of producing functional starch sugar through wheat starch | |
| CN113321580B (en) | Method for producing malic acid | |
| CN108949713B (en) | Preparation method of aspergillus oryzae fermentation broth and application of aspergillus oryzae fermentation broth in production of fructo-oligosaccharide | |
| CN101323838B (en) | Recombinant distiller's yeast and use thereof in eutrit production | |
| CN102703334B (en) | Strain producing erythritol and method for producing erythritol by using strain | |
| CN101979616A (en) | Method for producing erythritol by using broken rice | |
| CN109517745B (en) | Microbial composite bacteria for brewing wine and quinoa wine brewed by same | |
| CN101696429B (en) | Method for producing butanol by hydrolyzing and fermenting waste crops rich in hemicellulose | |
| CN108277240B (en) | Process for preparing citric acid by fermentation | |
| CN108374024B (en) | Method for co-producing ethanol, fructose and various byproducts by using sweet sorghum stalks and corns | |
| CN101857886B (en) | Method for preparing xylitol and co-producing L-arabinose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |