CN101186560B - Method for preparing polyatomic alcohol from crop straw - Google Patents
Method for preparing polyatomic alcohol from crop straw Download PDFInfo
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- CN101186560B CN101186560B CN2007100323154A CN200710032315A CN101186560B CN 101186560 B CN101186560 B CN 101186560B CN 2007100323154 A CN2007100323154 A CN 2007100323154A CN 200710032315 A CN200710032315 A CN 200710032315A CN 101186560 B CN101186560 B CN 101186560B
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Abstract
The invention relates to a method of preparing polyhydric alcohol by using crops straws, comprising the steps: counting by mass portion, 100 portions of organic solvent and 1 to 6 portions of catalystare evenly mixed, then 15 to 40 portions of crops straws are added under 80 to 210 DEG C, and the polyhydric alcohol can be obtained by reacting for 60 to 240min. The method fully utilizes rich and r eproducible agricultural residue; the hydroxyl value of the obtained polyhydric alcohol is 180 to 850mg KOH/g; crops straw catabolites of different contents and polyhydric alcohol of different hydroxyl values can be obtained by adjusting the production process and the portions according to requirements. The production process of the invention is simple and the invention can be directly used for synthesizing polyurethane foam plastics without the need of post-processing procedures of vacuum dehydration, product separation, etc.
Description
Technical field
The present invention relates to the preparation method of polyvalent alcohol, be specifically related to a kind of method of utilizing agricultural crop straw to prepare polyvalent alcohol.
Background technology
Urethane foam has excellent thermal insulation properties, good processing properties and mechanical property, is widely used in national economy and national defense industry every field.Mainly by polymer polyatomic alcohol and organic isocyanate reaction synthetic, these raw materials all come from petrochemicals to traditional urethane foam.Along with socioeconomic fast development, the petroleum resources that the mankind depend on for existence are withered day by day thirsty, in order to reduce the environmental problem that the dependency and the petrochemical complex of petroleum resources are brought, replace petroleum resources to prepare polyol compound having caused people's attention to enrich reproducible natural resources.
Publication number is " CN 1869184A "; the Chinese invention patent application that name is called " a kind of preparation method of vegetable oil polyol " discloses a kind of preparation method of vegetable oil polyol; this method is reacted vegetables oil and low substituted fatty acid or polyvalent alcohol in the presence of alkali; entire reaction course needs to react under protection of inert gas earlier; continue reaction then under vacuum condition, cooling at last promptly gets the polyvalent alcohol product.The Chinese invention patent application that publication number is called " a kind of rigid urethane foam that adopts rapeseed oil preparation " for " CN 1844183A " name discloses a kind of employing rapeseed oil and has prepared rigid urethane foam, at first rapeseed oil and epoxidizing agent are carried out epoxidation reaction in the presence of catalyzer, generate epoxy rapeseed oil; With epoxy rapeseed oil that generates and the nucleophilic generation epoxy bond ring-opening reaction that contains reactive hydrogen, generate and mix the hydroxy aliphatic acid glyceride again; Add the intensification of alcohol or hydramine again and carry out alcoholysis reaction, generate and mix hydroxy aliphatic acid monoester, i.e. biopolyol.These methods are raw material with soybean oil, rapeseed oil, Semen Maydis oil, sesame oil, peanut wet goods vegetables oil all, not only consume a large amount of grain resources, and complex manufacturing even need charge into harsh reaction conditions such as rare gas element or vacuum.
The Chinese invention patent application that publication number is called " utilizing vegetable fibre to produce the method for polyvalent alcohol " for " CN 1915947A " name discloses the method that a kind of vegetable fibres such as crust that utilize depleted corn, wheat, soybean prepare polyvalent alcohol, the aqueous solution of gained after the vegetable fibre hydrolysis is passed through steps such as hydrogenation, hydrogenolysis, separation, obtain the polyvalent alcohol of single component at last.This method mainly is to obtain single polyvalent alcohol by the series reaction to the hydrolysate of the vegetable fibres such as crust of corn, wheat, soybean with separating, the utilising efficiency of vegetable fibre is low, and whole reaction system is the aqueous solution, its production technique and product sepn process complexity.
Summary of the invention
The objective of the invention is provides a kind of method of utilizing agricultural crop straw to prepare polyvalent alcohol in order to overcome the above-mentioned shortcoming and defect of prior art.Method of the present invention comprises the steps:
According to the mass fraction, 100 parts of organic solvents, catalyzer are mixed for 1～6 part, add 15～40 parts of agricultural crop straws down at 80～210 ℃ then, reaction 60～240min postcooling promptly gets polyvalent alcohol.
Described solvent mainly comprises one or more the mixture in NSC 11801, propylene carbonate, ethylene glycol, glycol ether, polyoxyethylene glycol, glycerol, the gamma-butyrolactone.
Described polyoxyethylene glycol preferred molecular weight is 100～1000 polyoxyethylene glycol.More preferably molecular weight is 200～600 polyoxyethylene glycol.
Described catalyzer comprises one or more the mixture in hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid or the nitric acid.Described catalyzer is preferably one or more the mixture in hydrochloric acid, sulfuric acid or the phosphoric acid.
Described catalyzer also comprises sodium hydroxide.
Described agricultural crop straw comprises one or more the mixture in straw, wheat straw, maize straw, the soybean stalk.Described agricultural crop straw preferable particle size is pulverous straw of 20～120 purposes or maize straw.40～80 orders more preferably.
The described reaction times is preferably 90～180min; Temperature of reaction is preferably 120～170 ℃.
Compared with prior art, the present invention has following advantage:
Method of the present invention can be a raw material with the depleted agricultural crop straw, prepares urethane foam in order to replace the petrochemical complex polyol compound.
Agricultural crop straw mainly is made up of Mierocrystalline cellulose, hemicellulose and xylogen, contains a large amount of hydroxyls on its molecular chain, can be used as the starting material of synthesis of polyurethane, but because its crystalline texture and tridimensional network, the hydroxyl on the molecular chain loses reactive behavior.The technical solution used in the present invention is dissolved in the solvent agricultural crop straw by chemical reaction under the effect of described temperature and catalyzer, forms the polyvalent alcohol of the homogeneous phase solution system that is rich in a large amount of reactive hydroxyl groups.
The polyvalent alcohol that the present invention is prepared, according to actual requirement, can be by adjusting reaction raw materials and proportioning thereof, and reaction process condition, obtain the polyvalent alcohol product of different performance index, its agricultural crop straw content of degradation products can be that 400～2450mPaS, hydroxyl value are 180～850mgKOH/g 10～30% changes, viscosity, to adapt to the requirement of the urethane foam that synthesizes different performance.
The prepared polyvalent alcohol of the present invention is compared with petrochemical complex polyvalent alcohol or vegetable oil polyol, and also have the following advantages: (1) is cheap and easy to get, and it is convenient to buy, reproducible characteristics; (2) reaction conditions is simple, and entire reaction course is carried out under normal pressure, does not need the protection of rare gas element; (3) production technique is simple, and entire reaction course is carried out in non-aqueous system, and the polyvalent alcohol product of gained does not need vacuum hydro-extraction aftertreatment technology such as to separate with product, can be directly used in the synthesis of polyurethane porous plastics; (4) this method can be passed through to adjust reaction raw materials and proportioning thereof, and reaction process condition, obtains the polyvalent alcohol product of different performance index, to adapt to the requirement of the urethane foam that synthesizes different performance; (5) the polyvalent alcohol product of gained can directly all replace the petrochemical complex polyvalent alcohol, is used for the synthesis of polyurethane porous plastics, rather than part replaces.
Embodiment
Below enumerate the more excellent embodiment of the present invention, understand the present invention to help further, but protection scope of the present invention is not limited in this.
Used agricultural crop straw has maize straw and straw in following examples, all is Powdered, and its particle diameter is 20～80 orders, oven dry before using; Used solvent NSC 11801, ethylene glycol, polyoxyethylene glycol, glycerol etc. reach catalyst sulfuric acid and phosphoric acid and buy by market, and wherein the molecular weight of polyoxyethylene glycol is 200～600.
Embodiment 1
At first 100g ethylene glycol and the adding of 3g sulfuric acid are equipped with in the there-necked flask of mechanical stirring and prolong, stirring mixes it, and oil bath is preheated to 160 ℃; Under whipped state, add the 20g maize straw then, place the frozen water mixed solution to cool off termination reaction there-necked flask behind the isothermal reaction 150min, obtain containing the polyvalent alcohol of 16.3% maize straw degraded product, its viscosity is 750～1200mPaS, and hydroxyl value is 570～800mg KOH/g.
Embodiment 2
At first 80g polyoxyethylene glycol, 20g glycerol and 3g sulfuric acid are added and be equipped with in the there-necked flask of mechanical stirring and prolong, stirring mixes it, and oil bath is preheated to 150 ℃; Under whipped state, add the 20g straw then, place the frozen water mixed solution to cool off termination reaction there-necked flask behind the isothermal reaction 120min, obtain containing the polyvalent alcohol of 16.3% straw degraded product, its viscosity is 950～1480mPaS, and hydroxyl value is 280～450mg KOH/g.
Embodiment 3
At first 100g polyoxyethylene glycol and the adding of 3g sulfuric acid are equipped with in the there-necked flask of mechanical stirring and prolong, stirring mixes it, and oil bath is preheated to 150 ℃; Under whipped state, add the 30g maize straw then, place the frozen water mixed solution to cool off termination reaction there-necked flask behind the isothermal reaction 150min, obtain containing the polyvalent alcohol of 22.6% maize straw degraded product, its viscosity is 1150～1730mPaS, and hydroxyl value is 225～390mg KOH/g.
Embodiment 4
At first 100g NSC 11801 and the adding of 3g sulfuric acid are equipped with in the there-necked flask of mechanical stirring and prolong, stirring mixes it, and oil bath is preheated to 130 ℃; Under whipped state, add the 40g straw then, place the frozen water mixed solution to cool off termination reaction there-necked flask behind the isothermal reaction 120min, obtain containing the polyvalent alcohol of 28.0% straw degraded product, its viscosity is 1370～2020mPaS, and hydroxyl value is 420～690mg KOH/g.
Embodiment 5
At first 100g NSC 11801 and the adding of 5g phosphoric acid are equipped with in the there-necked flask of mechanical stirring and prolong, stirring mixes it, and oil bath is preheated to 150 ℃; Under whipped state, add the 30g maize straw then, place the frozen water mixed solution to cool off termination reaction there-necked flask behind the isothermal reaction 100min, obtain containing the polyvalent alcohol of 22.2% maize straw degraded product, its viscosity is 630～1050mPaS, and hydroxyl value is 530～780mg KOH/g.
Embodiment 6
At first 80g NSC 11801,20g ethylene glycol and 3g sulfuric acid are added and be equipped with in the there-necked flask of mechanical stirring and prolong, stirring mixes it, and oil bath is preheated to 150 ℃; Under whipped state, add the 30g straw then, place the frozen water mixed solution to cool off termination reaction there-necked flask behind the isothermal reaction 120min, obtain containing the polyvalent alcohol of 22.6% straw degraded product, its viscosity is 580～945mPaS, and hydroxyl value is 465～720mg KOH/g.
Claims (7)
1. a method of utilizing agricultural crop straw to prepare polyvalent alcohol is characterized in that, may further comprise the steps:
According to the mass fraction, 100 parts of organic solvents, catalyzer are mixed for 1～6 part, add 15～40 parts of agricultural crop straws down at 80～210 ℃ then, reaction 60～240min postcooling promptly gets polyvalent alcohol;
Described solvent is one or more the mixture in NSC 11801, propylene carbonate, ethylene glycol, glycol ether, polyoxyethylene glycol, glycerol, the gamma-butyrolactone; Described catalyzer is one or more the mixture in hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid or the nitric acid.
2. a kind of method of utilizing agricultural crop straw to prepare polyvalent alcohol according to claim 1 is characterized in that the molecular weight of described polyoxyethylene glycol is 100～1000.
3. a kind of method of utilizing agricultural crop straw to prepare polyvalent alcohol according to claim 2 is characterized in that the molecular weight of described polyoxyethylene glycol is 200～600.
4. a kind of method of utilizing agricultural crop straw to prepare polyvalent alcohol according to claim 1 is characterized in that, described catalyzer is one or more the mixture in hydrochloric acid, sulfuric acid or the phosphoric acid.
5. a kind of method of utilizing agricultural crop straw to prepare polyvalent alcohol according to claim 1 is characterized in that, described agricultural crop straw comprises one or more the mixture in straw, wheat straw, maize straw, the soybean stalk.
6. a kind of method of utilizing agricultural crop straw to prepare polyvalent alcohol according to claim 5 is characterized in that, described agricultural crop straw is that particle diameter is pulverous straw of 20～120 purposes or maize straw.
7. a kind of method of utilizing agricultural crop straw to prepare polyvalent alcohol according to claim 1 is characterized in that the described reaction times is 90～180min; Temperature of reaction is 120～170 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100323154A CN101186560B (en) | 2007-12-10 | 2007-12-10 | Method for preparing polyatomic alcohol from crop straw |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100323154A CN101186560B (en) | 2007-12-10 | 2007-12-10 | Method for preparing polyatomic alcohol from crop straw |
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| Publication Number | Publication Date |
|---|---|
| CN101186560A CN101186560A (en) | 2008-05-28 |
| CN101186560B true CN101186560B (en) | 2011-03-30 |
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| CN2007100323154A Expired - Fee Related CN101186560B (en) | 2007-12-10 | 2007-12-10 | Method for preparing polyatomic alcohol from crop straw |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| AU2012266334B2 (en) * | 2011-06-10 | 2016-05-12 | Queensland University Of Technology | Methods for converting lignocellulosic material to useful products |
| CN102304213B (en) * | 2011-07-18 | 2013-06-05 | 中国科学院过程工程研究所 | Method for preparing polyurethane from straw fermentation residua through polyatomic alcohol liquefaction |
| CN103086844A (en) * | 2013-01-30 | 2013-05-08 | 中科院广州化学有限公司 | Method for preparing polyalcohol by ultrasonic wave assisting rapidly liquefied plant biomass |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915947A (en) * | 2006-09-07 | 2007-02-21 | 山东西王糖业有限公司 | Method for producing polyalcohol by using plant fiber |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915947A (en) * | 2006-09-07 | 2007-02-21 | 山东西王糖业有限公司 | Method for producing polyalcohol by using plant fiber |
Non-Patent Citations (2)
| Title |
|---|
| 王高升等.玉米秸秆多羟基醇液化研究.生物质化学工程41 1.2007,41(1),14-18. |
| 王高升等.玉米秸秆多羟基醇液化研究.生物质化学工程41 1.2007,41(1),14-18. * |
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| CN101186560A (en) | 2008-05-28 |
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Address after: 510650 Tianhe District, Guangdong Province, willing to live in Guangzhou Patentee after: Guangzhou Chemistry Co., Ltd. Chinese Academy of Sciences Address before: 510650 Tianhe District, Guangdong Province, willing to live in Guangzhou Patentee before: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences |
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Granted publication date: 20110330 Termination date: 20201210 |
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