CN1200952C - Homogeneous chemical modification of hemicellulose of stalks - Google Patents
Homogeneous chemical modification of hemicellulose of stalks Download PDFInfo
- Publication number
- CN1200952C CN1200952C CN 02152187 CN02152187A CN1200952C CN 1200952 C CN1200952 C CN 1200952C CN 02152187 CN02152187 CN 02152187 CN 02152187 A CN02152187 A CN 02152187A CN 1200952 C CN1200952 C CN 1200952C
- Authority
- CN
- China
- Prior art keywords
- hemicellulose
- stalk
- reaction
- minutes
- present
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to a novel method of the homogeneous phase chemical modification hemicellulose of a stalk. Firstly, the hemicellulose is extracted from the stalk and is activated by distilled water. Secondly, acyl chloride which is 3 times of xylose hydroxy mole in formation of the hemicellulose is added into a homogeneous phase medium N, N-dimethylformamide or lithium chloride system to react, and a reaction mixture is poured into ethanol to be filtered, washed and dried. In the present invention, the hemicellulose is directly extracted from the stalk in an alkaline medium by hydrogen peroxide, and no sulfide is used for the whole process. Environment pollution is greatly reduced, and lignin content is low. The method of the present invention has the advantages of 5 to 10 times of reaction speed enhancement, output enhancement and production cost reduction. The chemically modified hemicellulose has great enhancement of hydrophobic property and can be used for preparing a degradable food packing film.
Description
(1) technical field
The present invention relates to the novel technique field, specifically be meant a kind of method of homogeneous chemistry modified straw hemicellulose.
(2) background technology
Scientist compares early the research of timber hemicellulose, but in recent decades, mainly based on selective extraction technology and structure determination research.As far back as nineteen fifty-nine, the Aspinall of Univ Edinburgh UK professor and research group thereof just measure hemicellulose level and structure in the various timber, but in afterwards 30 years, half-and-half cellulosic research is very few.Up to over past ten years, along with the rapid minimizing of world's area of woods and the raising of timber price, started for the first time the climax that research and development utilizes agricultural crop straw, particularly to the research of hemicellulose aspect.In China, stalk is always as the raw material of papermaking, people have carried out a large amount of research to Mierocrystalline cellulose and xylogen, and ignored the research of 30% left and right sides hemicellulose in the stalk, cause the reason of this carelessness, be because in traditional alkaline process, hemicellulose is degraded and is oxidized to formic acid, oxyacetic acid, lactic acid etc., can't utilize.In addition, traditional separation method is earlier stalk to be handled in acidic solution removing delignification with clorox, and then extracts with sodium hydroxide or potassium hydroxide aqueous solution, though extraction output height, this processing method causes the pollution to environment.Up to 1991, the method that Czechoslovakian scientist Kosikova and Ebringerova combine with steam treatment and alkaline extraction, extracting hemicellulose from timber and corn cob studies, and delivered many relevant papers, but the content height (8～15%) of xylogen in the hemicellulose that extracts.Since 1997, the scientific research personnel at professor Glasser of the U.S. and other biological investigation of materials center also explores with the method for steam high pressure explosion and extract hemicellulose from agricultural crop straw, but the hemicellulose molecular weight that extracts is too little, content of lignin height (10～30%).In recent years, our research group has explored the method that a kind of novel free of contamination alkaline hydrogen peroxide extracts stalk hemicellulose, has obtained suitable success.Found that, utilize dilute concentration hydrogen peroxide (2%H
2O
2) handle stalk, in specific alkaline medium (pH12～12.5), 85% xylogen is removed, 90% hemicellulose is dissolved, and it only is about 3% that the hemicellulose after the purification contains xylogen impurity.
With aspect industrial novel material research, scientist is more to timber hemicellulose chemical modification utilization research in the hemicellulose chemical modification, as the timber hemicellulose that utilizes modification is as the production paper additive, to increase paper strength and to improve bleaching effect.In industrial production, modified hemicellulose can be used as tensio-active agent, is applied in washing and the soap industry.In foodstuffs industry, hemicellulose can be used as food glue, thickening material and tackiness agent, as is applied in the volume and the water regain that can increase bread in the bread production, and improves the quality of bread.In medical science, can be used as edible fibre and have cholesterol and sugar degree in the blood of human body of reduction, and the effect that can improve insulin for treating diabetes.Research in recent years finds that also this natural hemicellulose can improve the immunologic function of human body, stops tumor growth and obvious antitumous effect.Simultaneously, this natural hemicellulose has certain anastalsis, can be used to produce hemostatic agent.But present most of chemical modification hemicellulose carries out in the out-phase medium, and hemicellulose is not carried out pre-activation treatment, thereby the productive rate of modified-reaction is low, and the cost height has limited industrial application.Up to now, still hemicellulose is not carried out the technology of pre-activation treatment and homogeneous chemistry modified straw hemicellulose.
(3) summary of the invention
Purpose of the present invention is exactly in order to solve the deficiencies in the prior art part, and a kind of new technology of hemicellulose being carried out pre-activation treatment and homogeneous chemistry modified straw hemicellulose is provided.
The method of a kind of homogeneous chemistry modified straw hemicellulose of the present invention is characterized in that, it comprises following processing condition and step:
The first step is utilized pollution-free alkaline hydrogen peroxide dilute solution (2%H
2O
2, pH12.0～12.5) and from stalk, extract hemicellulose, control reaction temperature is 40～60 ℃, and the reaction times is 5～18 hours, and the dissolved hemicellulose adopts two-step approach to separate and purification;
Hemicellulose after the purification oven dry of second step is at first through distilled water activation treatment (70～80 ℃, 5～10 minutes);
Hemicellulose after the 3rd step activation treatment is at equal phase medium N, react in dinethylformamide/lithium chloride system, the acyl chlorides (carbon company commander degree is 3～18) that adds 3 times of wood sugar hydroxyl moles in hemicellulose is formed, with the dimethylamino pyridine is that catalyzer and triethylamine are the disacidify agent, temperature of reaction is 50～80 ℃, and the reaction times is 15～60 minutes;
After the cooling of the 4th step, reaction mixture is poured in 95% ethanol of 4 times of volumes, filtered the precipitation of gained, after 95% washing with alcohol, air and constant temperature (50～60 ℃) oven dry gets final product precipitation again.
The present invention compared with prior art has following advantage and beneficial effect:
1. the present invention utilizes 2% hydrogen peroxide directly to extract hemicellulose in alkaline medium from stalk, and whole process has significantly reduced the pollution to environment without sulfide (decomposing hydrogen dioxide solution is water and oxygen) for this reason.
2. whole leaching process is to carry out under 40～60 ℃ and normal pressure, and hemicellulose only is dissolving, palliating degradation degree relatively low (between molecular weight 2～30,000), and contain xylogen quite low (3%) in the isolated hemicellulose.
3. 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.
4. the hemicellulose hydrophobicity after the chemical modification greatly improves, and can be used to prepare the degradable food packaging film.
(4) description of drawings
Fig. 1 is the schematic flow sheet of the inventive method the first step;
Fig. 2 is the inventive method reaction synoptic diagram in the 3rd step.
(5) embodiment
Below in conjunction with drawings and Examples, the present invention is done detailed description further.
Embodiment one
Stalk after the first step 50 grams are pulverized places the 3000ml glass reactor, adds the 2%H of 950ml
2O
2The aqueous solution, the pH value of adjusting solution with the 20%NaOH aqueous solution is 12.0, control reaction temperature is 40 ℃, under agitation reacted 18 hours, filter and wash residue with aquae destillata, merging filtrate is regulated acidity to pH=5.5 with the HCl solution of 6M then, concentrating under reduced pressure filtrate is to 500ml, 95% ethanol that adds 3 times of volumes makes solubility hemicellulose precipitation, after the filtration, hemicellulose and gas with 70% ethanol thorough washing gained are done, and promptly obtain the hemicellulose product of 10.8 grams;
Hemicelluloses after second step was purified 6.0 grams (be equivalent to 0.08 hemicellulose form in wood sugar hydroxyl mole) place the 1000ml glass reactor, add 100ml distilled water, 80 ℃ of stir abouts 5 minutes, dissolve fully until hemicellulose;
In the 3rd hemicellulose aqueous solution of step after dissolving, the N that adds 150ml, dinethylformamide, stirred 5 minutes at 80 ℃ again, utilize rotatory evaporator then, distilled water is removed in evaporation under 50 ℃ and reduced pressure, in the reaction system after removing distilled water, adds the N of 100ml again, dinethylformamide, add 22.2 gram propionyl chlorides (being equivalent to 0.24 mole) then successively, 1.5 grams lithium chloride, 0.5 gram dimethylamino pyridine (catalyzer), and stir and controlled temperature under 75 ℃, slowly add 21.6 and restrain triethylamine (disacidify agent, about 5 minutes), continue to stir after 5 minutes, stop heating, existing side by side soon, reactor places tap water to cool off;
The 4th step, cooled reaction mixture was under agitation poured in 95% ethanol of 1000ml, room temperature was placed after 6 hours, filtering-depositing, precipitation is with 95% alcohol flushing 3 times, dry air is after 24 hours then, and in thermostatic drying chamber, controlled temperature is under 50 ℃ again, dried 12 hours, and promptly obtained gamma value and be the hemicellulose after 1.5 chemical modifications.
As mentioned above, can realize the present invention preferably.
Embodiment two
Stalk after the first step 50 grams are pulverized places the 3000ml glass reactor, adds the 2%H of 950ml
2O
2The aqueous solution, the pH value of adjusting solution with the 20%NaOH aqueous solution is 12.3, control reaction temperature is 50 ℃, under agitation reacted 12 hours, filter and wash residue with aquae destillata, merging filtrate is regulated acidity to pH=5.5 with the HCl solution of 6M then, concentrating under reduced pressure filtrate is to 600ml, 95% ethanol that adds 4 times of volumes makes solubility hemicellulose precipitation, after the filtration, hemicellulose and gas with 70% ethanol thorough washing gained are done, and promptly obtain the hemicellulose product of 14.1 grams;
Hemicelluloses after second step was purified 6.0 grams (be equivalent to 0.08 hemicellulose form in wood sugar hydroxyl mole) place the 1000ml glass reactor, add 100ml distilled water, 80 ℃ of stir abouts 5 minutes, dissolve fully until hemicellulose;
In the 3rd hemicellulose aqueous solution of step after dissolving, the N that adds 150ml, dinethylformamide, stirred 5 minutes at 80 ℃ again, utilize rotatory evaporator then, distilled water is removed in evaporation under 50 ℃ and reduced pressure, in the reaction system after removing distilled water, adds the N of 100ml again, dinethylformamide, add 72.6 gram stearic acid chlorides (being equivalent to 0.24 mole) then successively, 1.5 grams lithium chloride, 0.5 gram dimethylamino pyridine (catalyzer), and stir and controlled temperature under 80 ℃, slowly add 9.6 and restrain triethylamine (disacidify agent, about 10 minutes), continue to stir after 20 minutes, stop heating, existing side by side soon, reactor places tap water to cool off;
The 4th step, cooled reaction mixture was under agitation poured in 95% ethanol of 1000ml, room temperature was placed after 6 hours, filtering-depositing, precipitation is with 95% alcohol flushing 3 times, dry air is after 24 hours then, and in thermostatic drying chamber, controlled temperature is under 55 ℃ again, dried 12 hours, and promptly obtained gamma value and be the hemicellulose after 1.8 chemical modifications.
As mentioned above, can realize the present invention preferably.
Embodiment three
Stalk after the first step 50 grams are pulverized places the 3000ml glass reactor, adds the 2%H of 950ml
2O
2The aqueous solution, the pH value of adjusting solution with the 20%NaOH aqueous solution is 12.5, control reaction temperature is 60 ℃, under agitation reacted 5 hours, filter and wash residue with aquae destillata, merging filtrate is regulated acidity to pH=6.0 with the HCl solution of 6M then, concentrating under reduced pressure filtrate is to 800ml, 95% ethanol that adds 4 times of volumes makes solubility hemicellulose precipitation, after the filtration, hemicellulose and gas with 70% ethanol thorough washing gained are done, and promptly obtain the hemicellulose product of 16.6 grams;
Second step placed the 1000ml glass reactor with the 6.0 grams back hemicelluloses (be equivalent to 0.08 hemicellulose form in wood sugar hydroxyl mole) of purifying, and added 100ml distilled water, 70 ℃ of stir abouts 10 minutes, dissolved fully until hemicellulose;
In the 3rd hemicellulose aqueous solution of step after dissolving, the N that adds 150ml, dinethylformamide, stirred 5 minutes at 80 ℃ again, utilize rotatory evaporator then, distilled water is removed in evaporation under 50 ℃ and reduced pressure, in the reaction system after removing distilled water, adds the N of 100ml again, dinethylformamide, add 17.0 acyl chlorides (being equivalent to 0.12 mole) of restraining oneself then successively, 1.5 grams lithium chloride, 0.5 gram dimethylamino pyridine (catalyzer), and stir and controlled temperature under 50 ℃, slowly add 20.0 and restrain triethylamine (disacidify agent, about 20 minutes), continue to stir after 35 minutes, stop heating, existing side by side soon, reactor places tap water to cool off;
The 4th step, cooled reaction mixture was under agitation poured in 95% ethanol of 1000ml, room temperature was placed after 6 hours, filtering-depositing, precipitation is with 95% alcohol flushing 3 times, dry air is after 24 hours then, and in thermostatic drying chamber, controlled temperature is under 60 ℃ again, dried 12 hours, and promptly obtained gamma value and be the hemicellulose after 1.1 chemical modifications.
As mentioned above, can realize the present invention preferably.
Claims (1)
1. the method for a homogeneous chemistry modified straw hemicellulose is characterized in that, it comprises following processing condition and step:
The first step utilizes pollution-free alkaline hydrogen peroxide dilute solution to extract hemicellulose from stalk, and control reaction temperature is 40～60 ℃, and the reaction times is 5～18 hours, and the dissolved hemicellulose adopts two-step approach to separate and purification;
Hemicellulose after the purification oven dry of second step is at first through the distilled water activation treatment, and treatment temp is 70～80 ℃, and the treatment time is 5～10 minutes;
Hemicellulose after the 3rd step activation treatment is at equal phase medium N, carry out in dinethylformamide/lithium chloride system, the acyl chlorides that adds 3 times of wood sugar hydroxyl moles in hemicellulose is formed, with the dimethylamino pyridine is that catalyzer and triethylamine are the disacidify agent, temperature of reaction is 50～80 ℃, and the reaction times is 15～60 minutes;
After the cooling of the 4th step, reaction mixture is poured in 95% ethanol of 4 times of volumes, filtered the precipitation of gained, after 95% washing with alcohol, air and 50～60 ℃ of constant temperature dryings get final product precipitation again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02152187 CN1200952C (en) | 2002-12-10 | 2002-12-10 | Homogeneous chemical modification of hemicellulose of stalks |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02152187 CN1200952C (en) | 2002-12-10 | 2002-12-10 | Homogeneous chemical modification of hemicellulose of stalks |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424332A CN1424332A (en) | 2003-06-18 |
| CN1200952C true CN1200952C (en) | 2005-05-11 |
Family
ID=4752140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02152187 Expired - Fee Related CN1200952C (en) | 2002-12-10 | 2002-12-10 | Homogeneous chemical modification of hemicellulose of stalks |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1200952C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500989C (en) * | 2005-08-09 | 2009-06-17 | 华南理工大学 | Full component separation for cell wall of agricultural refuse |
| CN100402556C (en) * | 2006-03-03 | 2008-07-16 | 才景志 | Sodium carboxymethyl hemicellulose with paper-making black liquor as raw material and producing method thereof |
| CN100593599C (en) * | 2007-01-31 | 2010-03-10 | 中国科学院化学研究所 | Method for extracting cellulose from straw |
| FI124724B (en) * | 2009-02-13 | 2014-12-31 | Upm Kymmene Oyj | A process for preparing modified cellulose |
| TW201114906A (en) * | 2009-04-30 | 2011-05-01 | Annikki Gmbh | Process for the production of carbohydrate cleavage products from a lignocellulosic material |
| CN101649570B (en) * | 2009-09-01 | 2011-02-09 | 陕西科技大学 | Process for preparing wheatgrass cellulose with low pollution |
| CN101838348B (en) * | 2010-05-18 | 2012-06-20 | 华南理工大学 | Hemicellulose derivative with two functional groups as well as preparation method and application thereof |
| CN102206917B (en) * | 2011-03-29 | 2012-06-27 | 中国林业科学研究院林产化学工业研究所 | Method for manufacturing methyl malei-eleostearate anhydride modified wood fiber |
| CN102659956B (en) * | 2012-04-26 | 2013-10-30 | 江南大学 | Modified ultraviolet absorbing agent based on araboxylan and preparation method thereof |
| CN102850470B (en) * | 2012-10-08 | 2014-06-11 | 江南大学 | Method for separating and purifying water-soluble hemicellulose from green tea leaves |
| CN103145881B (en) * | 2013-03-29 | 2015-04-22 | 南开大学 | Method for preparing hemicellulose from maize straws by adopting solid base catalyst |
| FI126042B (en) | 2014-03-31 | 2016-06-15 | Upm Kymmene Corp | Process for the manufacture of nanofibrillar cellulose and nanofibrillar cellulose product |
| CN110981976B (en) * | 2019-12-12 | 2020-12-11 | 北京化工大学 | Cellulose-based hydrophobic nano material and preparation method and application thereof |
| CN111773133B (en) * | 2020-06-15 | 2023-05-26 | 天津科技大学 | Cosmetic preservative |
| CN115369689B (en) * | 2022-08-17 | 2023-06-20 | 山鹰国际控股股份公司 | Pre-dyeing process for papermaking |
-
2002
- 2002-12-10 CN CN 02152187 patent/CN1200952C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1424332A (en) | 2003-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1200952C (en) | Homogeneous chemical modification of hemicellulose of stalks | |
| KR100321678B1 (en) | Biomass Pretreatment Method | |
| US4395543A (en) | Selective solvent extraction of cellulosic material | |
| AU2004202019B2 (en) | Polysaccharide compositions and uses thereof | |
| AU2009278045B2 (en) | Process for the co-production of chitin, its derivatives and polymers containing glucose, mannose and/or galactose, by the fermentation of the yeast Pichia pastoris | |
| US20150173408A1 (en) | Method of Producing Nanofibrillar Cellulose with High Absorptivity to Fat and Cholate | |
| BRPI1014723B1 (en) | process for cellulose hydrolysis | |
| CN105568744A (en) | Cornstalk nanocellulose whiskers and preparation method and application thereof | |
| CN112695009A (en) | Method for preparing bacterial cellulose by in-situ fermentation | |
| US5905035A (en) | Fungus useful for chitin production | |
| CN101168570B (en) | Method for degrading kelp polysaccharide sulfate | |
| CN110283255B (en) | Preparation method and application of modified morchella polysaccharide | |
| JP2021531789A (en) | A method for preparing a purified solution of poplaroxylo-oligosaccharide, and a purified solution of poplar-oxylo-oligosaccharide prepared thereby, a solid of xylooligosaccharide and its use thereof. | |
| JP2001226409A (en) | Xylooligosaccharide composition | |
| CN111088310A (en) | Soybean peptide with α -glucosidase activity inhibition function, and preparation method and application thereof | |
| JP2587268B2 (en) | Method for producing low-viscosity hyaluronic acid or salt thereof | |
| CN109136307B (en) | Method for preparing chitosan oligosaccharide by using helicase and application thereof | |
| JP2003048901A (en) | Long-chain xylooligosaccharide composition and method for producing the same | |
| CA2615904C (en) | Methods of biomass pretreatment | |
| CN105795355B (en) | Method for increasing content of soluble dietary fiber in black soybean hulls | |
| CN110218263B (en) | Hericium erinaceus fungus chaff polysaccharide, preparation method and application | |
| KR101584208B1 (en) | Manufacturing method of xylose-rich xylan utilizing corn bran | |
| CN1763211A (en) | Method for conversing agricultural waste into xylo-oligosaccharides by high specific activity xylan hydrolyzing ferment | |
| CN1258993C (en) | Method for preparing food fibre using fermentation liquor of biomass preparing ethanol system | |
| CN117247474A (en) | Sweet potato polysaccharide and extraction method thereof |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |