CN109354663A - A method of polyether polyol is prepared based on pretreated agricultural crop straw liquefaction is irradiated - Google Patents
A method of polyether polyol is prepared based on pretreated agricultural crop straw liquefaction is irradiated Download PDFInfo
- Publication number
- CN109354663A CN109354663A CN201811197110.6A CN201811197110A CN109354663A CN 109354663 A CN109354663 A CN 109354663A CN 201811197110 A CN201811197110 A CN 201811197110A CN 109354663 A CN109354663 A CN 109354663A
- Authority
- CN
- China
- Prior art keywords
- agricultural crop
- crop straw
- polyether polyol
- liquefaction
- pretreated
- 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.)
- Pending
Links
- 239000010902 straw Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229920000570 polyether Polymers 0.000 title claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 22
- 229920005862 polyol Polymers 0.000 title claims abstract description 16
- 150000003077 polyols Chemical class 0.000 title claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000001678 irradiating effect Effects 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000001954 sterilising effect Effects 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 36
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 240000008042 Zea mays Species 0.000 claims description 19
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 19
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 19
- 235000005822 corn Nutrition 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 235000011187 glycerol Nutrition 0.000 claims description 10
- 239000010907 stover Substances 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 238000004917 polyol method Methods 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- 230000005251 gamma ray Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000012467 final product Substances 0.000 abstract 1
- 241000196324 Embryophyta Species 0.000 description 15
- 229920002488 Hemicellulose Polymers 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 150000005846 sugar alcohols Polymers 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- 241000209094 Oryza Species 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000002657 fibrous material Substances 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000013475 authorization Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method of polyether polyol is prepared based on pretreated agricultural crop straw liquefaction is irradiated, it is the segment that drying agricultural crop straw is first cut into 2-4cm long, be placed in irradiation devices and carries out irradiation pretreatment, irradiation dose is 800~1200kGy, take 100 parts of organic solvent, 1~5 part of the concentrated sulfuric acid by weight again, by irradiating pretreated 15~30 parts of agricultural crop straw, it mixes, it is subsequently placed in high-pressure sterilizing pot, at 118~121 DEG C, cooling polyether polyol to obtain the final product after 30~60min is reacted.This method is easy to operate, and condensing temperature is low, and required time is short, and liquefied fraction is high.
Description
Technical field
The invention belongs to biomass comprehensives to utilize field, be related to a kind of side of agricultural crop straw liquefaction preparation polyether polyol
Method, it is especially a kind of based on the method for irradiating pretreated agricultural crop straw liquefaction preparation polyether polyol.
Background technique
Agricultural crop straw amount is big, cheap, easy to collect, and is very important lignocellulose-like biomass material.
China ploughs more than 1,500,000,000 mu, the annual stalk for generating about 700,000,000 tons, these stalks remove a part of direct returning to farmland as fertilizer and
Small part as animal feed outside, greatly all directly burning, not only cause serious environmental pollution, also waste
Valuable resource.The main chemical compositions of stalk are cellulose, hemicellulose and lignin, and three accounts for the 90% of stalk quality
More than.Stalk liquefaction is a kind of method of efficient stalk resource comprehensive utilization.Although the ingredient of stalk is changed than petroleum etc.
Complicated more of stone resource, but and the hydrocarbon containing great amount of hydroxy group, can be transformed by liquefied method
The industrial chemicals that can be utilized, for synthesizing various high molecular materials.
Convert solid-state stalk material to the process of liquid, be broadly divided into high temperature and pressure liquefaction, rapidly pyrolysing and liquefying and often
Press catalytic liquefaction.First two technology is mainly for the preparation of bio-fuel-oil and chemical products etc., and normal pressure catalytic liquefaction is often with polyalcohol
Or phenol is liquefier, the liquefaction products of acquisition can partially substitute polyester or polyether polyol from petroleum chemicals.Using
After polyalcohol handles lignocellulose-like biomass as liquefier, obtained product is mainly that the alcoholysis of lignocellulose produces
Object, due to containing in the main chemical structure of lignocellulose-like biomass and hydroxyl structure, Ke Yihe in polyalcohol liquefier
Isocyanates, which reacts, is made the polyurethane material that function admirable has biological degradability again.
Use polyalcohol liquefaction of lignocellulose material generally with polyethylene glycol (PEG), glycerol etc. for liquefied reagent, with sulphur
Acid is that catalyst liquefies under normal pressure at 150-200 DEG C, and polyethylene glycol, glycerol inherently prepare the common original of polyurethane
Material, product can directly be reacted with isocyanates without separation after plant fiber is degraded wherein prepares polyurethane, after reducing
The problem that phase isolates and purifies.But current polyalcohol liquefied straw method there is also some problems: on the one hand, due to wood fibre
Plain close structure, there are very strong resistance so that liquefaction of corn straw that there are liquefying times is long, temperature is high, it is at high cost, complicated for operation,
The problems such as low efficiency.Two aspects, in liquefaction process, liquid-solid ratio is usually all higher, so that the dosage of liquefier is larger.Due to straw
Stalk class raw material absorbs the very capable of liquefaction solvent, if not having to higher liquid-solid ratio, solvent just can not be abundant by plant fiber
Infiltration cannot be carried out sufficiently and uniformly so as to cause reaction.And if liquefaction reaction progress is insufficient, plant fiber material is not
Energy fully degraded, can also make the final liquefaction products i.e. hydroxyl value of plant polyatomic alcohol relatively low, cannot meet very well and prepare poly- ammonia
The requirement of ester.For example, [Xu Yang, the liquefaction of Tang fruit east straw generate technical study [J] Huaiyin teacher of polyalcohol by Xu Yang, Tang Guodong
Model institute journal (natural science edition), 2017,16 (1): 39-43] straw is pre-processed with microwave, glycerine is liquefaction
Agent, the concentrated sulfuric acid as catalyst, investigated respectively straw partial size under different condition, liquid-solid ratio, the reaction time, catalyst content and
Influence of the liquefaction reaction temperature to liquefaction efficiency obtains the Optimizing Process Parameters of straw liquefaction polyalcohol are as follows: straw partial size is 20
~80 mesh, liquid-solid ratio 9:1, concentrated sulfuric acid content 6%, liquefying time 1h, 160 DEG C of temperature, the liquefied fraction for the system that liquefies is
81.4%.Wang Ning etc. [Wang Ning, Tian Chunrong, woods know microwave liquefaction research [J] biomass chemical process of the rice straw such as gorgeous,
2013,47 (1): 33-38] using phenol as liquefier, glycerol is auxiliary liquefier, to rice straw under sulphuric acid catalysis effect
Microwave liquefaction is carried out, show that in microwave power 500W, liquid-solid ratio 7: 1, m (phenol): m (glycerol) be 4:1, concentrated sulfuric acid dosage is
5%, 150 DEG C, reaction time 22.5min, residue obtained rate is minimum, is 7.17%.Lu Tingting etc. is with polyethylene glycol 400 (PEG-
400) and glycerine is mixed liquor agent, carries out liquefaction 150min to bamboo wood scrap material at 150 DEG C, obtains rich in active group
The deficiencies of liquefaction products, residue rate is but long there is also the reaction time down to 5%, at high cost.For another example, Authorization Notice No. CN
The Chinese patent of 101429282B discloses a kind of vegetable fiber-based polyether polyol and preparation method thereof, this method utilize without
Raw material pretreated liquefaction produces polyether polyol, and polyether polyol produced can be used for producing function of heat insulation
Hard polyurethane foam.But closely due to straw cell wall structure, liquefied reagent is difficult to penetrate into plant fiber original
Material.Therefore, this method is added by dry plant fiber material in the liquefied reagent for having been heated to 120~160 DEG C,
Plant fiber material is added by several times；Every time after charging, temperature before charging is risen to；Keep 10~20min of thermotonus, charging
After, 20~120min of thermotonus is kept, solid base to reaction system pH-value is added and is in neutrality to improve liquefaction products
Yield, complicated for operation and reaction time are long.The Chinese patent application of Publication No. CN101172932A discloses a kind of plant straw
The method that stalk liquefaction prepares biomass polyalcohol is first to handle stalk with the mode of steam blasting, destroys stalk institutional framework, make
Liquefied reagent is easily accessible, to reduce liquefaction condition, improves liquefaction effect, by the stalk of Steam explosion treatment,
Liquefaction effect improves 8%-15% than the raw material without Steam explosion treatment, can be seen that immediately from the effect of embodiment
By Steam explosion treatment, after corn stover and wheat stalk liquefaction, however it remains 10% or so residue rate.
In addition, lignocellulosic material complicated composition, the components such as cellulose, hemicellulose and lignin therein and liquefaction
Reagent reflex action has larger difference, and lignin and hemicellulose relatively easily liquefy, and cellulose is due to crystallinity height, and liquefaction is more
Difficulty will realize that stalk integrally liquefies, and be bound to liquefaction reaction temperature and time to be increased.But the hemicellulose in stalk
It as low molecular compound, is easy to that oxidation reaction occurs in liquefaction, forms carboxylic acid, so that target product composition be made to become
Complexity is unfavorable for later use.In order to solve three big main component (cellulose, hemicellulose and lignin) liquid in stalk
Change nonsynchronous problem, Authorization Notice No. is that the Chinese patent of CN101245566B proposes a kind of wooden fibre of phenol selectivity liquefaction
The method for tieing up element, 50% or more cellulose remains in liquefied residue in the method for selective liquefaction of lignocellulose with phynol
In, and 70% or more hemicellulose and lignin conversion are liquid product.What selective liquefaction of lignocellulose with phynol obtained
Liquefaction products can produce biology base phenolic resin, and not liquefied cellulose can be used for simultaneous saccharification and fermentation production alcohol fuel,
To realize that lignocellulosic sources high added value comprehensively utilizes, but fiber is isolated from liquefied hemicellulose and lignin
Element is relatively difficult.The Chinese patent of Authorization Notice No. CN101885825B discloses a kind of plant fiber-based polylol and preparation side
Method and application, preparation method include that the component of plant fiber material splits two steps of liquefaction with plant fiber material.The party
Method removes the hemicellulose in plant fiber material in the way of high-temperature high-voltage reaction or room temperature alkali process, makes plant fiber
Raw material is more loose, is conducive to the infiltration of liquefier, reduces resulting liquefaction products complicated composition.However, plant fiber is former
For material under high-temperature and high-pressure conditions, hemicellulose degradation not fully, and under the conditions of room temperature alkali process, can also make a part of wood
Quality is dissolved into lye, degrades utilization rate of the plant fiber as liquefaction raw material.
In conclusion that there are liquefying times is long, complicated for operation, liquefier dosage is big, efficiency for existing liquefaction of corn straw technology
The problems such as low.
Summary of the invention
The object of the present invention is in view of the above shortcomings of the prior art, provide a kind of based on the pretreated crops of irradiation
The method of liquefaction of corn straw preparation polyether polyol.
In order to achieve the above object, the technical solution adopted by the present invention is that: one kind is based on the pretreated agricultural crop straw liquid of irradiation
Change the method for preparation polyether polyol, the method steps are as follows:
(1) agricultural crop straw is taken, segment is cut into and is placed in irradiation devices, is used under the conditions of natural room temperature60Co- gamma-rays
Irradiation is pre-processed, and irradiation dose is 800kGy~1200kGy；
(2) 100 parts of organic solvent, 1~5 part of catalyst are taken by weight and by irradiating pretreated agricultural crop straw 15
It~30 parts, is uniformly mixed, is subsequently placed in high-pressure sterilizing pot, it is cooling to get polyethers in 118~121 DEG C of 30~60min of reaction
Polyalcohol；
Wherein, above-mentioned catalyst is the concentrated sulfuric acid (mass fraction 98%).
Agricultural crop straw in above-mentioned steps (1) refer to by dry naturally or artificial drying after water content less than 10% straw
Stalk is cut into 2-4cm long, which is one or more of rice straw, corn stover or rape stalk.
Organic solvent in above-mentioned steps (2) is one of ethylene glycol, diethylene glycol (DEG), polyethylene glycol or glycerine or several
Kind.Preferably, the molecular weight of polyethylene glycol is 200~1000.
Compared with prior art, the invention has the benefit that (1) destroys the wooden fibre of stalk by irradiation pretreatment
The structure of element is tieed up, so that liquefied reagent is more easier to react with stalk, so that liquefying speed is fast, required temperature is low, and liquefied fraction is high.
Moreover, simple using irradiation preprocess method, labor intensity is low, pollution-free.(2) by irradiation pretreatment, part can be removed
(e.g., the hemicellulose level in the corn stover by 1000kGy radiation treatment is dropped to hemicellulose by 15.56%
5.75%), reduce the probability that hemicellulose forms carboxylic acid in liquefaction reaction, target product ingredient is simpler.(3) with it is existing
Report liquefaction need to compare using oil bath with high-pressure reactor, equipment required for the present invention is simple, and safety is high, it is only necessary to use
High-pressure steam sterilizing pan can be achieved with.(4) after high dosage irradiation processing, stalk becomes fragile broken, can make without further crushing
With, and mobility increases, and the ability for absorbing liquefaction solvent dies down, and wettability is greatly enhanced, solid-to-liquid ratio can be reduced,
Save liquefied reagent.
Specific embodiment
Embodiment 1
Corn stover is collected, the segment of 2-4cm long is cut into after drying naturally, is placed in irradiation devices, in natural room temperature item
It is used under part60Co- gamma-ray irradiation is pre-processed, irradiation dose 1200kGy；Taking polyethylene glycol (molecular weight by weight
400) 100 parts, 3 parts of the concentrated sulfuric acid and process irradiate pretreated 25 parts of corn stover, are uniformly mixed, are subsequently placed in high-pressure sterilizing pot
It is interior, it is cooling to get polyether polyol in 118 DEG C of reaction 60min.
The present embodiment corn stover liquefied fraction is 93.2%.And it crushed without pretreated corn stalk raw material is irradiated
After 20 meshes, same solvent and catalyst are added in same ratio, is reacted under identical condition, corn stover is absolutely not
Liquefaction.
Embodiment 2
Corn and rape stalk are collected, the segment of 2-4cm long is cut into after artificial drying, is placed in irradiation devices, in nature
It uses under room temperature60Co- gamma-ray irradiation is pre-processed, irradiation dose 1000kGy；By weight, ethylene glycol and two are taken
Totally 100 parts of mixture (ethylene glycol: diethylene glycol (DEG)=4:1), 5 parts of the concentrated sulfuric acid and the process of glycol irradiate pretreated corn and rape
It 20 parts of stalk, is uniformly mixed, is subsequently placed in high-pressure sterilizing pot, it is cooling to get polyether polyol in 121 DEG C of reaction 30min.
The present embodiment corn and rape stalk liquefied fraction are 91.6%.Without the pretreated corn of irradiation and rape stalk
After raw material crushed 20 meshes, same solvent and catalyst are added in same ratio, is reacted under identical condition, stalk is complete
It does not liquefy entirely.
Embodiment 3
Corn, rape and rice straw are collected, the segment of 2-4cm long is cut into after drying naturally, is placed in irradiation devices,
It is used under the conditions of natural room temperature60Co- gamma-ray irradiation is pre-processed, irradiation dose 800kGy；Taking polyethylene glycol by weight
100 parts of (molecular weight 800), 1 part of the concentrated sulfuric acid and process irradiate pretreated 30 parts of stalk, are uniformly mixed, are subsequently placed in high pressure and go out
It is cooling to get polyether polyol in 120 DEG C of reaction 40min in bacterium pot.
The present embodiment corn, rape and rice straw liquefied fraction are 90.4%.Without the pretreated corn of irradiation, rape
And after rice straw raw material crushed 20 meshes, same solvent and catalyst, under identical condition are added in same ratio
Reaction, stalk absolutely not liquefy.
Embodiment 4
Rape stalk is collected, the segment of 2-4cm long is cut into after drying naturally, is placed in irradiation devices, in natural room temperature item
It is used under part60Co- gamma-ray irradiation is pre-processed, irradiation dose 900kGy；Taking polyethylene glycol (molecular weight by weight
1000) and totally 100 parts of glycerine (polyethylene glycol (molecular weight 1000): glycerine=1:1), 4 parts of the concentrated sulfuric acid and process irradiation are pre-
15 parts of the rape stalk of processing is uniformly mixed, is subsequently placed in high-pressure sterilizing pot, cooling to get poly- in 120 DEG C of reaction 50min
Ethoxylated polyhydric alcohol.
The present embodiment rape stalk liquefied fraction is 92.7%.It crushed 20 without pretreated rape stalk raw material is irradiated
After mesh, same solvent and catalyst are added in same ratio, is reacted under identical condition, stalk absolutely not liquefies.
In the various embodiments described above, with reference to Li Xueqin et al., (Li Xueqin, Li Xiangyu, QiWei wait to the measuring method of liquefied fraction
Research [J] solar energy journal of poplar bits multicomponent solvent liquefaction technique, 2015,36 (4): 971-975) method carry out.
Have been described in detail above embodiments of the present invention, but this is only to facilitate the example for understanding and lifting, it should not be by
It is considered as and limits the scope of the present invention.Equally, any person of ordinary skill in the field can technology according to the present invention
Various possible equivalent changes or replacement are made in the description of scheme and its preferred embodiment, but all these changes or replacement are all
It should belong to scope of protection of the claims of the invention.
Claims (6)
1. a kind of based on the method for irradiating pretreated agricultural crop straw liquefaction preparation polyether polyol, which is characterized in that the party
Steps are as follows for method:
(1) agricultural crop straw is taken, segment is cut into and is placed in irradiation devices, is used under the conditions of natural room temperature60Co- gamma-ray irradiation
It is pre-processed, irradiation dose is 800kGy~1200kGy；
(2) 100 parts of organic solvent, 1~5 part of catalyst are taken by weight and by irradiating pretreated agricultural crop straw 15~30
Part, it is uniformly mixed, is subsequently placed in high-pressure sterilizing pot, it is cooling to get polyether polyols in 118~121 DEG C of 30~60min of reaction
Alcohol；
Wherein, above-mentioned catalyst is the concentrated sulfuric acid.
2. as described in claim 1 a kind of based on the side for irradiating pretreated agricultural crop straw liquefaction preparation polyether polyol
Method, which is characterized in that the agricultural crop straw in the step (1) refer to by dry naturally or artificial drying after water content be less than
10% stalk.
3. as claimed in claim 2 a kind of based on the side for irradiating pretreated agricultural crop straw liquefaction preparation polyether polyol
Method, which is characterized in that the agricultural crop straw is one or more of rice straw, corn stover or rape stalk.
4. as described in claim 1 a kind of based on the side for irradiating pretreated agricultural crop straw liquefaction preparation polyether polyol
Method, which is characterized in that the organic solvent in the step (2) is one of ethylene glycol, diethylene glycol (DEG), polyethylene glycol or glycerine
Or it is several.
5. as claimed in claim 4 a kind of based on the side for irradiating pretreated agricultural crop straw liquefaction preparation polyether polyol
Method, which is characterized in that the molecular weight of the polyethylene glycol is 200~1000.
6. as described in claim 1 a kind of based on the side for irradiating pretreated agricultural crop straw liquefaction preparation polyether polyol
Method, which is characterized in that be cut into segment in the step (1) and refer to and be cut into 2-4cm long.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811197110.6A CN109354663A (en) | 2018-10-15 | 2018-10-15 | A method of polyether polyol is prepared based on pretreated agricultural crop straw liquefaction is irradiated |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811197110.6A CN109354663A (en) | 2018-10-15 | 2018-10-15 | A method of polyether polyol is prepared based on pretreated agricultural crop straw liquefaction is irradiated |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109354663A true CN109354663A (en) | 2019-02-19 |
Family
ID=65349343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811197110.6A Pending CN109354663A (en) | 2018-10-15 | 2018-10-15 | A method of polyether polyol is prepared based on pretreated agricultural crop straw liquefaction is irradiated |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109354663A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316253A (en) * | 2021-11-15 | 2022-04-12 | 浙江大学 | Plant-based polyether polyol, and preparation method and application thereof |
| CN115612390A (en) * | 2022-09-29 | 2023-01-17 | 深圳陆城装饰设计工程有限公司 | High emulsification polyurethane mortar terrace coating structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617821A (en) * | 2012-04-17 | 2012-08-01 | 中国工程物理研究院化工材料研究所 | Polyurethane foaming plastic taking rice hull as raw material as well as preparation method of polyurethane foaming plastic |
| CN102633886A (en) * | 2011-02-11 | 2012-08-15 | 李翠花 | Method for preparing plant-based polyether polyol by straw liquefaction |
| CN104017157A (en) * | 2009-06-16 | 2014-09-03 | 亨斯迈国际有限责任公司 | Release compositions for lignocellulosic composites |
| CN105238021A (en) * | 2015-09-18 | 2016-01-13 | 滁州市莎朗新材料科技有限公司 | Heatproof plant type soft polyurethane foam for seamless wallpaper, and preparation method thereof |
| CN105601945A (en) * | 2016-02-01 | 2016-05-25 | 上海应用技术学院 | Method for preparing bio-based polyether polyol by carrying out microwave-assisted liquefaction on rape stalks |
-
2018
- 2018-10-15 CN CN201811197110.6A patent/CN109354663A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017157A (en) * | 2009-06-16 | 2014-09-03 | 亨斯迈国际有限责任公司 | Release compositions for lignocellulosic composites |
| CN102633886A (en) * | 2011-02-11 | 2012-08-15 | 李翠花 | Method for preparing plant-based polyether polyol by straw liquefaction |
| CN102617821A (en) * | 2012-04-17 | 2012-08-01 | 中国工程物理研究院化工材料研究所 | Polyurethane foaming plastic taking rice hull as raw material as well as preparation method of polyurethane foaming plastic |
| CN105238021A (en) * | 2015-09-18 | 2016-01-13 | 滁州市莎朗新材料科技有限公司 | Heatproof plant type soft polyurethane foam for seamless wallpaper, and preparation method thereof |
| CN105601945A (en) * | 2016-02-01 | 2016-05-25 | 上海应用技术学院 | Method for preparing bio-based polyether polyol by carrying out microwave-assisted liquefaction on rape stalks |
Non-Patent Citations (2)
| Title |
|---|
| FERDOUS KHAN: "γ-Radiation Induced Changes in the Physical and Chemical Properties of Lignocellulose", 《BIOMACROMOLECULES》 * |
| 张春艳: "辐照预处理对油菜秸秆降解产糖效果的影响及机理研究", 《中国博士学位论文全文数据库工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316253A (en) * | 2021-11-15 | 2022-04-12 | 浙江大学 | Plant-based polyether polyol, and preparation method and application thereof |
| CN115612390A (en) * | 2022-09-29 | 2023-01-17 | 深圳陆城装饰设计工程有限公司 | High emulsification polyurethane mortar terrace coating structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen | Lignocellulose biorefinery engineering: principles and applications | |
| CN101805629B (en) | Method for producing fuel oil by biomass hydrothermal liquefaction | |
| CN102702144B (en) | Method for preparing furan or furfural compound from biomass cellulose | |
| CN101586136B (en) | Method of high-efficiency pretreatment on biomass | |
| Ibrahim | Pretreatment of straw for bioethanol production | |
| CN100484648C (en) | Household gabbage chemical stability treatment method | |
| CN102153528B (en) | Method for preparing furfural, polyether polyalcohol, phenolic resin and nanometer silicon dioxide from straw | |
| CN101708844B (en) | Method for preparing jatropha curcas shell-based activated carbon | |
| CN104004582A (en) | Method for preparing bio-oil reactant and bio-oil from lignocellulosic biomass | |
| CN105330869B (en) | A kind of method for hydrolysis of lignocellulose raw material | |
| CN111499454A (en) | Method for converting domestic wet garbage into humic acid organic fertilizer with high added value by hydrothermal catalysis method | |
| CN109354663A (en) | A method of polyether polyol is prepared based on pretreated agricultural crop straw liquefaction is irradiated | |
| CN106191135A (en) | Lignocellulose is the biorefinery method of raw material coproduction multi-product | |
| CN101407727A (en) | Method for preparing biomass liquefied oil by biomass catalytic liquefaction | |
| CN102321993B (en) | Pretreatment method for biomass fiber material | |
| CN105000981A (en) | Carbonized particle fermented organic fertilizer and preparation method therefor | |
| CN101805777B (en) | Poly-generation method for steam-exploded primary refining of dioscorea raw materials | |
| CN109321607A (en) | The method for preparing biogas using wood fiber raw material anaerobic fermentation | |
| Ganorkar et al. | Waste valorization of water hyacinth using biorefinery approach: a sustainable route | |
| CN104774636A (en) | Preparation method of biological oil | |
| CN101691494B (en) | Method for circulating and liquefying the mixture of plant biomass and waste polyester in supercritical fluid | |
| CN101850958A (en) | Method for improving yield of biomass porous carbon | |
| FI129396B (en) | Porous, formable growing substrate and method for manufacturing the same | |
| CN102092681A (en) | CO2 removing process for hydrogen production through biomass gasification in supercritical water | |
| Sun et al. | Effect of TEMPO and characterization of bio-oil from cellulose liquefaction in supercritical ethanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190219 |
|
| RJ01 | Rejection of invention patent application after publication |