CN103086844A - Method for preparing polyalcohol by ultrasonic wave assisting rapidly liquefied plant biomass - Google Patents
Method for preparing polyalcohol by ultrasonic wave assisting rapidly liquefied plant biomass Download PDFInfo
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- CN103086844A CN103086844A CN201310037271XA CN201310037271A CN103086844A CN 103086844 A CN103086844 A CN 103086844A CN 201310037271X A CN201310037271X A CN 201310037271XA CN 201310037271 A CN201310037271 A CN 201310037271A CN 103086844 A CN103086844 A CN 103086844A
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Abstract
The invention discloses a method for preparing polyalcohol by an ultrasonic wave assisting rapidly liquefied plant biomass, and belongs to the field of thermochemical liquefaction of plant biomass. The method concretely comprises the steps of evenly mixing 100 parts of liquefier and 1-6 parts of acid catalyst, heating to 110-150 DEG C in oil bath; adding 5-30 parts of plant biomass to mix evenly; carrying out constant-temperature reaction for 10-90 minutes under the effect of an ultrasonic wave of which the power is 100-800 W and the frequency is 20kHz, and cooling by ice-water bath to terminate the reaction and obtain the plant polyalcohol. The measured reaction residue rate is greatly reduced; the structure and the property of the obtained product are similar as those of the product liquefied by traditional oil bath. The method is low in liquefaction temperature, low in ultrasonic power, fast in velocity, and high in efficiency; the plant fiber material polyalcohol with high reaction activity and high functionality is obtained; and the requirements of the liquefied product for preparing different polyurethane materials are met.
Description
Technical field
The invention belongs to plant biomass Thermochemical Liquefaction field, particularly a kind of ultrasonic wave booster action that utilizes, realize that under mild conditions the fast liquefying of plant material prepares biomass polyalcohol, and improve liquefaction efficiency and reduce the method for liquefaction reaction condition.
Background technology
Plant biomass is a kind of modal, reproducible natural, ecological material.Plant biomass three major polymers: cellulose, hemicellulose and xylogen three parts form, and various components all contain great amount of hydroxy group isoreactivity group.The plant biomass raw material resources of China are very abundant, but resource utilization is low, and major part is to be directly used in burning and effectively not to be converted into the useful materials of high value.There are a lot of researchers to begin research to it in the eighties in 20th century, adopt the organic solvent liquefaction plant biomass such as phenol and polyvalent alcohol to prepare polyvalent alcohol, the solid-state biomass macromolecules degradation is become the liquid small molecules with reactive behavior, and liquefied product is used for preparing new macromolecular material, as tackiness agent, injection plastic, porous plastics, filamentary material etc.Liquefying biomass mainly uses atmospheric solvent process both at home and abroad, mainly concentrates at present polyvalent alcohols such as utilizing phenol, carbonates, ethylene glycol and polyoxyethylene glycol; Abroad particularly Japan is comparatively outstanding for plant biomass liquefaction research, to liquefaction process and liquefied product should be used as systematic research, the people such as Japanese scholars Shiraishi have proposed the technology take polyhydroxy-alcohol as liquefied reagent, but this method is consuming time longer; The people such as Yamada have proposed the method for fast liquefying plant biomass in NSC 11801, but NSC 11801 is expensive, are unfavorable for that the further production of the method is promoted.Domestic Zhang Qiuhui etc. has inquired into the liquefaction of China fir and white poplar phenol, adopt phosphoric acid (85%), the low vitriol oil (36%), hydrochloric acid (37%), (99.5%) four kind of mineral acid of oxalic acid, carried out the liquefaction test of timber under differing temps, result shows that phosphoric acid and the low vitriol oil are effective catalyzer.Chen Fan more waited the people to study the bagasse liquefaction behavior under microwave heating in 2011, but microwave has aggravated the generation of side reaction, and low than oil bath liquefaction of the hydroxyl value of the liquefied product of gained, is unfavorable for the application of product, and the microwave heating treatment amount is little, is unfavorable for the popularization of the method.There is the scholar to report the method for utilizing bamboo powder, maize straw and bagasse to prepare plant polyatomic alcohol at Chinese patent CN101260186A, CN101205287B, CN101186560B and CN1271106C philosophy.
The shortcoming of above-mentioned document is: (1) liquefaction reaction is needed chronic; (2) temperature of reaction of liquefaction is high, and general liquefaction reaction is with oil bath, liquefaction solvent to be heated to 150～180 ℃; (3) liquefied reagent toxicity is large or cost is higher, is unfavorable for realizing industrialization, and liquefaction reaction is thorough not.
Ultrasonic wave is that a kind of frequency is the mechanical vibration wave of 2 * 104～107Hz, and wavelength is short, and frequency is high, and energy is huge, can make the particle of medium produce significant acoustic pressure effect, has the strong characteristics with being easy to concentrate energy by focusing on of beam; Its principal feature is the acoustic cavitation effect, and its huge energy can make the medium particle in liquid medium obtain very large acceleration, and produces high temperature and high pressure, causes free radical to form and produce great shockwave and microjet.Ultrasonic wave has a wide range of applications in fields such as chemistry, physics, biology, medical science, industrial and agricultural production and measurements at present.Tang Ailing etc. have studied ultrasonic pretreatment plant wood fibre structure, and discovery can improve enzymic hydrolysis efficient; The report ultrasonic pretreatment such as Wang Xianling can promote saccharification of cellulose efficient; Kang Guangbo with ultrasonic wave respectively with acid, alkali combined pretreatment straw, find after ultrasonication, saccharification efficient and fermentation efficiency to be improved, produce more alcohol; Liao Bing, Zhang Hairong etc. (CN102320921A) be not in additionally heating, utilizing the high-power ultrasonic liquefying biomass under the organic acid catalysis condition, and its method long reaction time, energy consumption are large, and the phenol equal solvent is noxious solvent, dangerous environmental protection.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of method of utilizing the auxiliary fast liquefying plant biomass of ultrasonic wave to prepare polyvalent alcohol; By ultrasonic wave assist, oil bath heating, inorganic acid catalyzed method, shortened the plant biomass liquefaction reaction time, reduce liquefaction temperature, improved Degree of Liquefaction, provide a kind of new method for utilizing plant biological material fast liquefying to prepare polyvalent alcohol.
Purpose of the present invention is achieved through the following technical solutions: a kind of method of utilizing the auxiliary fast liquefying plant biomass of ultrasonic wave to prepare polyvalent alcohol, comprise the steps: 100 mass parts liquefying agents and 1～6 mass parts acid catalyst are mixed, be placed in oil bath and be warming up to 110～150 ℃; The plant biomass that adds the dry constant weight of 5～30 mass parts, mix, open the ultrasonic cell disruption instrument device, power is 100～800W, frequency is 20kHz, isothermal reaction 10～90min, the cooling termination reaction of ice bath, obtain plant polyatomic alcohol, assaying reaction residue rate, product hydroxyl value and viscosity.
Described liquefying agent is polyoxyethylene glycol, or is the polyoxyethylene glycol of 1:1～100:1 and the mixture that low molecular polylol forms by mass ratio; Polyoxyethylene glycol used be average molecular mass be 200,400,600,800 and 1000 a kind of; Low molecular polylol used is at least a of ethylene glycol, propylene glycol and glycerol.
Described acid catalyst is at least a of hydrochloric acid, sulfuric acid, phosphoric acid and p-methyl benzenesulfonic acid.
Described plant biomass is at least a of bagasse, maize straw, wheat straw, bamboo and straw, preferred bagasse; The plant biomass particle diameter is 20～120 orders, preferred 40～80 orders.
Described power is preferably 100～400W.
The mensuration of described residue rate is according to document (Yao, Y, G Yoshioka, M Shiraishi, N, Combined liquefaction of wood and starch in a polyethylene/glycol glycerin blended solvent.Mokuzai Gakkaishi, 1993,39 (8): 930-938.) carry out; The mensuration of hydroxyl value is carried out according to GB12008.3-1989, and the mensuration of viscosity is carried out according to GB/T1200818-92.
The ultimate principle of present method is as follows:
Destroy the structure of fibrous tissue of plant biomass by ultrasonic wave, molecular motion is accelerated in the oil bath heating, makes liquefaction solvent be easier to infiltration, thereby has realized the fast liquefying of plant fiber material, and reduced the liquefaction reaction condition; Structural damage makes that to have reactive group exposed is more, realizes high reaction activity and the high functionality of plant fiber material polylol, and high hydroxyl value satisfies the needs of preparation polyurethane material.
Liquifying method of the present invention has following advantage compared with prior art:
(1) liquefaction temperature is lower, Liquefaction Rate is fast: the conventional oil bath liquefaction reaction reaches the lower liquefied residue rate 90～120min that generally need to liquefy under 150～180 ℃ could realize, (liquefaction reaction of bagasse reaches preparation and the sign based on the urethane of liquefied product as Liu Juanjuan, Master's thesis, 2010:21-28.) etc. the bagasse measured of people residue rate after 150 ℃ of reaction 90min in the PEG400/ glycerol be 6.2%, and in the embodiment of the present invention 1, the liquefaction holding temperature is 130 ℃, after the auxiliary liquefaction of ultrasonic wave 20min, the residue rate is 2.5%.This shows, the auxiliary liquefaction of ultrasonic wave is compared with conventional oil bath liquefaction, and the holding temperature of its reaction reduces greatly, and liquefaction efficiency greatly improves, and the reaction times has also shortened 80%.
(2) ultrasonic power is low, the residue rate is low: power of the present invention is 100～800W, preferred 100～400W, have the advantages such as low power, less energy-consumption and low residue rate, as ultrasonic power 2500W in Chinese patent application (CN102320921A) embodiment, ultrasonic frequency 20kHz, ultrasonic 30min liquefied residue rate is 13.7%; In the embodiment of the present invention 2,140 ℃ of oil bath insulations, ultrasonic power 800W, ultrasonic frequency 20kHz, the residue rate of the liquefied product that obtains after ultrasonic 10min is 2.4%.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
80g polyoxyethylene glycol (molecular weight 400), 20g glycerol and the 3g vitriol oil are added mechanical stirring mixing in the there-necked flask that prolong is housed, put into oil bath and be warming up to 130 ℃, add 10g bagasse under whipped state, then insert the ultrasonic cell disruptor horn, open Vltrasonic device, after ultrasonic 20min under ultrasonic power 400W, ultrasonic frequency 20kHz, there-necked flask is placed in the cooling termination reaction of ice-water bath, the residue rate of the liquefied product that obtains is 2.5%, viscosity is 200～900mPaS, and hydroxyl value is 240～380mg KOH/g.
Embodiment 2
50g polyoxyethylene glycol (molecular weight 200), 50g glycerol and the 3g vitriol oil are added mechanical stirring mixing in the there-necked flask that prolong is housed, put into oil bath and be warming up to 140 ℃, add 30g bagasse under whipped state, then insert the ultrasonic cell disruptor horn, open Vltrasonic device, at ultrasonic power 800W, under ultrasonic frequency 20kHz after ultrasonic 10min, there-necked flask is placed in the cooling termination reaction of ice-water bath, the residue rate of the liquefied product that obtains is 2.4%, viscosity is 600～1000mPaS, and hydroxyl value is 300～450mg KOH/g.
Embodiment 3
100g glycerol and the 3g vitriol oil are added mechanical stirring mixing in the there-necked flask that prolong is housed, put into oil bath and be warming up to 110 ℃, add 20g bagasse under whipped state, then insert the ultrasonic cell disruptor horn, open Vltrasonic device, at ultrasonic power 100W, under ultrasonic frequency 20kHz after ultrasonic 30min, there-necked flask is placed in the cooling termination reaction of ice-water bath, the residue rate of the liquefied product that obtains is 10.1%, viscosity is 400～1100mPaS, and hydroxyl value is 500～700mg KOH/g.
Embodiment 4
100g polyoxyethylene glycol (molecular weight 400) and the 3g vitriol oil are added mechanical stirring mixing in the there-necked flask that prolong is housed, put into oil bath and be warming up to 130 ℃, add 20g bagasse under whipped state, then insert the ultrasonic cell disruptor horn, open Vltrasonic device, at ultrasonic power 200W, under ultrasonic frequency 20kHz after ultrasonic 20min, there-necked flask is placed in the cooling termination reaction of ice-water bath, the residue rate of the liquefied product that obtains is 7.3%, viscosity is 600～1200mPaS, and hydroxyl value is 200～540mgKOH/g.
Embodiment 5
100g ethylene glycol and 6g p-methyl benzenesulfonic acid are added machine mechanical stirring mixing in the there-necked flask that prolong is housed, put into oil bath and be warming up to 140 ℃, add 30g bagasse under whipped state, then insert the ultrasonic cell disruptor horn, open Vltrasonic device, after ultrasonic 60min under ultrasonic power 100W, ultrasonic frequency 20kHz, there-necked flask is placed in the cooling termination reaction of ice-water bath, the residue rate of the liquefied product that obtains is 7.5%, viscosity is 400～850mPaS, and hydroxyl value is 360～600mg KOH/g.
Embodiment 6
80g polyoxyethylene glycol (molecular weight 400), 20g ethylene glycol and 3g p-methyl benzenesulfonic acid are added mechanical stirring mixing in the there-necked flask that prolong is housed, put into oil bath and be warming up to 150 ℃, add 10g bagasse under whipped state, then insert the ultrasonic cell disruptor horn, open Vltrasonic device, at ultrasonic power 200W, under ultrasonic frequency 20kHz after ultrasonic 40min, there-necked flask is placed in the cooling termination reaction of ice-water bath, the residue rate of the liquefied product that obtains is 5.9%, viscosity is 450～1050mPaS, and hydroxyl value is 200～350mg KOH/g.
Embodiment 7
80g polyoxyethylene glycol (molecular weight 400), 20g ethylene glycol and the 1g vitriol oil are added mechanical stirring mixing in the there-necked flask that prolong is housed, put into oil bath and be warming up to 110 ℃, add 20g bagasse under whipped state, then insert the ultrasonic cell disruptor horn, open Vltrasonic device, at power 100W, under frequency 20kHz after ultrasonic 90min, there-necked flask is placed in the cooling termination reaction of ice-water bath, the residue rate that records liquefied product is 4.5%, viscosity is 300～850mPaS, and hydroxyl value is 220～320mg KOH/g.
The comparative example:
(1) conventional oil bath liquefaction process: 80g polyoxyethylene glycol, 20g ethylene glycol and the 1g vitriol oil are added in the there-necked flask that prolong is housed, the mechanical stirring mixing, put into oil bath and be warming up to 110 ℃, add 20g bagasse under whipped state, isothermal reaction 90min, obtain product, the residue rate that records liquefied product is 16.3%.
(2) (CN102320921A) ultrasonic method such as Liao Bing: 100g ethylene glycol and 1g sulfuric acid are added in the there-necked flask that prolong is housed, the mechanical stirring mixing, add 20g Eucalyptus powder under whipped state, at ultrasonic power 2500W, under ultrasonic frequency 20kHz after ultrasonic 30min, the cooling termination reaction of frozen water, obtaining the residue rate is 13.7%, viscosity is 540～1240mPaS, and hydroxyl value is 380～740mg KOH/g.
As seen the present invention under the ultrasonic wave synergistic reaction than low reaction temperatures, lower-wattage, has realized higher transformation efficiency.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (8)
1. one kind is utilized ultrasonic wave to assist the fast liquefying plant biomass to prepare the method for polyvalent alcohol, and it is characterized in that comprising following steps: with 100 mass parts liquefying agents and 1～6 mass parts acid catalyst mixing, oil bath is heated to 110～150 ℃; Adding 5～30 mass parts plant biomass mixings, is that 100～800W, frequency are under the ul-trasonic irradiation of 20kHz at power, isothermal reaction 10～90min, and the cooling termination reaction of ice-water bath obtains plant polyatomic alcohol.
2. a kind of ultrasonic wave of utilizing according to claim 1 assists the fast liquefying plant biomass to prepare the method for polyvalent alcohol, it is characterized in that: described liquefying agent is polyoxyethylene glycol, or is the polyoxyethylene glycol of 1:1～100:1 and the mixture that low molecular polylol forms by mass ratio; Polyoxyethylene glycol used be average molecular mass be 200,400,600,800 and 1000 wherein a kind of; Low molecular polylol used is at least a of ethylene glycol, propylene glycol and glycerol.
3. a kind of ultrasonic wave of utilizing according to claim 1 assists the fast liquefying plant biomass to prepare the method for polyvalent alcohol, and it is characterized in that: described acid catalyst comprises at least a of hydrochloric acid, sulfuric acid, phosphoric acid and p-methyl benzenesulfonic acid.
4. a kind of ultrasonic wave of utilizing according to claim 1 assists the fast liquefying plant biomass to prepare the method for polyvalent alcohol, and it is characterized in that: described plant biomass is at least a of bagasse, maize straw, wheat straw, bamboo and straw.
5. a kind of ultrasonic wave of utilizing according to claim 4 assists the fast liquefying plant biomass to prepare the method for polyvalent alcohol, and it is characterized in that: described plant biomass is bagasse.
6. a kind of ultrasonic wave of utilizing according to claim 1 assists the fast liquefying plant biomass to prepare the method for polyvalent alcohol, and it is characterized in that: the particle diameter of described plant biomass is 20～120 orders.
7. a kind of ultrasonic wave of utilizing according to claim 6 assists the fast liquefying plant biomass to prepare the method for polyvalent alcohol, and it is characterized in that: the particle diameter of described plant biomass is 40～80 orders.
8. a kind of ultrasonic wave of utilizing according to claim 1 assists the fast liquefying plant biomass to prepare the method for polyvalent alcohol, and it is characterized in that: described ultrasonic power is 100～400W.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642512A (en) * | 2013-11-28 | 2014-03-19 | 福建农林大学 | Method for liquidizing biomass by virtue of ultrasonic wave in combination with microwave |
| CN113416106A (en) * | 2021-06-21 | 2021-09-21 | 山东农业大学 | Preparation method of liquefied bio-based coated controlled release material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040175806A1 (en) * | 2003-03-03 | 2004-09-09 | Battelle Memorial Institute | Methods of producing compounds from plant material |
| CN101172932A (en) * | 2006-11-01 | 2008-05-07 | 中国科学院过程工程研究所 | Method for producing biomass polyalcohol with plants stalk liquescence |
| CN101186560A (en) * | 2007-12-10 | 2008-05-28 | 中国科学院广州化学研究所 | Method for preparing polyatomic alcohol from crop straw |
| CN101260186A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院广州化学研究所 | Circulation liquefaction preparation method for polyether ester polyatomic alcohol by using bamboo powder as raw material |
| CN102320921A (en) * | 2011-05-12 | 2012-01-18 | 中科院广州化学有限公司 | Method for preparing biomass polylol by using ultrasonic waves and application thereof |
-
2013
- 2013-01-30 CN CN201310037271XA patent/CN103086844A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040175806A1 (en) * | 2003-03-03 | 2004-09-09 | Battelle Memorial Institute | Methods of producing compounds from plant material |
| CN101172932A (en) * | 2006-11-01 | 2008-05-07 | 中国科学院过程工程研究所 | Method for producing biomass polyalcohol with plants stalk liquescence |
| CN101186560A (en) * | 2007-12-10 | 2008-05-28 | 中国科学院广州化学研究所 | Method for preparing polyatomic alcohol from crop straw |
| CN101260186A (en) * | 2008-04-15 | 2008-09-10 | 中国科学院广州化学研究所 | Circulation liquefaction preparation method for polyether ester polyatomic alcohol by using bamboo powder as raw material |
| CN102320921A (en) * | 2011-05-12 | 2012-01-18 | 中科院广州化学有限公司 | Method for preparing biomass polylol by using ultrasonic waves and application thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103642512A (en) * | 2013-11-28 | 2014-03-19 | 福建农林大学 | Method for liquidizing biomass by virtue of ultrasonic wave in combination with microwave |
| CN103642512B (en) * | 2013-11-28 | 2016-05-11 | 福建农林大学 | A kind of method of ultrasonic-microwave coupling liquefying biomass |
| CN113416106A (en) * | 2021-06-21 | 2021-09-21 | 山东农业大学 | Preparation method of liquefied bio-based coated controlled release material |
| CN113416106B (en) * | 2021-06-21 | 2023-03-14 | 山东农业大学 | Preparation method of liquefied bio-based coated controlled release material |
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Application publication date: 20130508 |