CN103755817B - A kind of preparation method of nano micro crystal cellulose - Google Patents
A kind of preparation method of nano micro crystal cellulose Download PDFInfo
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- CN103755817B CN103755817B CN201310674258.5A CN201310674258A CN103755817B CN 103755817 B CN103755817 B CN 103755817B CN 201310674258 A CN201310674258 A CN 201310674258A CN 103755817 B CN103755817 B CN 103755817B
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Abstract
The invention discloses the preparation method of a kind of nano micro crystal cellulose, comprise the steps: that (1) processes microcrystalline Cellulose with N methyl morpholine N oxide and ionic liquid；(2) recycling agent.Advantages of the present invention is: with microcrystalline Cellulose as raw material, and microcrystalline Cellulose can extract from plant, not only wide material sources, and substantially increases the utilization rate of natural plant fibre；Coupling uses N methyl morpholine N oxide and ionic liquid, processes the nano micro crystal cellulose obtaining fragmentation；The most recyclable recycling after N methyl morpholine N oxide and ionic liquid process, reduces the production cost of nano micro crystal cellulose；The preparation process of nano micro crystal cellulose is simple, environmental protection, there is not the problem such as equipment corrosion or environmental pollution.
Description
Technical field
The present invention relates to the preparation method of a kind of cellulose, particularly relate to the preparation method of a kind of nano micro crystal cellulose,
Belong to biochemical industry and field of chemical engineering.
Background technology
Cellulose is to be distributed the widest, content is most a kind of polysaccharide in nature, has degradable, renewable, density is little
And ecological environment is not produced the advantages such as pollution, the cellulose that the whole world is synthesized by photosynthesis every year up to hundreds billion of tons,
Therefore, cellulose becomes people is respectively provided with friendly, non-petroleum analogous environmental protection resource by environment.But, natural
No matter cellulose exists in physical aspect or chemical property that some defects, such as heat of solution are poor, not resistance to chemical attack, strong
Spend limited etc..Nano micro crystal cellulose (Nanocrystalline Cellulose, NCC) refers on yardstick the most one-dimensional
Reaching the cellulose of 100nm or below 100nm, compared with cellulose or microcrystalline Cellulose, nano micro crystal cellulose has more
Crystal region and higher degree of crystallinity, under nanoscale, cellulose surface exposes substantial amounts of hydroxyl, so nano microcrystalline is fine
Dimension element has high-hydrophilic, high stability and high response, the most also has high transparent high with liquid crystal liquid crystal property and specific surface area
Feature.Owing to nano micro crystal cellulose is compounded with the advantage of native cellulose and nano-substance, therefore receive in last decade
The highest attention of various countries scientific research personnel, it is believed that these characteristics of nano micro crystal cellulose will be utilized and be applied to people
Every field in class life.
At present, the chemical degradation processing method of sulphuric acid/hydrochloric acid is used to be common in numerous development nano micro crystal celluloses
In report.Although the nano micro crystal cellulose suspension of sulfuric acid process hydrolysis preparation has high stability, but needs in preparation process
Want sulphuric acid and the hydrochloric acid of higher concentration of a large amount of high concentrations, therefore easily cause the corrosion of equipment and the pollution of environment, so
Sulfuric acid process hydrolysis is the most still limited only to the laboratory research stage, it is impossible to enter the industrialization phase of batch production.Meanwhile, high
The press mechanical pressing method of dissociating has begun to enter medium scale mass-production stage, however the excessive problem of power consumption the most not by
Solve.If using timber to extract nano-cellulose, face the problem of environmental pollution as paper industry equally；Fine from antibacterial
When dimension element extracts nano-cellulose, face and yield poorly, the problem that throughput rate is low；Extract from tunicate cellulose
During nano-cellulose, face the problem yielded poorly too；When extracting from the agricultural product by-product that some fibre cellulose content is low,
Then face the problem that the performance of inefficiency and end product is relatively low.
Summary of the invention
Goal of the invention: it is an object of the invention to provide a kind of nano micro crystal cellulose with low cost, environmental protection and prepare
Method.
Technical scheme: the preparation method of nano micro crystal cellulose of the present invention, comprises the steps:
(1) process microcrystalline Cellulose: first, process microcrystalline Cellulose with the aqueous solution of N-methylmorpholine-N-oxide, make
The fiber of microcrystalline Cellulose is swelling, obtains mixed solution；Secondly, after ultrasonic Treatment mixed solution, add ionic liquid, stir
Mix uniformly, then use ultrasonic Treatment；Then, adding water and stir, mixed solution natural subsidence is also divided into levels, under collection
Layer, removes impurity, and lyophilization obtains nano micro crystal cellulose；
(2) recycling agent: take the supernatant, decompression is distilled off moisture, and is separately recovered N-methylmorpholine-N-oxidation
Thing and ionic liquid.
In step (1), the mass concentration of described N-methylmorpholine-N-oxide water solution is 10%-80%.
Described microcrystalline Cellulose is 1:10-100 with the weight ratio of N-methylmorpholine-N-oxide.
Described ionic liquid is hydrogen phosphate class ionic liquid or bisulfate ion class ionic liquid.
The ionic liquid added is 1:1-20 with the weight ratio of N-methylmorpholine-N-oxide.
0.5-1 times that water is N-methylmorpholine-N-oxide solution volume added.
The power of described ultrasound wave is 60w-90w.
The time of described ultrasonic Treatment is 20-30min.
In step (2), the thermograde of described decompression distillation is 80-90 DEG C of decompression distillation 30min, 140-150 DEG C of decompression
Distillation 30min.
Reaction mechanism: N-methylmorpholine-N-oxide has certain oxidisability and the dissolving function to cellulose, ion
Liquid has the function processing cellulose, and N-methylmorpholine-N-oxide couples use, obtains cellulose molten with ionic liquid
Solving and process mixed solution with better function, N-methylmorpholine-N-oxide can make cellulose long-chain with oxidation scission cellulose
Fragmenting into nano level cellulose segment, i.e. nano-cellulose, therefore this method can produce nano micro crystal cellulose in a large number.
Beneficial effect: compared with prior art, its remarkable advantage is 1 to the present invention, with microcrystalline Cellulose as raw material, and crystallite
Cellulose can extract from plant, not only wide material sources, and substantially increases the utilization rate of natural plant fibre；2, N-methyl
Methylmorpholine-N-oxide couples use with ionic liquid, processes the nano micro crystal cellulose obtaining fragmentation；3, N-methylmorpholine-
The most recyclable recycling after N-oxide and ionic liquid process, reduces the production cost of nano micro crystal cellulose；4, nanometer is micro-
The preparation process of crystalline cellulose is simple, environmental protection, there is not the problem such as equipment corrosion or environmental pollution.
Accompanying drawing explanation
Fig. 1 is the TEM figure preparing nano micro crystal cellulose by the inventive method.
Detailed description of the invention
Below technical scheme is described in detail.
Embodiment 1: first, take 1g microcrystalline Cellulose adding 100g mass fraction is 10%N-methyhnorpholine-N-oxide
In aqueous solution, 50 DEG C of insulated and stirred process 20min, and the fiber making microcrystalline Cellulose is the most swelling, obtains mixed solution；Secondly,
After the ultrasonic Treatment mixed solution 30min of 60w, add 10g hydrogen phosphate class ionic liquid, stir, then surpass with 60w
Sonicated 30min；Then, adding water and stir, amount of water is 0.5 times of N-methylmorpholine-N-oxide solution volume, mixed
Closing solution natural subsidence and be divided into levels, collecting lower floor, removing impurity, lyophilization obtains nano micro crystal cellulose；Finally,
Reclaiming inorganic agent, take the supernatant, 10000r/min is centrifuged 5min, 80 DEG C decompression distillation 30min, in order to remove water and
Low boiling impurity；140 DEG C decompression distillation 30min, N-methylmorpholine-N-oxide distil, with this be separately recovered N-methylmorpholine-
N-oxide and ionic liquid.
Embodiment 2: first, take 1g microcrystalline Cellulose adding 200g mass fraction is 50%N-methyhnorpholine-N-oxide
In aqueous solution, 70 DEG C of insulated and stirred process 5min, and the fiber making microcrystalline Cellulose is the most swelling, obtains mixed solution；Secondly, use
After the ultrasonic Treatment mixed solution 25min of 80w, add 5g hydrogen sulfate ion liquid, stir, then use 80w ultrasound wave
Process 25min；Then, adding water and stir, amount of water and N-methylmorpholine-N-oxide solution equal-volume, mixed solution is certainly
So settling and be divided into levels, collect lower floor, remove impurity, lyophilization obtains nano micro crystal cellulose；Finally, to inorganic agent
Reclaiming, take the supernatant, 10000r/min is centrifuged 5min, 90 DEG C of decompression distillation 30min；150 DEG C of heating decompression distillations
30min removes moisture, and N-methylmorpholine-N-oxide distils, and is separately recovered N-methylmorpholine-N-oxide and ionic liquid with this
Body.
Embodiment 3:
First, take 1g microcrystalline Cellulose and add the aqueous solution that 100g mass fraction is 80%N-methyhnorpholine-N-oxide
In, 60 DEG C of insulated and stirred process 10min, and the fiber making microcrystalline Cellulose is the most swelling, obtains mixed solution；Secondly, with 90w's
After ultrasonic Treatment mixed solution 20min, add 8g hydrogen phosphate class ionic liquid, stir, then use 90w ultrasonic Treatment
20min；Then, adding water and stir, amount of water is 0.6 times of N-methylmorpholine-N-oxide solution volume, and mixed solution is certainly
So settling and be divided into levels, collect lower floor, remove impurity, lyophilization obtains nano micro crystal cellulose；Finally, to inorganic agent
Reclaiming, take the supernatant, 10000r/min is centrifuged 5min, 85 DEG C of decompression distillation 30min, 145 DEG C of heating decompression distillations
30min removes moisture, and N-methylmorpholine-N-oxide distils, and is separately recovered N-methylmorpholine-N-oxide and ionic liquid with this
Body.
Embodiment 4: detect the nano micro crystal cellulose of above-mentioned preparation.
Seeing Fig. 1, the nano-cellulose preparing embodiment 1-3 carries out TEM detection respectively, and result shows the fiber of preparation
Element is different rod-like crystal granules sized by being respectively formed a large amount of pattern, the most high-visible, between a diameter of 20-60nm.
Claims (9)
1. the preparation method of a nano micro crystal cellulose, it is characterised in that comprise the steps: (1) process microcrystalline Cellulose:
First, processing microcrystalline Cellulose with the aqueous solution of N-methylmorpholine-N-oxide, the fiber making microcrystalline Cellulose is swelling, obtains
Mixed solution；Secondly, after ultrasonic Treatment mixed solution, add ionic liquid, stir, then use ultrasonic Treatment；So
After, adding water and stir, mixed solution natural subsidence is also divided into levels, collects lower floor, removes impurity, and lyophilization obtains and receives
Rice microcrystalline Cellulose；(2) recycling agent: take the supernatant, decompression is distilled off moisture, and be separately recovered N-methylmorpholine-
N-oxide and ionic liquid.
The preparation method of nano micro crystal cellulose the most according to claim 1, it is characterised in that: in step (1), described N-
The mass fraction of methyhnorpholine-N-oxide aqueous solution is 10%-80%.
The preparation method of nano micro crystal cellulose the most according to claim 1, it is characterised in that: in step (1), described micro-
Crystalline cellulose is 1:10-100 with the weight ratio of N-methylmorpholine-N-oxide.
The preparation method of nano micro crystal cellulose the most according to claim 1, it is characterised in that: in step (1), described from
Sub-liquid is hydrogen phosphate class ionic liquid or bisulfate ion class ionic liquid.
The preparation method of nano micro crystal cellulose the most according to claim 1, it is characterised in that: in step (1), addition
Ionic liquid is 1:1-20 with the weight ratio of N-methylmorpholine-N-oxide.
The preparation method of a kind of nano micro crystal cellulose the most according to claim 1, it is characterised in that: in step (1), add
The water entered is 0.5-1 times of N-methylmorpholine-N-oxide solution volume.
The preparation method of nano micro crystal cellulose the most according to claim 1, it is characterised in that: in step (1), described super
The power of sound wave is 60w-90w.
The preparation method of a kind of nano micro crystal cellulose the most according to claim 1, it is characterised in that: in step (1), institute
The time stating ultrasonic Treatment is 20-30min.
The preparation method of a kind of nano micro crystal cellulose the most according to claim 1, it is characterised in that: in step (2), institute
The thermograde stating decompression distillation is 80-90 DEG C of decompression distillation 30min, and 140-150 DEG C of decompression distillation 30min obtains N-methyl
Quinoline-N-oxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104532645B (en) * | 2014-11-11 | 2016-06-29 | 浙江理工大学 | A kind of method preparing nano micro crystal cellulose for raw material with waste and old corrugated board |
| CN104437633B (en) * | 2014-12-12 | 2016-08-24 | 江苏科技大学 | A kind of preparation method of mimic cellulose enzyme |
| CN106192040B (en) * | 2016-08-08 | 2018-09-04 | 四川大学 | A kind of preparation method of high aspect fibers element nanofiber |
| CN106674357A (en) * | 2016-12-21 | 2017-05-17 | 广西大学 | Method for preparing nano cellulose in EmimOAc system |
| CN107236048A (en) * | 2017-06-12 | 2017-10-10 | 齐鲁工业大学 | A kind of method that nano-crystal cellulose is prepared in ionic liquid/solid acid system |
| CN109467608B (en) * | 2018-11-16 | 2020-11-06 | 江苏科技大学 | Preparation method of mulberry fiber-derived nano microcrystalline cellulose |
| CN112522988B (en) * | 2020-12-10 | 2022-11-04 | 江门市高力依科技实业有限公司 | Special efficient agent containing sulfur-doped nanocrystalline cellulose for papermaking and preparation method thereof |
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| CN1470552A (en) * | 2003-06-16 | 2004-01-28 | 东华大学 | Method for preparing nano-level cellulose granule |
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| CN101654522A (en) * | 2009-09-08 | 2010-02-24 | 中国科学院过程工程研究所 | Anti-degradable solvent for dissolving cellulose and preparation method of spinning dope thereof |
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| CN1470552A (en) * | 2003-06-16 | 2004-01-28 | 东华大学 | Method for preparing nano-level cellulose granule |
| CN101139805A (en) * | 2007-08-15 | 2008-03-12 | 清华大学 | High-voltage static atomizing preparing technique for nano-grade cellulosic material |
| US20100129633A1 (en) * | 2008-11-27 | 2010-05-27 | Stephen Law | Absorbent Material |
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