CN103469662A - Method for preparing nano cellulose by catalyzing and hydrolyzing ionic liquid - Google Patents
Method for preparing nano cellulose by catalyzing and hydrolyzing ionic liquid Download PDFInfo
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- CN103469662A CN103469662A CN2013104331047A CN201310433104A CN103469662A CN 103469662 A CN103469662 A CN 103469662A CN 2013104331047 A CN2013104331047 A CN 2013104331047A CN 201310433104 A CN201310433104 A CN 201310433104A CN 103469662 A CN103469662 A CN 103469662A
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Abstract
The invention discloses a method for preparing nano cellulose by catalyzing and hydrolyzing ionic liquid. The method comprises the following steps: adding paper pulp into the ionic liquid, raising the temperature to 50-70 DEG C under the effect of ultrasonic, reacting for 1-3 hours, quickly freezing for 20min by using liquid nitrogen, and then slowly melting, raising the temperature to 50-70 DEG.C; repeating the operations of quick-freezing by using the liquid nitrogen, slowly melting and raising temperature for a plurality of times, extracting ionic liquid from a suspension, centrifuging and purifying residual liquid to obtain milky cellulose colloid, freezing and drying in vacuum for 24 hours to obtain nano-crystalline cellulose powder. The method disclosed by the invention is small in equipment corrosivity, small in environment pollution, small in cellulose degradation damage and high in nano cellulose yield, the ionic liquid can be reused, and the defect that the traditional liquid acid is used to prepare the nano cellulose is overcome.
Description
Technical field
The invention belongs to the biomass cellulose field, be specifically related to a kind of method that ionic liquid-catalyzed hydrolysis prepares nano-cellulose of applying.
Background technology
Cellulose is to connect with β-Isosorbide-5-Nitrae-glycosidic bond the linear macromolecule formed each other by D-glucopyranose ring, at occurring in nature, contains abundant renewable resource.It can make the glucosides fracture under suitable environmental condition, and the degree of polymerization descends, and finally forms the nanofiber that degree of crystallinity is very high (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.NCC has been used as pharmaceutical carrier, nanometer strengthener, coating thickener, dispersant, drug excipient, food additives, cosmetic base, molecular filter etc. at present.
The routine techniques of preparation NCC generally all will relate to acid treatment process or alkali treatment process at present, and its preparation process is serious to equipment corrosion, big for environment pollution.Therefore, find a kind of eco-friendly method for preparing NCC under temperate condition and become the difficult problem that must solve in the nano-cellulose production process.The countries such as the U.S., Japan, Britain drop into a large amount of man power and materials in this field.
Ionic liquid is the liquid be comprised of the yin, yang ion fully, with traditional chemical solvent, compares, and 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, and inorganic and organic material are shown to good solvability; 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 are good, have very wide liquid scope (96 ~ 300 ℃); Designability is strong etc.Due to the excellent properties of ionic liquid, it is 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 that ionic liquid-catalyzed hydrolysis prepares nano-cellulose of applying, have little to equipment corrosion, environmental pollution is little, little to cellulose degradation damage, and the advantages such as the nano-cellulose yield is high, ionic liquid is reusable, overcome the shortcoming that traditional liquid acid prepares nano-cellulose.
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), temperature is risen to 50 ~ 70 ℃ under ul-trasonic irradiation, after reaction 1 ~ 3h, by the liquid nitrogen snap frozen, process 20min; Then slowly melt, and temperature is risen to 50 ~ 70 ℃;
(2) after the liquid nitrogen snap frozen of repeating step (1)-slowly melt-warming temperature 2 ~ 6 times, extract ionic liquid from turbid liquid, raffinate high speed centrifugation purifying, obtain milky cellulose colloid, through vacuum freeze drying 24h, obtain the 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, little to cellulose degradation damage, the nano-cellulose yield is high, length, width distribution are more concentrated, the advantages such as ionic liquid is reusable, overcome traditional liquid acid and prepared nano-cellulose to shortcomings such as equipment corrosion are large, big for environment pollution.
The specific embodiment
embodiment 1
Take in the ionic liquid chlorination 1-allyl that 2g paper pulp joins 50ml-3-methylimidazole [Amim] Cl, under the ul-trasonic irradiation that is 300W at power, temperature is risen to 70 ℃, and after reaction 1h, will be with liquid nitrogen snap frozen processing 20min; Then slowly melt, and temperature is risen to 70 ℃.After repeating liquid nitrogen snap frozen-slowly melt-warming temperature 2 times, will from turbid liquid, extract ionic liquid, by the further high speed centrifugation purifying of raffinate, obtain milky cellulose colloid through vacuum freeze drying 24h, make the nano-cellulose powder.
The Morfi Compact fibre morphology analyzer that utilizes French Techpap company to produce is analyzed cellulosic morphosis.Record average length 589 nm of this nano-cellulose; Mean breadth 46 nm; Length mainly is distributed in 450 ~ 750nm, and length 550 ~ 650nm accounts for 93.2%.
embodiment 2
Take in the ionic liquid bromination 1-octyl group that 5g paper pulp joins 100ml-3-methylimidazole [Omim] Br, under the ul-trasonic irradiation that is 500W at power, temperature is risen to 50 ℃, and after reaction 3h, will be with liquid nitrogen snap frozen processing 20min; Then slowly melt, and temperature is risen to 50 ℃.After repeating liquid nitrogen snap frozen-slowly melt-warming temperature 5 times, will from turbid liquid, extract ionic liquid, by the further high speed centrifugation purifying of raffinate, obtain milky cellulose colloid through vacuum freeze drying 24h, make the nano-cellulose powder.
The Morfi Compact fibre morphology analyzer that utilizes French Techpap company to produce is analyzed cellulosic morphosis.Record average length 381 nm of this nano-cellulose; Mean breadth 32 nm; Length mainly is distributed in 300 ~ 450nm, and length 350 ~ 400nm accounts for 90.8%.
embodiment 3
The paper pulp that takes 3g joins in the chlorination 1-butyl of 80ml-3-methylimidazole [Bmim] Cl, under the ul-trasonic irradiation that is 400W at power, temperature is risen to 60 ℃, and, after reaction 2h, will process 20min by the liquid nitrogen snap frozen; Then slowly melt, and temperature is risen to 60 ℃.After repeating liquid nitrogen snap frozen-slowly melt-warming temperature 4 times, will from turbid liquid, extract ionic liquid, by the further high speed centrifugation purifying of raffinate, obtain milky cellulose colloid through vacuum freeze drying 24h, make the nano-cellulose powder.
The Morfi Compact fibre morphology analyzer that utilizes French Techpap company to produce is analyzed cellulosic morphosis.Record average length 508 nm of this nano-cellulose; Mean breadth 39 nm; Length mainly is distributed in 400 ~ 650nm, and length 450 ~ 550nm accounts for 94.3%.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing 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 ionic liquid-catalyzed hydrolysis prepares nano-cellulose for one kind, it is characterized in that: comprise the following steps:
(1) take 2 ~ 5g paper pulp and join in 50 ~ 100ml ionic liquid, under ul-trasonic irradiation, temperature is risen to 50 ~ 70 ℃, after reacting 1 ~ 3h, by the liquid nitrogen snap frozen, process 20min; Then slowly melt, and temperature is risen to 50 ~ 70 ℃;
(2) after the liquid nitrogen snap frozen of repeating step (1)-slowly melt-warming temperature 2 ~ 6 times, extract ionic liquid from turbid liquid, raffinate high speed centrifugation purifying, obtain milky cellulose colloid, through vacuum freeze drying 24h, obtain the nano-cellulose powder.
2. the ionic liquid-catalyzed hydrolysis of application according to claim 1 prepares the method for nano-cellulose, it is characterized in that: the ultrasonic power of step (1) is 300 ~ 500W.
3. the ionic liquid-catalyzed hydrolysis of application according to claim 1 prepares the method for nano-cellulose, it is characterized in that: the described ionic liquid of step (1) is a kind of 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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| CN201310433104.7A CN103469662B (en) | 2013-09-23 | 2013-09-23 | A kind of method applied ionic liquid-catalyzed hydrolysis and prepare nano-cellulose |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740867A (en) * | 2014-01-02 | 2014-04-23 | 上海大学 | Method for preparing glucose by hydrolyzing straw celluloses |
| CN105220552A (en) * | 2015-09-09 | 2016-01-06 | 郑州轻工业学院 | Utilize the cellulosic method of imidazoles asymmetric Gemini ionic liquid extract |
| CN107761426A (en) * | 2016-08-17 | 2018-03-06 | 中国科学院化学研究所 | A kind of method for preparing low polymerization degree cellulose using freezing, grinding and products thereof and application |
| CN110105455A (en) * | 2019-05-21 | 2019-08-09 | 河北科技大学 | A kind of ionic liquid, its application and Cellulose nanocrystal body material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740867A (en) * | 2014-01-02 | 2014-04-23 | 上海大学 | Method for preparing glucose by hydrolyzing straw celluloses |
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| CN107761426A (en) * | 2016-08-17 | 2018-03-06 | 中国科学院化学研究所 | A kind of method for preparing low polymerization degree cellulose using freezing, grinding and products thereof and application |
| 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 |
| CN110105455A (en) * | 2019-05-21 | 2019-08-09 | 河北科技大学 | A kind of ionic liquid, its application and Cellulose nanocrystal body material and preparation method thereof |
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| CN103469662B (en) | 2015-08-12 |
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