CN103469662B - A kind of method applied ionic liquid-catalyzed hydrolysis and prepare nano-cellulose - Google Patents
A kind of method applied ionic liquid-catalyzed hydrolysis and prepare nano-cellulose Download PDFInfo
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- CN103469662B CN103469662B CN201310433104.7A CN201310433104A CN103469662B CN 103469662 B CN103469662 B CN 103469662B CN 201310433104 A CN201310433104 A CN 201310433104A CN 103469662 B CN103469662 B CN 103469662B
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Abstract
The invention discloses a kind of method applied ionic liquid-catalyzed hydrolysis and prepare nano-cellulose, paper pulp is joined in ionic liquid, under ul-trasonic irradiation, temperature is risen to 50 ~ 70 DEG C, after reaction 1 ~ 3h, with liquid nitrogen snap frozen process 20min; Then slowly melt, and temperature is risen to 50 ~ 70 DEG C; For several times, from turbid liquid, extract ionic liquid, raffinate high speed centrifugation purifying, obtains milky cellulose colloid to repetition liquid nitrogen snap frozen-slowly melt-warming temperature, through vacuum freeze drying 24h, obtains nano-cellulose powder.The present invention have little to equipment corrosion, environmental pollution is little, little to cellulose degradation damage, and the advantage such as nano-cellulose yield is high, ionic liquid is reusable, overcomes the shortcoming that nano-cellulose is prepared in traditional liquid acid.
Description
Technical field
The invention belongs to biomass cellulose field, be specifically related to a kind of method applied ionic liquid-catalyzed hydrolysis and prepare nano-cellulose.
Background technology
Cellulose be by D-glucopyranose ring each other with the linear macromolecule that β-Isosorbide-5-Nitrae-glycosidic bond connects, contain abundant renewable resource at occurring in nature.It is under suitable environmental condition, and glucosides can be made to rupture, and the degree of polymerization declines, and finally forms the very high nanofiber of degree of crystallinity (nanocrystalline cellulose is called for short NCC).NCC has huge specific area and surface atom number and special skin effect, and still has cellulosic crystal formation and character.Current NCC has been used as pharmaceutical carrier, nanometer strengthener, coating thickener, dispersant, drug excipient, food additives, cosmetic base, molecular filter etc.
The routine techniques of current preparation NCC generally all will relate to acid treatment process or alkali treatment process, and its preparation process is serious to equipment corrosion, big for environment pollution.Therefore, find a kind of eco-friendly method preparing NCC in a mild condition and become the difficult problem that must solve in nano-cellulose production process.The country such as the U.S., Japan, Britain drops into a large amount of man power and materials in this field.
Ionic liquid is the liquid be made up of anions and canons completely, and compared with traditional chemical solvent, ionic liquid has that vapour pressure is little, non-volatile, non-combustible, toxicity is little, can be used in vacuum systems; Solubility property is good, shows good solvability to inorganic and organic material; Be easy to and other separating substances, can recycle; Electrical conductivity is high, potential windows is large (can reach 4 V); Heat endurance and chemical stability good, there is very wide liquid state range (-96 ~ 300 DEG C); Designability is strong.Due to the excellent properties of ionic liquid, it is made to be used widely in fields such as separation, catalysis, electrochemistry, organic syntheses.
Summary of the invention
The object of the invention is to provide a kind of method applied ionic liquid-catalyzed hydrolysis and prepare nano-cellulose, have little to equipment corrosion, environmental pollution is little, to cellulose degradation damage little, and the advantage such as nano-cellulose yield is high, ionic liquid is reusable, overcome the shortcoming that nano-cellulose is prepared in traditional liquid acid.
For achieving the above object, the present invention adopts following technical scheme:
A kind ofly apply the method that ionic liquid-catalyzed hydrolysis prepares nano-cellulose and comprise the following steps:
(1) taking 2 ~ 5g paper pulp joins in 50 ~ 100ml ionic liquid (chlorination 1-allyl-3-methylimidazole [Amim] Cl or chlorination 1-butyl-3-methylimidazole [Bmim] Cl or bromination 1-octyl group-3-methylimidazole [Omim] Br or 1-butyl-3-methylimidazolium bromide [Bmim] Br), under ul-trasonic irradiation, temperature is risen to 50 ~ 70 DEG C, after reaction 1 ~ 3h, with liquid nitrogen snap frozen process 20min; Then slowly melt, and temperature is risen to 50 ~ 70 DEG C;
(2) after repeating liquid nitrogen snap frozen-the slowly melt-warming temperature 2 ~ 6 times of step (1), from turbid liquid, extract ionic liquid, raffinate high speed centrifugation purifying, obtains milky cellulose colloid, through vacuum freeze drying 24h, obtain nano-cellulose powder.
The ultrasonic power of step (1) is 300 ~ 500W.
Remarkable advantage of the present invention is: the present invention have little to equipment corrosion, environmental pollution is little, to cellulose degradation damage little, nano-cellulose yield is high, length, width distribution are more concentrated, the advantages such as ionic liquid is reusable, overcome traditional liquid acid and prepare the shortcomings such as nano-cellulose is large to equipment corrosion, big for environment pollution.
Detailed description of the invention
embodiment 1
Taking 2g paper pulp to join in ionic liquid chlorination 1-allyl-3-methylimidazole [Amim] Cl of 50ml, is, under the ul-trasonic irradiation of 300W, temperature is risen to 70 DEG C at power, and after reacting 1h, will with liquid nitrogen snap frozen process 20min; Then slowly melt, and temperature is risen to 70 DEG C.After repetition liquid nitrogen snap frozen-slowly melt-warming temperature 2 times, ionic liquid will be extracted from turbid liquid, by further for raffinate high speed centrifugation purifying, obtain milky cellulose colloid through vacuum freeze drying 24h, be i.e. obtained nano-cellulose powder.
Cellulosic morphosis analyzed by the Morfi Compact fibre morphology analyzer utilizing French Techpap company to produce.Record average length 589 nm of this nano-cellulose; Mean breadth 46 nm; Length is mainly distributed in 450 ~ 750nm, and length 550 ~ 650nm accounts for 93.2%.
embodiment 2
Taking 5g paper pulp to join in ionic liquid bromination 1-octyl group-3-methylimidazole [Omim] Br of 100ml, is, under the ul-trasonic irradiation of 500W, temperature is risen to 50 DEG C at power, and after reacting 3h, will with liquid nitrogen snap frozen process 20min; Then slowly melt, and temperature is risen to 50 DEG C.After repetition liquid nitrogen snap frozen-slowly melt-warming temperature 5 times, ionic liquid will be extracted from turbid liquid, by further for raffinate high speed centrifugation purifying, obtain milky cellulose colloid through vacuum freeze drying 24h, be i.e. obtained nano-cellulose powder.
Cellulosic morphosis analyzed by the Morfi Compact fibre morphology analyzer utilizing French Techpap company to produce.Record average length 381 nm of this nano-cellulose; Mean breadth 32 nm; Length is mainly distributed in 300 ~ 450nm, and length 350 ~ 400nm accounts for 90.8%.
embodiment 3
The paper pulp taking 3g joins in chlorination 1-butyl-3-methylimidazole [Bmim] Cl of 80ml, is, under the ul-trasonic irradiation of 400W, temperature is risen to 60 DEG C at power, and after reacting 2h, will with liquid nitrogen snap frozen process 20min; Then slowly melt, and temperature is risen to 60 DEG C.After repetition liquid nitrogen snap frozen-slowly melt-warming temperature 4 times, ionic liquid will be extracted from turbid liquid, by further for raffinate high speed centrifugation purifying, obtain milky cellulose colloid through vacuum freeze drying 24h, be i.e. obtained nano-cellulose powder.
Cellulosic morphosis analyzed by the Morfi Compact fibre morphology analyzer utilizing French Techpap company to produce.Record average length 508 nm of this nano-cellulose; Mean breadth 39 nm; Length is mainly distributed in 400 ~ 650nm, and length 450 ~ 550nm accounts for 94.3%.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (3)
1. apply the method that nano-cellulose is prepared in ionic liquid-catalyzed hydrolysis, it is characterized in that: comprise the following steps:
(1) taking 2 ~ 5g paper pulp joins in 50 ~ 100ml ionic liquid, under ul-trasonic irradiation, temperature is risen to 50 ~ 70 DEG C, after reaction 1 ~ 3h, with liquid nitrogen snap frozen process 20min; Then slowly melt, and temperature is risen to 50 ~ 70 DEG C;
(2) after repeating liquid nitrogen snap frozen-the slowly melt-warming temperature 2 ~ 6 times of step (1), from turbid liquid, extract ionic liquid, raffinate high speed centrifugation purifying, obtains milky cellulose colloid, through vacuum freeze drying 24h, obtain nano-cellulose powder.
2. the method for nano-cellulose is prepared in the ionic liquid-catalyzed hydrolysis of application according to claim 1, it is characterized in that: the ultrasonic power of step (1) is 300 ~ 500W.
3. the method for nano-cellulose is prepared in the ionic liquid-catalyzed hydrolysis of application according to claim 1, it is characterized in that: the ionic liquid described in step (1) is the one in chlorination 1-allyl-3-methylimidazole, chlorination 1-butyl-3-methylimidazole, bromination 1-octyl group-3-methylimidazole, 1-butyl-3-methylimidazolium bromide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103740867A (en) * | 2014-01-02 | 2014-04-23 | 上海大学 | Method for preparing glucose by hydrolyzing straw celluloses |
| CN105220552B (en) * | 2015-09-09 | 2017-03-29 | 郑州轻工业学院 | Using the method for the asymmetric Gemini ionic liquid extracts cellulose of imidazoles |
| CN107761426B (en) * | 2016-08-17 | 2019-11-12 | 中国科学院化学研究所 | It is a kind of to utilize freezing, the grinding method for preparing low polymerization degree cellulose and products thereof and application |
| CN110105455B (en) * | 2019-05-21 | 2022-02-11 | 河北科技大学 | Ionic liquid, application thereof, cellulose nanocrystal material and preparation method thereof |
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| CN101182686A (en) * | 2007-12-07 | 2008-05-21 | 华南理工大学 | Decrystallizing method of cellulose in ion liquid |
| CN101298620A (en) * | 2007-05-10 | 2008-11-05 | 河南科技大学 | Method for preparing ethanol by one-step fermentation after ion liquid stage treatments from native cellulose material |
| CN101580522A (en) * | 2009-06-11 | 2009-11-18 | 大连工业大学 | Method for separating lignin and cellulose from lignocellulose by using ionic liquid solvent |
| CN101949103A (en) * | 2010-10-08 | 2011-01-19 | 东北林业大学 | Preparation method of straw micro-nano cellulose |
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| JP5676860B2 (en) * | 2008-10-02 | 2015-02-25 | 株式会社Kri | Polysaccharide nanofibers and production method thereof, ionic liquid solution containing polysaccharide nanofibers and composite material |
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Patent Citations (4)
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| CN101298620A (en) * | 2007-05-10 | 2008-11-05 | 河南科技大学 | Method for preparing ethanol by one-step fermentation after ion liquid stage treatments from native cellulose material |
| CN101182686A (en) * | 2007-12-07 | 2008-05-21 | 华南理工大学 | Decrystallizing method of cellulose in ion liquid |
| CN101580522A (en) * | 2009-06-11 | 2009-11-18 | 大连工业大学 | Method for separating lignin and cellulose from lignocellulose by using ionic liquid solvent |
| CN101949103A (en) * | 2010-10-08 | 2011-01-19 | 东北林业大学 | Preparation method of straw micro-nano cellulose |
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