CN102060998A - 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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- CN102060998A CN102060998A CN2011100280776A CN201110028077A CN102060998A CN 102060998 A CN102060998 A CN 102060998A CN 2011100280776 A CN2011100280776 A CN 2011100280776A CN 201110028077 A CN201110028077 A CN 201110028077A CN 102060998 A CN102060998 A CN 102060998A
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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, its component need be split and separate, hemicellulose resolves into five-carbon sugar, and lignin extraction is come out, 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 gentleer at present, 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 hemicellulose is changed into five-carbon sugar, but remaining Mierocrystalline cellulose and xylogen be weave in still, hindered the accessibility of cellulase, 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 xylogen is extracted, and to separate with extraction agent behind the xylogen be by 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 invention provides the method for a kind of Mierocrystalline cellulose straw-like materials component fractionation and intensive processing, this method can make cellulose substances maximize the use.
The present invention is by the following technical solutions:
The method of a kind of Mierocrystalline cellulose straw-like materials component fractionation and intensive processing, remove in the straw-like materials of hemicellulose and add liquid alcohols material to removing hemicellulose 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; In liquid phase substance, add polyoxyethylene glycol or epoxy compounds reaction back refining biological multielement alcohol.
Before in liquid phase substance, adding polyoxyethylene 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 polyoxyethylene glycol doubly then, 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 biological multielement alcohol.
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.
Described liquid alcohols material is a polyvalent alcohol; Described mineral acid is sulfuric acid, hydrochloric acid or phosphoric acid; Described alkaline matter is potassium hydroxide or sodium hydroxide.
Described polyvalent alcohol is an ethylene glycol.
Described epoxy compounds is oxyethane, propylene oxide or butylene oxide ring; Described basic catalyst is potassium hydroxide or sodium hydroxide; Described rare gas element is nitrogen or carbonic acid gas.
Describedly remove that straw-like materials that hemicellulose or part remove hemicellulose refers to remove or part removes the straw-like materials of hemicellulose after hydrolysis or vapour are quick-fried.
The present invention discovers, xylogen can be dissolved in the liquid alcohol kind solvent at a certain temperature, and contain 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 separated fiber element and utilize the pure and mild polyether glycol of xylogen production biological multielement to merge, both having separated the cellulosic while also utilizes xylogen to produce polyvalent alcohol, reduced production link, reduced the isolating cost of xylogen and Mierocrystalline cellulose, lignin separation has been gone out during cellulase hydrolysis simultaneously, therefore greatly reduce 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
Maize straw disintegrating slag 1000 grams that remove behind the hemicellulose are separated in water intaking, put into reactor, add 5000 gram ethylene glycol, 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, and 4500 gram ethylene glycol 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, add sodium hydroxide adjust pH to 7, finish the reaction back refining biological multielement alcohol.
Embodiment 2
Get quick-fried maize straw disintegrating slag 1000 grams that remove behind the hemicellulose of vapour, put into reactor, add 2000 gram ethylene glycol, 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, and 400 ethylene glycol are removed in the liquid phase part evaporation, adds polyoxyethylene glycol 8000 grams then, add 80 gram sulfuric acid, be heated to 100 ℃ of reactions 4 hours, add sodium hydroxide adjust pH to 6, finish the reaction back refining biological multielement alcohol.
Embodiment 3
Maize straw disintegrating slag 1000 grams that remove behind the hemicellulose are separated in water intaking, put into reactor, add 8000 gram ethylene glycol, 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, and 4000 gram ethylene glycol are removed in the liquid phase part evaporation, adds cetomacrogol 1000 0 gram then, add 10 gram sulfuric acid, be heated to 170 ℃ of reactions 0.2 hour, add sodium hydroxide adjust pH to 8, finish the reaction back refining biological multielement alcohol.
Embodiment 4
Get quick-fried maize straw disintegrating slag 2000 grams that remove behind the hemicellulose of vapour, put into reactor, add 8000 gram ethylene glycol, 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, ethylene glycol 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 ethylene glycol then, the sodium hydroxide that adds propylene oxide quality 0.1%, feed nitrogen, 150 ℃ were reacted 1 hour, finished the refining lignin-base polyether glycol that obtains in reaction back.
Embodiment 5
Maize straw disintegrating slag 2000 grams that remove behind the hemicellulose are separated in water intaking, put into reactor, add 8000 gram ethylene glycol, 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, ethylene glycol 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 ethylene glycol then, the sodium hydroxide that adds butylene oxide ring quality 3%, feed carbonic acid gas, 80 ℃ were reacted 3 hours, finished the refining lignin-base polyether glycol that obtains in reaction back.
Embodiment 6
Get quick-fried maize straw disintegrating slag 2000 grams that remove behind the hemicellulose of vapour, put into reactor, add 8000 gram ethylene glycol, 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, ethylene glycol 2000 grams are removed in the liquid phase part evaporation, the oxyethane that adds 10 times of total liquid masies behind the evaporation ethylene glycol then, the sodium hydroxide that adds oxyethane quality 5%, feed nitrogen, 110 ℃ were reacted 2 hours, finished the refining lignin-base polyether glycol that obtains in reaction back.
Claims (7)
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 hemicellulose and add liquid alcohols material by solid-liquid mass ratio 1:2-8 to removing hemicellulose or part, extracted 1-4 hour down at 60-180 ℃, solid-liquid separation, liquid phase substance are the alcoholic solution that contains xylogen; In liquid phase substance, add polyoxyethylene glycol or epoxy compounds reaction back refining biological multielement alcohol.
2. the method for Mierocrystalline cellulose straw-like materials component fractionation as claimed in claim 1 and intensive processing, it is characterized in that: before in liquid phase substance, adding polyoxyethylene 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 polyoxyethylene glycol doubly then, the 0.1-3% that presses the polyoxyethylene glycol quality again adds mineral acid, controlled temperature 100-170 ℃, reacts 0.2-4 hour, add alkaline matter adjust pH 6-8 at last, refining biological multielement alcohol.
3. the method for Mierocrystalline cellulose straw-like materials component fractionation as claimed in claim 1 and intensive processing, it is characterized in that: 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.
4. the method for Mierocrystalline cellulose straw-like materials component fractionation as claimed in claim 2 and intensive processing, it is characterized in that: described liquid alcohols material is a polyvalent alcohol; Described mineral acid is sulfuric acid, hydrochloric acid or phosphoric acid; Described alkaline matter is potassium hydroxide or sodium hydroxide.
5. the method for Mierocrystalline cellulose straw-like materials component fractionation as claimed in claim 4 and intensive processing, it is characterized in that: described polyvalent alcohol is an ethylene glycol.
6. the method for Mierocrystalline cellulose straw-like materials component fractionation as claimed in claim 3 and intensive processing, it is characterized in that: described epoxy compounds is oxyethane, propylene oxide or butylene oxide ring; Described basic catalyst is potassium hydroxide or sodium hydroxide; Described rare gas element is nitrogen or carbonic acid gas.
7. split as each described Mierocrystalline cellulose straw-like materials component of claim 1-6 and the method for intensive processing, it is characterized in that: describedly remove that straw-like materials that hemicellulose or part remove hemicellulose refers to remove or part removes the straw-like materials of hemicellulose after hydrolysis or vapour are quick-fried.
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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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622957A (en) * | 2014-11-05 | 2016-06-01 | 中国石油化工集团公司 | Lignin polyether polyol preparation method |
| CN111662426A (en) * | 2020-06-01 | 2020-09-15 | 浙江高裕家居科技股份有限公司 | 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 |
| CN112724394A (en) * | 2020-12-28 | 2021-04-30 | 山东一诺威新材料有限公司 | Preparation method of cellulose polyether polyol |
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2011
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622957A (en) * | 2014-11-05 | 2016-06-01 | 中国石油化工集团公司 | Lignin polyether polyol preparation method |
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| CN111662426A (en) * | 2020-06-01 | 2020-09-15 | 浙江高裕家居科技股份有限公司 | 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 |
| CN112724394A (en) * | 2020-12-28 | 2021-04-30 | 山东一诺威新材料有限公司 | Preparation method of cellulose polyether polyol |
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| CN102060998B (en) | 2012-10-03 |
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