CN102060998B - Method for splitting and deeply processing cellulose straw substance components - Google Patents
Method for splitting and deeply processing cellulose straw substance components Download PDFInfo
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- CN102060998B CN102060998B CN201110028077A CN201110028077A CN102060998B CN 102060998 B CN102060998 B CN 102060998B CN 201110028077 A CN201110028077 A CN 201110028077A CN 201110028077 A CN201110028077 A CN 201110028077A CN 102060998 B CN102060998 B CN 102060998B
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Abstract
The invention belongs to the technical field of splitting and deeply processing cellulose straw substance components and particularly relates to a method for splitting and deeply processing the cellulose straw substance components. The method is realized by the following steps of: adding liquid alcohol substances into the straw substances of which hemicellulose or partial hemicellulose is desorbed according to the solid-liquid quality ratio of 1: (2-8); extracting at the temperature of 60-180DEG C for 1-4 hours; carrying out solid-liquid separation, wherein the liquid phase substance is an alcohol solution containing lignin; and adding polyethylene glycol or epoxy compound into the liquid phase substance and refining to obtain biological polyol. According to the invention, by fusing the separated cellulose with biological polyol and polyether polyol produced by using the lignin, the cellulose can be separated and the polyol can be produced by using the lignin. The polyol as the polyether production raw material with extremely high value can be obtained by adopting a simple energy-saving manner and creates huge wealth for enterprises and society.
Description
Technical field
The invention belongs to straw-like materials intensive processing technical field, be specifically related to the method for a kind of Mierocrystalline cellulose straw-like materials component fractionation and intensive processing.
Background technology
At present, along with the petrochemical industry resource reduces day by day, people begin to seek reproducible Biological resources and replace petrochemical materials, utilize reproducible agricultural stalk to develop multiple Chemicals.Want to make full use of the stalk cellulose material, need its component be split and separate, semicellulose resolves into five-carbon sugar, comes out lignin extraction, and Mierocrystalline cellulose resolves into hexose.Mierocrystalline cellulose resolves into the existing very proven technique of five-carbon sugar, but the extraction of xylogen and cellulosic hydrolysis are still waiting exploitation.Mierocrystalline cellulose decomposes relatively gentleness at present, and relatively the method for environmental protection surely belongs to cellulase hydrolysis, although we can utilize diluted acid or the quick-fried method of vapour to separate so that semicellulose is changed into five-carbon sugar; But remaining Mierocrystalline cellulose and xylogen be weave in still, has hindered the accessibility of cellulase, and enzyme utilizes low; Disaggregated cost is higher relatively, in order to reduce the consumption of cellulase, Mierocrystalline cellulose is fully decomposed; Best bet be exactly earlier and the Mierocrystalline cellulose lignin separation of being bundled together that interweaves fall; Alcoholic solvent can reach the purpose of separating of Mierocrystalline cellulose and xylogen from the Mierocrystalline cellulose straw-like materials, to extract xylogen, and to separate with extraction agent behind the xylogen be through adding several times cold water the xylogen precipitate and separate to be come out at present but extract; This method consumed energy is bigger, and is isolating thorough inadequately.
Summary of the invention
The present invention provides the method for a kind of Mierocrystalline cellulose straw-like materials component fractionation and intensive processing, and this method can make cellulose substances maximize the use.
The present invention adopts following technical scheme:
The method of a kind of Mierocrystalline cellulose straw-like materials component fractionation and intensive processing; Remove in the straw-like materials of semicellulose and add liquid alcohols material to removing semicellulose or part by solid-liquid mass ratio 1:2-8; Extracted 1-4 hour down at 60-180 ℃; Solid-liquid separation, liquid phase substance are the alcoholic solution that contains xylogen; It is refining that biological multielement is pure in liquid phase substance, to add polyoxyethylene glycol or epoxy compounds reaction back.
Before in liquid phase substance, adding polyoxyethylene glycol; The liquid alcohols material of 20-95% is removed in liquid phase substance evaporation earlier, adds the liquid alcohols material mass 1-100 in evaporation back polyoxyethylene glycol doubly then, and the 0.1-3% that presses the polyoxyethylene glycol quality again adds mineral acid; Controlled temperature 100-170 ℃; Reacted 0.2-4 hour, and added alkaline matter adjust pH 6-8 at last, refining that biological multielement is pure.
Before in liquid phase substance, adding epoxy compounds; The liquid alcohols material of 20-95% is removed in liquid phase substance evaporation earlier; Add the total liquid mass 0.1-10 in evaporation back epoxy compounds doubly then; The basic catalyst that adds epoxy compound amount 0.1-5% again, in atmosphere of inert gases, 80-150 ℃ reaction 1-3 hour, refining polyether glycol.
Said liquid alcohols material is a polyvalent alcohol; Said mineral acid is sulfuric acid, hydrochloric acid or phosphoric acid; Said alkaline matter is Pottasium Hydroxide or sodium hydroxide.
Said polyvalent alcohol is a terepthaloyl moietie.
Said epoxy compounds is oxyethane, propylene oxide or butylene oxide ring; Said basic catalyst is Pottasium Hydroxide or sodium hydroxide; Said rare gas element is nitrogen or carbonic acid gas.
Saidly remove that straw-like materials that semicellulose or part remove semicellulose refers to after hydrolysis or vapour are quick-fried, to remove or part removes the straw-like materials of semicellulose.
The present invention discovers that xylogen can be dissolved in the liquid alcohol kind solvent at a certain temperature, and contains a plurality of hydroxyls in the xylogen in the molecular structure; Can generate polyvalent alcohol with polyoxyethylene glycol or epoxy compounds reaction under certain condition; Utilize this specific character of polyvalent alcohol and xylogen, the present invention is with the de-fibering element and utilize the pure and mild polyether glycol of xylogen production biological multielement to merge, and has both separated the cellulosic while and has also utilized xylogen to produce polyvalent alcohol; Reduced production link; Reduce the isolating cost of xylogen and Mierocrystalline cellulose, lignin separation has been gone out during cellulase hydrolysis simultaneously, therefore greatly reduced the cost of cellulose hydrolysis; Adopt simple energy-conservation mode to obtain to be worth very high production of polyester raw material-polyvalent alcohol, for enterprise and society create very big wealth.
Embodiment
Embodiment 1
Corn straw disintegrating slag 1000 grams that remove behind the semicellulose are separated in water intaking, put into reaction kettle, add 5000 gram terepthaloyl moietie; The 155 ℃ of boilings 3 hours of heating, with mixture solid-liquid separation after the boiling, hexose is produced in the hydrolysis of solid matter available enzyme; 4500 gram terepthaloyl moietie are removed in the liquid phase part evaporation, add the Polyethylene Glycol-600 gram then, add 18 gram sulfuric acid; Be heated to 150 ℃ of reactions 2.5 hours, adding sodium hydroxide adjust pH to 7, completion reaction back is refining that biological multielement is pure.
Embodiment 2
Get quick-fried corn straw disintegrating slag 1000 grams that remove behind the semicellulose of vapour, put into reaction kettle, add 2000 gram terepthaloyl moietie; The 60 ℃ of boilings 4 hours of heating, with mixture solid-liquid separation after the boiling, hexose is produced in the hydrolysis of solid matter available enzyme; 400 terepthaloyl moietie are removed in the liquid phase part evaporation, add polyoxyethylene glycol 8000 grams then, add 80 gram sulfuric acid; Be heated to 100 ℃ of reactions 4 hours, adding sodium hydroxide adjust pH to 6, completion reaction back is refining that biological multielement is pure.
Embodiment 3
Corn straw disintegrating slag 1000 grams that remove behind the semicellulose are separated in water intaking, put into reaction kettle, add 8000 gram terepthaloyl moietie; The 180 ℃ of boilings 1 hour of heating, with mixture solid-liquid separation after the boiling, hexose is produced in the hydrolysis of solid matter available enzyme; 4000 gram terepthaloyl moietie are removed in the liquid phase part evaporation, add cetomacrogol 1000 0 gram then, add 10 gram sulfuric acid; Be heated to 170 ℃ of reactions 0.2 hour, adding sodium hydroxide adjust pH to 8, completion reaction back is refining that biological multielement is pure.
Embodiment 4
Get quick-fried corn straw disintegrating slag 2000 grams that remove behind the semicellulose of vapour, put into reaction kettle, add 8000 gram terepthaloyl moietie; The 150 ℃ of boilings 3 hours of heating, with mixture solid-liquid separation after the boiling, hexose is produced in the hydrolysis of solid matter available enzyme; Terepthaloyl moietie 7000 grams are removed in the liquid phase part evaporation; The propylene oxide that adds 0.1 times of total liquid mass behind the evaporation terepthaloyl moietie then adds the sodium hydroxide of propylene oxide quality 0.1%, feeds nitrogen; 150 ℃ were reacted 1 hour, accomplished the refining lignin-base polyether glycol that obtains in reaction back.
Embodiment 5
Corn straw disintegrating slag 2000 grams that remove behind the semicellulose are separated in water intaking, put into reaction kettle, add 8000 gram terepthaloyl moietie; The 150 ℃ of boilings 3 hours of heating, with mixture solid-liquid separation after the boiling, hexose is produced in the hydrolysis of solid matter available enzyme; Terepthaloyl moietie 5000 grams are removed in the liquid phase part evaporation; The butylene oxide ring that adds 3 times of total liquid masies behind the evaporation terepthaloyl moietie then adds the sodium hydroxide of butylene oxide ring quality 3%, feeds carbonic acid gas; 80 ℃ were reacted 3 hours, accomplished the refining lignin-base polyether glycol that obtains in reaction back.
Embodiment 6
Get quick-fried corn straw disintegrating slag 2000 grams that remove behind the semicellulose of vapour, put into reaction kettle, add 8000 gram terepthaloyl moietie; The 150 ℃ of boilings 3 hours of heating, with mixture solid-liquid separation after the boiling, hexose is produced in the hydrolysis of solid matter available enzyme; Terepthaloyl moietie 2000 grams are removed in the liquid phase part evaporation; The oxyethane that adds 10 times of total liquid masies behind the evaporation terepthaloyl moietie then adds the sodium hydroxide of oxyethane quality 5%, feeds nitrogen; 110 ℃ were reacted 2 hours, accomplished the refining lignin-base polyether glycol that obtains in reaction back.
Claims (5)
1. a Mierocrystalline cellulose straw-like materials component splits and the method for intensive processing; It is characterized in that: remove in the straw-like materials of semicellulose and add liquid alcohols material by solid-liquid mass ratio 1:2-8 to removing semicellulose or part; Extracted 1-4 hour down at 60-180 ℃; Solid-liquid separation, liquid phase substance are the alcoholic solution that contains xylogen; It is refining that biological multielement is pure in liquid phase substance, to add polyoxyethylene glycol or epoxy compounds reaction back;
Before in liquid phase substance, adding polyethylene glycol; The liquid alcohols material of 20-95% is removed in liquid phase substance evaporation earlier; Add the liquid alcohols material mass 1-100 in evaporation back polyethylene glycol doubly then; The 0.1-3% that presses the polyethylene glycol quality again adds inorganic acid; 100-170 ℃ of control temperature; Reacted 0.2-4 hour, and added alkaline matter adjust pH 6-8 at last, refining that biological multielement is pure;
Before in liquid phase substance, adding epoxy compounds; The liquid alcohols material of 20-95% is removed in liquid phase substance evaporation earlier; Add the total liquid mass 0.1-10 in evaporation back epoxy compounds doubly then; The basic catalyst that adds epoxy compound amount 0.1-5% again, in atmosphere of inert gases, 80-150 ℃ reaction 1-3 hour, refining polyether glycol.
2. the method for Mierocrystalline cellulose straw-like materials component fractionation as claimed in claim 1 and intensive processing, it is characterized in that: said liquid alcohols material is a polyvalent alcohol; Said mineral acid is sulfuric acid, hydrochloric acid or phosphoric acid; Said alkaline matter is Pottasium Hydroxide or sodium hydroxide.
3. the method for Mierocrystalline cellulose straw-like materials component fractionation as claimed in claim 2 and intensive processing, it is characterized in that: said polyvalent alcohol is a terepthaloyl moietie.
4. the method for Mierocrystalline cellulose straw-like materials component fractionation as claimed in claim 1 and intensive processing, it is characterized in that: said epoxy compounds is oxyethane, propylene oxide or butylene oxide ring; Said basic catalyst is Pottasium Hydroxide or sodium hydroxide; Said rare gas element is nitrogen or carbonic acid gas.
5. split like each described Mierocrystalline cellulose straw-like materials component of claim 1-4 and the method for intensive processing, it is characterized in that: saidly remove that straw-like materials that semicellulose or part remove semicellulose refers to after hydrolysis or vapour are quick-fried, to remove or part removes the straw-like materials of semicellulose.
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| CN201110028077A CN102060998B (en) | 2011-01-26 | 2011-01-26 | Method for splitting and deeply processing cellulose straw substance components |
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| CN201110028077A CN102060998B (en) | 2011-01-26 | 2011-01-26 | Method for splitting and deeply processing cellulose straw substance components |
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| CN102060998A CN102060998A (en) | 2011-05-18 |
| CN102060998B true CN102060998B (en) | 2012-10-03 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105622957B (en) * | 2014-11-05 | 2018-05-04 | 中国石油化工集团公司 | A kind of preparation method of lignin polyether polyalcohol |
| CN111440284A (en) * | 2020-06-01 | 2020-07-24 | 浙江高裕家居科技有限公司 | Strong-support high-elasticity polyurethane soft foam material and preparation method thereof |
| CN111662458A (en) * | 2020-06-01 | 2020-09-15 | 浙江高裕家居科技股份有限公司 | Lignin-based block copolymer molecular-level combined polyether, preparation method thereof and application thereof in preparation of polyurethane flexible foam material |
| CN112724394B (en) * | 2020-12-28 | 2023-03-17 | 山东一诺威新材料有限公司 | Preparation method of cellulose polyether polyol |
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| CN101186559A (en) * | 2007-12-10 | 2008-05-28 | 中国科学院广州化学研究所 | Method for preparing corn straw polyatomic alcohol |
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| CN101696261A (en) * | 2009-10-29 | 2010-04-21 | 华南理工大学 | Lignin polyurethane and preparation method thereof |
| CN101928373A (en) * | 2010-08-27 | 2010-12-29 | 华南理工大学 | Plant fiber component-based polyalcohol and preparation method thereof |
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| US20030041982A1 (en) * | 2001-08-31 | 2003-03-06 | Prior Eric S. | Organic biomass fractionation process |
| CN101787086B (en) * | 2010-02-11 | 2011-09-14 | 南京工业大学 | Device and method for hydrolyzing plant hemicellulose by using fermented citric acid wastewater |
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Patent Citations (4)
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| CN101186559A (en) * | 2007-12-10 | 2008-05-28 | 中国科学院广州化学研究所 | Method for preparing corn straw polyatomic alcohol |
| CN101643796A (en) * | 2009-08-28 | 2010-02-10 | 上海中科清洁能源技术发展中心 | Method for utilizing straw biomass by grades |
| CN101696261A (en) * | 2009-10-29 | 2010-04-21 | 华南理工大学 | Lignin polyurethane and preparation method thereof |
| CN101928373A (en) * | 2010-08-27 | 2010-12-29 | 华南理工大学 | Plant fiber component-based polyalcohol and preparation method thereof |
Non-Patent Citations (5)
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| 刘育红,席丹.以木质素为原料合成聚氨酯的研究进展.《聚氨酯工业》.2003,第18卷(第3期), * |
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