CN101182361A - Method for preparing acetylated hemicellulose by employing catalysis of iodine - Google Patents
Method for preparing acetylated hemicellulose by employing catalysis of iodine Download PDFInfo
- Publication number
- CN101182361A CN101182361A CNA2007100322560A CN200710032256A CN101182361A CN 101182361 A CN101182361 A CN 101182361A CN A2007100322560 A CNA2007100322560 A CN A2007100322560A CN 200710032256 A CN200710032256 A CN 200710032256A CN 101182361 A CN101182361 A CN 101182361A
- Authority
- CN
- China
- Prior art keywords
- hemicellulose
- iodine
- wheat straw
- straw waste
- added
- 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
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a method of applying iodine catalysis to prepare for acetylated hemicellulose. Firstly, KOH solution is used to dispose delignified wheat straw, then, dissolved alkali-soluble hemicellulose in filtrate is processed for purification and separation; subsequently, the hemicellulose after separation is added into 1-butyl-3-methyl imidazole chloride solution, the catalyst iodine with the weight of corresponding 10 percent to 15 percent of the hemicellulose is added, then the acetic anhydride which is 16 to 28 times of xylan hydroxyl in the compositions of the hemicellulose is added to react for 20 to 30 minutes under 90 DEG C to 110 DEG C and cooled, saturated sodium thiosulfate is added into a mixture, and ethanol is used for washing and drying to obtain the acetylated hemicellulose. The invention can obtain the acetylated hemicellulose with high substitution degree; compared with a heterogeneous system, the invention improved the reaction speed by five to ten times, increases the output and reduces the production cost, the hydrophobic nature of the hemicellulose after chemical modification is improved greatly, and the invention can be used for preparing for the degradable food-packing film.
Description
Technical field
The present invention relates to the modification hemicellulose, be specifically related to a kind of method of preparing acetylated hemicellulose by employing catalysis of iodine.
Background technology
A frontier-biomass chemistry that Green Chemistry is opened up, study the chemical conversion of green plants exactly, promptly find out the effective and inexpensive method that Mierocrystalline cellulose, hemicellulose and xylogen branch are come, again they are decomposed into glucose monomer, alcohol and other Organic Chemicals, thereby the huge green wild plant of reserves on the earth is converted into human food and cattle food, the energy and Organic Chemicals.In three kinds of main components of plant resources, what the human use was maximum is Mierocrystalline cellulose, and utilizing minimum is hemicellulose, and the most difficult utilization is xylogen.Hemicellulose is the biosynthetic polysaccharide polymers of trees, and according to estimates, the annual hemicellulose that generates of the plant in the whole world has 3.5 * 10
10Ton.Therefore the rich and recyclability of hemicellulose has caused people's extensive interest.Scientist compares early the research of timber hemicellulose, but mainly based on selective extraction technology and structure determination.As far back as nineteen fifty-nine, the Aspinall of Univ Edinburgh UK just measures various timber hemicellulose levels and structure, but in afterwards 30 years, half-and-half cellulosic research is very few.Before 10 years, along with the rapid minimizing of world's area of woods and the raising of timber price, started for the first time and researched and developed the climax of utilizing agricultural crop straw, particularly to the research of hemicellulose aspect, the research of aspects such as the separation of hemicellulose, modification and application becomes more and more important in cell walls.
Ionic liquid is a kind of green solvent that has application prospect of rising in recent years, with its distinctive good dissolubility, strong polarity, non-volatile, not oxidation, premium propertiess such as water and air is stable are subjected to extensive concern, be applied at numerous areas such as chemosynthesis, electrochemistry, extracting and separating, material preparations rapidly, and be considered to replace volatile chemical solvents in a lot of fields.Over the past two years, ionic liquid began to be applied in the cellulose materials processing, and its application at the aspects such as modification of cellulose materialss such as cellulosic dissolving, homogeneous phase derivatize and paper, fiber, timber appears in the newspapers repeatly.Yet, the acetylization reaction of hemicellulose in ionic liquid be yet there are no report so far.
With the hemicellulose chemical modification is the research of industrial novel material, and the utilization of timber hemicellulose chemical modification is subjected to scientist's favor always.The annual wheat straw waste output of China reaches 5.7 hundred million, most of directly burning heat production, and small part is as the raw material of feed, fertilizer and pulp and paper industry.Hemicellulose content in wheat straw waste reaches 30%～35%, how to utilize the problem of hemicelluloses a large amount of in the wheat straw waste more and more to be subject to people's attention.The hydrophobicity that esterification by the hemicellulose hydroxyl increases hemicellulose is a kind of feasible method.The oh group derivatization of hemicellulose can reduce the snappiness that hemicellulose forms the network of hydrogen bonded and increases film.Hydrophobic increase can improve the application potential of esterification hemicellulose in plastics-production, especially for the biodegradable plastic in the production foodstuffs industry and environment-degradable plastic, resin, film etc.French scientist Thiebaud utilizes pyridine to make solvent the hemicellulose in the wood chip have been carried out acetylization reaction, obtain the low esterification hemicellulose of substitution value, yet there has been toxicity problem in pyridine, needs washing extracting pyridinium salt, thereby has increased reaction cost.Up to the present, most of chemical modification hemicellulose carries out in the out-phase medium, and the productive rate of modified-reaction is low, and the cost height has limited industrial application.Publication number is that CN 1200952C Chinese invention patent has related to the pre-activation of hemicellulose and at N, the method for the homogeneous phase esterification of dinethylformamide/lithium chloride system obtains the higher esterification hemicellulose of substitution value.But these reaction mediums all have toxicity; yet there are no report about the homogeneous phase acetylization reaction of hemicellulose in ionic liquid; with the molecular iodine is new catalyst; can improve hemicellulose acetylization reaction efficient; improve the substitution value of product; and ionic liquid can recycle, can reduce production costs.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists at prior art, and a kind of raising hemicellulose acetylization reaction efficient is provided, and ionic liquid can recycle, the method for the preparing acetylated hemicellulose by employing catalysis of iodine that reduces production costs.
Purpose of the present invention is achieved through the following technical solutions:
A kind of method of preparing acetylated hemicellulose by employing catalysis of iodine comprises the steps and processing condition:
(1) with the wheat straw waste of KOH solution-treated delignification, the caustic solubility hemicellulose to dissolved in filtrate carries out purifying and separates then;
(2) hemicellulose after will separating joins in 1-butyl-3-methyl imidazolitm chloride solution, and control hemicellulose concentration is handled 1.5～2.0h at 90～100 ℃ in 2.5wt%～4.0wt% scope, to dissolving fully;
(3) the catalyzer iodine of the relative hemicellulose weight 10%～15% of adding adds 16～28 moles of diacetyl oxides doubly of xylan hydroxyl in the hemicellulose composition again, at 90～110 ℃, and reaction 20～30min;
(4) after the cooling, saturated Sulfothiorine is added in the mixture, it is 0.08～0.15ml that every gramion liquid adds Sulfothiorine, shake up, add 80% ethanol of 3～4 times of mixeding liquid volumes again, magnetic agitation 30min, filter, precipitation is dried 12h naturally again through 80% and 95% washing with alcohol, and the back is at 45 ℃ of vacuum-drying 24h.
For further realizing the object of the invention, the wheat straw waste of delignification is to obtain by the following method in the described step (1): the toluene and the ethanol wheat straw waste 6h that extracting 50g grinds in Soxhlet extractor that with volume ratio are 2: 1 earlier, use 1000ml water at 75 ℃ of extracting 2h then, residual substance is handled 2h with the 75g Textone in 75 ℃ 1000ml water, use the acetate adjust pH between 3.6～3.8.
Described step (1) is meant that with the wheat straw waste of KOH solution-treated delignification the wheat straw waste of delignification and the solid-to-liquid ratio of KOH solution are 1: 20～1: 25gml
-1Condition under, be that 8～10wt%KOH is at 20～30 ℃ of extracting wheat straw waste holocellulose 8～12h with concentration.
Described catalyzer iodine is chemical pure iodine.
The principle of the invention:
The present invention compared with prior art has following advantage and beneficial effect:
1. the chemical modification hemicellulose is all carrying out in the phase medium, and speed of response has been than having improved 5～10 times in traditional out-phase medium, thereby has improved output, has reduced production cost.
2. the use of iodine catalyst can improve hemicellulose acetylization reaction efficient, compares with not adding catalyzer, and the product substitution value can improve 16%.
3. ionic liquid can recycle, greatly reduces production cost.
4. the hemicellulose hydrophobicity after the chemical modification improves greatly, can be used for preparing the degradable food packaging film.
Embodiment
In order to understand technical characterstic of the present invention better,, need to prove that embodiment is not a limiting the scope of the invention below in conjunction with the present invention being further described by embodiment.
Embodiment 1
Wheat straw waste elder generation toluene-ethanol that the first step 50g grinds (2: 1, v/v) extracting 6h in Soxhlet extractor.Add 1000ml water then and remove water miscible hemicellulose at 75 ℃ of extracting 2h.Residual substance is handled 2h (using the acetate adjust pH between 3.6～3.8) with the 75g Textone in 75 ℃ 1000ml water.At the wheat straw waste of delignification and the solid-to-liquid ratio of KOH solution is 1: 20gml
-1Condition under be that 10wt%KOH is at 23 ℃ of extracting 10h with concentration.The filtrate that obtains is used 6mol/l acetate adjust pH to 5.5, uses 95% ethanol sedimentation of 3 times of volumes then, filters, and uses acidifying 70% washing with alcohol at last, and dry air 12h dries by the fire 16h down at 60 ℃.
Hemicellulose (being equivalent to xylan hydroxyl mole in the 0.1 hemicellulose composition) after second step was purified 6.6g places three mouthfuls of reaction flasks of 500ml, add 260g 1-butyl-3-methyl chlorination imidazole ion liquid, at 90 ℃ of following reaction 1.5h, dissolve fully to hemicellulose.
The 3rd step fed nitrogen to the hemicellulose ionic liquid, added the 0.99g molecular iodine, approximately needed 2～5s molecular iodine all to dissolve, at 100 ℃ of diacetyl oxides that add 20 times of xylan hydroxyl moles in hemicellulose is formed down, reaction 30min.After reaction stops, cooling.
Add saturated Sulfothiorine 25ml in the cooled mixing solutions of the 4th step, shake up, mixing solutions becomes oyster white from black immediately.Pour mixing solutions 80% ethanol of 4 times of volumes into, magnetic agitation 30min filters, and precipitation is again through 80% and 95% washing with alcohol, and oven dry 12h naturally afterwards at 45 ℃ of vacuum-drying 24h, promptly obtains substitution value and be 1.53 acetylated hemicellulose.
Through weight scaling method and infrared measurement, the substitution value of prepared acetylated hemicellulose is 1.53.
Embodiment 2
Wheat straw waste elder generation toluene-ethanol that the first step 50g grinds (2: 1, v/v) extracting 6h in Soxhlet extractor.Add 1000ml water then and remove water miscible hemicellulose at 75 ℃ of extracting 2h.Residual substance is handled 2h (using the acetate adjust pH between 3.6～3.8) with the 75g Textone in 75 ℃ 1000ml water.At the wheat straw waste of delignification and the solid-to-liquid ratio of KOH solution is 1: 20gml
-1Condition under be that 10wt%KOH is at 23 ℃ of extracting 10h with concentration.The filtrate that obtains is used 6mol/l acetate adjust pH to 5.5, uses 95% ethanol sedimentation of 3 times of volumes then, filters, and uses acidifying 70% washing with alcohol at last, and dry air 12h dries by the fire 16h down at 60 ℃.
Hemicellulose after second step was purified 6.6g (be equivalent to 0.1 hemicellulose form in xylan hydroxyl mole) places three mouthfuls of reaction flasks of 500ml, adds the 260g ionic liquid, at 90 ℃ of reaction 1.5h down, dissolves fully to hemicellulose.
The 3rd step fed nitrogen to the hemicellulose ionic liquid, added the 0.99g molecular iodine, approximately needed 2～5s molecular iodine all to dissolve, at 100 ℃ of diacetyl oxides that add 28 times of xylan hydroxyl moles in hemicellulose is formed down, reaction 30min.After reaction stops, cooling.
Add saturated Sulfothiorine 25ml in the cooled mixing solutions of the 4th step, shake up, mixing solutions becomes oyster white from black immediately.Pour mixing solutions 80% ethanol of 4 times of volumes into, magnetic agitation 30min filters, and precipitation is again through 80% and 95% washing with alcohol, and oven dry 12h naturally afterwards at 45 ℃ of vacuum-drying 24h, promptly obtains substitution value and be 1.51 chemical modification hemicellulose.
Embodiment 3
Wheat straw waste elder generation toluene-ethanol that the first step 50g grinds (2: 1, v/v) extracting 6h in Soxhlet extractor.Add 1000ml water then and remove water miscible hemicellulose at 75 ℃ of extracting 2h.Residual substance is handled 2h (using the acetate adjust pH between 3.6～3.8) with the 75g Textone in 75 ℃ 1000ml water.At the wheat straw waste of delignification and the solid-to-liquid ratio of KOH solution is 1: 25gml
-1Condition under be that 10wt%KOH is at 23 ℃ of extracting 10h with concentration.The filtrate that obtains is used 6mol/l acetate adjust pH to 5.5, uses 95% ethanol sedimentation of 3 times of volumes then, filters, and uses acidifying 70% washing with alcohol at last, and dry air 12h dries by the fire 16h down at 60 ℃.
Hemicellulose after second step was purified 8.8g (be equivalent to 0.133 hemicellulose form in xylan hydroxyl mole) places three mouthfuls of reaction flasks of 500ml, adds the 260g ionic liquid, at 90 ℃ of reaction 2.0h down, dissolves fully to hemicellulose.
The 3rd step fed nitrogen to the hemicellulose ionic liquid, added the 0.88g molecular iodine, approximately needed 2～5s molecular iodine all to dissolve, at 100 ℃ of diacetyl oxides that add 20 times of xylan hydroxyl moles in hemicellulose is formed down, reaction 30min.After reaction stops, cooling.
Add saturated Sulfothiorine 22ml in the cooled mixing solutions of the 4th step, shake up, mixing solutions becomes oyster white from black immediately.Pour mixing solutions 80% ethanol of 4 times of volumes into, magnetic agitation 30min filters, and precipitation is again through 80% and 95% washing with alcohol, and oven dry 12h naturally afterwards at 45 ℃ of vacuum-drying 24h, promptly obtains substitution value and be 1.48 chemical modification hemicellulose.
As mentioned above, can realize the present invention preferably.
Claims (4)
1. the method for a preparing acetylated hemicellulose by employing catalysis of iodine is characterized in that, this method comprises the steps and processing condition:
(1) with the wheat straw waste of KOH solution-treated delignification, the caustic solubility hemicellulose to dissolved in filtrate carries out purifying and separates then;
(2) hemicellulose after will separating joins in 1-butyl-3-methyl imidazolitm chloride solution, and control hemicellulose concentration is handled 1.5～2.0h at 90～100 ℃ in 2.5wt%～4.0wt% scope, to dissolving fully;
(3) the catalyzer iodine of the relative hemicellulose weight 10%～15% of adding adds 16～28 moles of diacetyl oxides doubly of xylan hydroxyl in the hemicellulose composition again, at 90～110 ℃, and reaction 20～30min;
(4) after the cooling, saturated Sulfothiorine is added in the mixture, it is 0.08～0.15ml that every gramion liquid adds Sulfothiorine, shake up, add 80% ethanol of 3～4 times of mixeding liquid volumes again, magnetic agitation 30min, filter, precipitation is dried 12h naturally again through 80% and 95% washing with alcohol, and the back is at 45 ℃ of vacuum-drying 24h.
2. the method for a kind of preparing acetylated hemicellulose by employing catalysis of iodine according to claim 1; it is characterized in that; the wheat straw waste of delignification is to obtain by the following method in the described step (1): the toluene and the ethanol wheat straw waste 6h that extracting 50g grinds in Soxhlet extractor that with volume ratio are 2: 1 earlier; use 1000ml water at 75 ℃ of extracting 2h then; residual substance is handled 2h with the 75g Textone in 75 ℃ 1000ml water, use the acetate adjust pH between 3.6～3.8.
3. according to the method for claim 1 or 2 described a kind of preparing acetylated hemicellulose by employing catalysis of iodine; it is characterized in that described step (1) is meant that with the wheat straw waste of KOH solution-treated delignification the wheat straw waste of delignification and the solid-to-liquid ratio of KOH solution are 1: 20～1: 25gml
-1Condition under, be that 8～10wt%KOH is at 20～30 ℃ of extracting wheat straw waste holocellulose 8～12h with concentration.
4. according to the method for claim 1 or 2 described a kind of preparing acetylated hemicellulose by employing catalysis of iodine, it is characterized in that described catalyzer iodine is chemical pure iodine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100322560A CN100558749C (en) | 2007-12-07 | 2007-12-07 | A kind of method of preparing acetylated hemicellulose by employing catalysis of iodine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100322560A CN100558749C (en) | 2007-12-07 | 2007-12-07 | A kind of method of preparing acetylated hemicellulose by employing catalysis of iodine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101182361A true CN101182361A (en) | 2008-05-21 |
| CN100558749C CN100558749C (en) | 2009-11-11 |
Family
ID=39447800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100322560A Expired - Fee Related CN100558749C (en) | 2007-12-07 | 2007-12-07 | A kind of method of preparing acetylated hemicellulose by employing catalysis of iodine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100558749C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649570B (en) * | 2009-09-01 | 2011-02-09 | 陕西科技大学 | Process for preparing wheatgrass cellulose with low pollution |
| CN101974109A (en) * | 2010-10-26 | 2011-02-16 | 华南理工大学 | Method for preparing maleylation hemicellulose |
| CN102172517A (en) * | 2011-02-24 | 2011-09-07 | 贾正平 | Chiral column chromatographic packing and synthesis method thereof |
| CN101628948B (en) * | 2009-07-31 | 2011-11-09 | 上海师范大学 | Straw stalk hemicellulose B preparation method |
| CN103588883A (en) * | 2013-11-22 | 2014-02-19 | 南开大学 | Manufacturing method for modified cellulose membrane material based on ionic liquid |
| CN111036185A (en) * | 2020-01-16 | 2020-04-21 | 福州大学 | Amphiphilic cellulose-based adsorbent and preparation method thereof |
| CN112745536A (en) * | 2021-01-15 | 2021-05-04 | 王忠良 | Glasses repairing gel and preparation method thereof |
| CN114561169A (en) * | 2022-02-28 | 2022-05-31 | 上海昶法新材料有限公司 | Preparation method of hemicellulose coating adhesive |
| CN115991798A (en) * | 2023-02-16 | 2023-04-21 | 南京工业大学 | Bio-based hemicellulose film material and preparation method thereof |
| CN116211723A (en) * | 2023-04-07 | 2023-06-06 | 江西广恩和药业股份有限公司 | Nourishing and moisturizing lotion and preparation method thereof |
-
2007
- 2007-12-07 CN CNB2007100322560A patent/CN100558749C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628948B (en) * | 2009-07-31 | 2011-11-09 | 上海师范大学 | Straw stalk hemicellulose B preparation method |
| CN101649570B (en) * | 2009-09-01 | 2011-02-09 | 陕西科技大学 | Process for preparing wheatgrass cellulose with low pollution |
| CN101974109A (en) * | 2010-10-26 | 2011-02-16 | 华南理工大学 | Method for preparing maleylation hemicellulose |
| CN101974109B (en) * | 2010-10-26 | 2013-02-13 | 华南理工大学 | Method for preparing maleylation hemicellulose |
| CN102172517A (en) * | 2011-02-24 | 2011-09-07 | 贾正平 | Chiral column chromatographic packing and synthesis method thereof |
| CN103588883A (en) * | 2013-11-22 | 2014-02-19 | 南开大学 | Manufacturing method for modified cellulose membrane material based on ionic liquid |
| CN111036185A (en) * | 2020-01-16 | 2020-04-21 | 福州大学 | Amphiphilic cellulose-based adsorbent and preparation method thereof |
| CN111036185B (en) * | 2020-01-16 | 2021-07-13 | 福州大学 | Amphiphilic cellulose-based adsorbent and preparation method thereof |
| CN112745536A (en) * | 2021-01-15 | 2021-05-04 | 王忠良 | Glasses repairing gel and preparation method thereof |
| CN114561169A (en) * | 2022-02-28 | 2022-05-31 | 上海昶法新材料有限公司 | Preparation method of hemicellulose coating adhesive |
| CN115991798A (en) * | 2023-02-16 | 2023-04-21 | 南京工业大学 | Bio-based hemicellulose film material and preparation method thereof |
| CN115991798B (en) * | 2023-02-16 | 2024-02-06 | 南京工业大学 | Bio-based hemicellulose film material and preparation method thereof |
| CN116211723A (en) * | 2023-04-07 | 2023-06-06 | 江西广恩和药业股份有限公司 | Nourishing and moisturizing lotion and preparation method thereof |
| CN116211723B (en) * | 2023-04-07 | 2024-05-03 | 江西广恩和药业股份有限公司 | Nourishing and moisturizing lotion and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100558749C (en) | 2009-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100558749C (en) | A kind of method of preparing acetylated hemicellulose by employing catalysis of iodine | |
| Periyasamy et al. | Chemical, physical and biological methods to convert lignocellulosic waste into value-added products. A review | |
| van Osch et al. | Ionic liquids and deep eutectic solvents for lignocellulosic biomass fractionation | |
| Yin et al. | The pretreatment of lignocelluloses with green solvent as biorefinery preprocess: a minor review | |
| Tsao et al. | Fermentation substrates from cellulosic materials: production of fermentable sugars from cellulosic materials | |
| Meninno | Valorization of waste: Sustainable organocatalysts from renewable resources | |
| CN102101915B (en) | Separation method for agriculture and forestry biomass components | |
| CN112144309A (en) | Method for cleaning and separating main components of wood fiber | |
| CN102321251A (en) | Method for separating xylogen from agricultural waste by using compound ion liquid | |
| JP2009531424A (en) | Lignocellulose fractionation and reagent recycle based on cellulose solvent under mild reaction conditions | |
| CN103711017A (en) | Normal pressure ultrasonic-assisted method for preparing cellulose and lignin by using high boiling alcohol as solvent | |
| Kumar et al. | Optimization of reaction conditions for grafting of α-cellulose isolated from Lantana camara with acrylamide | |
| CN108884187A (en) | Ionomer and its purposes in processing biological | |
| CN101974109B (en) | Method for preparing maleylation hemicellulose | |
| CN104761554A (en) | Preparation method and application of ionic compound solution | |
| CN105713050B (en) | A kind of method that degradation selectivity corncob hemicellulose improves xylose yield | |
| CN104164801A (en) | Method for separating and recycling cellulose, semicellulose and lignin in lignocellulosic biomass at one time | |
| CN104710390A (en) | Method for preparing 5-hydroxymethylfurfural with chitin/chitosan as raw material | |
| CN103435717B (en) | Chitosan oligosaccharide | |
| CN102675484B (en) | Synthetic method of 4-hydrazoic benzoyl chitosan | |
| CN106480128B (en) | Method for improving efficiency of cellulose in hydrolyzing rice straws by using lactic acid and guanidine hydrochloride | |
| CN105385722B (en) | A method of pretreatment wood fiber biomass improves its sugar yield | |
| CN106519260A (en) | Method for separating lignin from agricultural waste by using composite ionic liquid | |
| CN114085252A (en) | Comprehensive utilization method for separating wood fiber by organic acid catalysis two-phase system | |
| Singh et al. | Exploring rice straw’s potential from a sustainable biorefinery standpoint: Towards valorization and diverse product production |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091111 Termination date: 20171207 |