CN103643578A - Method for preparing nanocrystalline cellulose from coupling system of N-methyl morpholine-n-oxide and magnetic graphene - Google Patents
Method for preparing nanocrystalline cellulose from coupling system of N-methyl morpholine-n-oxide and magnetic graphene Download PDFInfo
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- CN103643578A CN103643578A CN201310674745.1A CN201310674745A CN103643578A CN 103643578 A CN103643578 A CN 103643578A CN 201310674745 A CN201310674745 A CN 201310674745A CN 103643578 A CN103643578 A CN 103643578A
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- methyl morpholine
- morpholine oxide
- graphite alkene
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Abstract
The invention discloses a method for preparing nanocrystalline cellulose from a coupling system of N-methyl morpholine-n-oxide and magnetic graphene. The method comprises the steps of processing microcrystalline cellulose through a N-methyl morpholine-n-oxide water solution to ensure that fiber is swelled so as to obtain a mixed solution; and carrying out microwave treatment on the mixed solution, adding the magnetic graphene, stirring, carrying out microwave treatment, adding water, stirring, recovering the magnetic graphene through a magnet, settling the solution into an upper layer and a lower layer, and carrying out reduced pressure distillation on supernatant liquid to recover the N-methyl morpholine-n-oxide while removing impurities of the lower layer, and freeze-drying to obtain the nanocrystalline cellulose. The method, which takes the microcrystalline cellulose as a raw material, has the advantages of wide source and high utilization rate of natural plant fiber; the segmental nanocrystalline cellulose is prepared by coupling the N-methyl morpholine-n-oxide and the magnetic graphene; the preparation method is simple and easy to implement, and has an environment-friendly effect; the two processing agents can be recycled after being used, thus reducing production cost.
Description
Technical field
The present invention relates to a kind of preparation method of nanofiber, the Fourier Series expansion technique that relates in particular to a kind of N-of utilization methyl morpholine oxide and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, belongs to biochemical industry and field of chemical engineering.
Background technology
Cellulose is the main component of the high plant cell walls such as cotton, timber, flax, careless class, can produce hundred million tons of hundreds ofs every year by photosynthesis, is that nature is inexhaustible, nexhaustible, the free of contamination renewable resource of degradable; But it is as natural high molecular substance, no matter in physical aspect or chemical property, there are some defects,, not resistance to chemical attack poor such as heat of solution, intensity are limited etc.And nano micro crystal cellulose (Nanocrystalline Cellulose, NCC) refer to and on yardstick, have at least one dimension to reach 100nm or the cellulose below 100nm, possesses small-size effect, quantum effect, skin effect and macro quanta tunnel effect etc., it is as the reproducible nanometer new material of a kind of high added value, now become life science, the hot technology of material science and field of chemical engineering crossing research, especially in nearly ten years, be subject to showing great attention to of various countries scientific research personnel, it is believed that these characteristics of nano micro crystal cellulose are applied to the every field in human lives, must produce good economic benefit and social value.
At present, people adopt the methods such as machinery, chemistry or biology to extract nano micro crystal cellulose from plant cellulose, bacteria cellulose, tunicate (tunicate) cellulose.Especially the degradation process method such as physical mechanical method, sulphuric acid hydrolysis or clorox is common in the report of numerous research nano micro crystal celluloses.Although the method that adopts high-pressure machinery to dissociate has started to enter the medium scale batch production stage, yet the excessive problem of power consumption is not still solved.Although the prepared nano micro crystal cellulose suspension out of sulfuric acid process hydrolysis has high stability, yet owing to needing the sulfuric acid of a large amount of high concentrations and the hydrochloric acid of higher concentration in preparation process, therefore easily cause the corrosion of equipment and the pollution of environment, so sulfuric acid process hydrolysis is still only confined to the stage of laboratory research so far, cannot enter the industrialization phase of batch production.From the feedstock analysis of preparing nano microcrystalline cellulose, by timber, extract nano micro crystal cellulose, face equally the problem of environmental pollution the same with paper industry; While extracting nano micro crystal cellulose from bacteria cellulose, face and yield poorly, the problem that throughput rate is low; While extracting nano micro crystal cellulose from tunicate cellulose, face too the problem yielding poorly; While extracting, face usefulness low from the low agricultural product accessory substance of some fibre cellulose content, and the lower problem of the performance of end product.
Summary of the invention
Goal of the invention: the object of this invention is to provide a kind of Fourier Series expansion technique of utilizing N-methyl morpholine oxide and magnetic graphite alkene with low cost, environmental protection and prepare the method for nano micro crystal cellulose.
Technical scheme: the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide of the present invention and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, comprises the steps:
(1) with the N-methyl morpholine oxide aqueous solution, process microcrystalline cellulose, make the filament expansion of microcrystalline cellulose, obtain mixed solution;
(2) mixed solution is first used to microwave treatment, then add magnetic graphite alkene to stir, carry out again microwave treatment, then adding water stirs, with magnet, reclaim magnetic graphite alkene again, solution natural subsidence is divided into levels: get supernatant liquor decompression distillation and remove moisture, reclaim N-methyl morpholine oxide; Collect lower floor simultaneously, remove impurity wherein, freeze drying obtains nano micro crystal cellulose.
Wherein, in step (1), the mass concentration of the described N-methyl morpholine oxide aqueous solution is 50%-80%.
The weight ratio of described microcrystalline cellulose and N-methyl morpholine oxide is 1:50-100.
In step (2), the magnetic graphite alkene adding and the weight ratio of N-methyl morpholine oxide are 1:10-100.
The power of described microwave treatment is 100w-200w, and the microwave time is 1-5min.
The water adding is 0.5-3 times of N-methyl morpholine oxide liquor capacity.
Described magnetic graphite alkene is magnetic oxygenated Graphene.
Described microwave treatment is closed processes in microwave synthesizer.
Thermograde during described decompression distillation is 100-120 ℃ of decompression distillation 20min, 150-160 ℃ of decompression distillation 20min.
Use bag filter dialysis except the impurity in sub-cloud.
Reaction mechanism: the N-methyl morpholine oxide aqueous solution that mass concentration is 50%-80% plays expansion to cellulosic long fiber, and magnetic oxygenated Graphene surface has sulfonate radical, salt acid group isoreactivity group, these active groups can be fractured into the long fiber of expansion little short-movie section, thus to the nano micro crystal cellulose of fragmentation.
Beneficial effect: compared with prior art, its remarkable advantage is in the present invention: 1, take microcrystalline cellulose as raw material, and microcrystalline cellulose can extract from plant, wide material sources not only, and greatly improved the utilization rate of natural plant fibre; 2, N-methyl morpholine oxide and the coupling of magnetic graphite alkene are used, process the nano micro crystal cellulose that obtains fragmentation, and preparation method is simple, environmental protection, pollution-free; 3, N-methyl morpholine oxide and magnetic graphite alkene all can recyclings after processing, and reduce the production cost of nano micro crystal cellulose.
Accompanying drawing explanation
The nano micro crystal cellulose SEM surface topography map (multiplication factor 10000 times) of Fig. 1 for adopting the inventive method to prepare.
The specific embodiment
Below technical scheme of the present invention is elaborated.
Embodiment 1:
First, 1g microcrystalline cellulose being joined to 100g mass concentration in the there-necked flask of 500ml is in the 50%N-methyl morpholine oxide aqueous solution, 60 ℃ of insulated and stirred are processed 30min, make the filament expansion of microcrystalline cellulose, obtain the mixed solution of N-methyl morpholine oxide and expansion cellulose;
Then, with this mixed solution of microwave synthesizer closed processes, wherein, microwave is 100w, and the processing time is 5min.Then 5g adds hydrogen phosphate class magnetic graphite alkene, stirs, then with adding the water of N-methyl morpholine oxide liquor capacity 50% after 100w microwave treatment 5min, stirs, and then allows liquid flow through magnetic pipeline, and magnetic oxygenated Graphene can reclaim completely.The suspension natural subsidence obtaining is divided into levels: get the centrifugal 5min of supernatant liquor 10000r/min, 100 ℃ of decompression distillation 20min, remove moisture.150 ℃ of decompression distillation 30min, the distillation of N-methyl morpholine oxide, passes into deionized water by the gas of distillation, recyclable N-methyl morpholine oxide; Collect lower floor's solid simultaneously, use bag filter dialysis to remove impurity wherein, freeze drying obtains nano micro crystal cellulose.
Embodiment 2:
First, in the there-necked flask of 500ml, getting 1g microcrystalline cellulose, to join mass concentration be that the 125g80%N-methyl morpholine oxide aqueous solution is processed, 70 ℃ of insulated and stirred are processed 15min, make the filament expansion of microcrystalline cellulose, obtain the mixed solution of N-methyl morpholine oxide and expansion cellulose;
Then, with this mixed solution of microwave synthesizer closed processes, wherein, microwave is 200w, and the processing time is 1min.Then add the magnetic oxygenated Graphene of 1g, stir, then with adding after 200w microwave treatment 1min and the isopyknic water of N-methyl morpholine oxide solution, stir, then allow liquid flow through magnetic pipeline, magnetic oxygenated Graphene can reclaim completely.The suspension natural subsidence obtaining is divided into levels: get the centrifugal 5min of supernatant liquor 10000r/min, 120 ℃ of decompression distillation 20min, remove moisture.160 ℃ of decompression distillation 30min,, N-methyl morpholine oxide China, passes into deionized water by the gas of distillation, recyclable N-methyl morpholine oxide; Collect lower floor's solid simultaneously, use bag filter dialysis to remove impurity wherein, freeze drying obtains nano micro crystal cellulose.
Embodiment 3:
First, in the there-necked flask of 500ml, getting 1g microcrystalline cellulose, to join mass concentration be that the 100g70%N-methyl morpholine oxide aqueous solution is processed, 65 ℃ of insulated and stirred are processed 20min, make the filament expansion of microcrystalline cellulose, obtain the mixed solution of N-methyl morpholine oxide and expansion cellulose;
Then, with this mixed solution of microwave synthesizer closed processes, wherein, microwave is 150w, and the processing time is 3min.Then add the magnetic oxygenated Graphene of 5g, stir, then with the water adding after 150w microwave treatment 3min with 3 times of volumes of N-methyl morpholine oxide solution, stir, then allow liquid flow through magnetic pipeline, magnetic oxygenated Graphene can reclaim completely.The suspension liquid natural subsidence obtaining is divided into levels: get the centrifugal 5min of supernatant liquor 10000r/min, 110 ℃ of decompression distillation 20min, remove moisture, 155 ℃ of decompression distillation 30min, N-methyl morpholine oxide China, passes into deionized water by the gas of distillation, recyclable N-methyl morpholine oxide; Collect lower floor's solid simultaneously, use bag filter dialysis to remove impurity wherein, freeze drying obtains nano micro crystal cellulose.
Embodiment 4:
For characterizing nano-cellulose surface configuration, by scanning electronic microscope (SEM), measure nano micro crystal cellulose prepared by embodiment 1-3.Fig. 1 is the SEM surface topography map of nano-cellulose, and Analysis of Surface Topography result shows, cellulose prepared by the inventive method has at least one dimension can reach nanoscale, observes nano-cellulose and is graininess, and diameter is not by 50nm to 110nm etc.
Claims (10)
1. utilize the Fourier Series expansion technique of N-methyl morpholine oxide and magnetic graphite alkene to prepare a method for nano micro crystal cellulose, it is characterized in that comprising the steps:
(1) with the N-methyl morpholine oxide aqueous solution, process microcrystalline cellulose, make the filament expansion of microcrystalline cellulose, obtain mixed solution;
(2) mixed solution is first used to microwave treatment, then add magnetic graphite alkene to stir, carry out again microwave treatment, then adding water stirs, with magnet, reclaim magnetic graphite alkene again, solution natural subsidence is divided into levels: get supernatant liquor decompression distillation and remove moisture, reclaim N-methyl morpholine oxide; Collect lower floor simultaneously, remove impurity wherein, freeze drying obtains nano micro crystal cellulose.
2. the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide according to claim 1 and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, it is characterized in that: in step (1), the mass concentration of the described N-methyl morpholine oxide aqueous solution is 50%-80%.
3. the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide according to claim 1 and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, it is characterized in that: in step (1), the weight ratio of described microcrystalline cellulose and N-methyl morpholine oxide is 1:50-100.
4. the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide according to claim 1 and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, it is characterized in that: in step (2), the magnetic graphite alkene adding and the weight ratio of N-methyl morpholine oxide are 1:10-100.
5. the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide according to claim 1 and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, it is characterized in that: in step (2), the power of described microwave treatment is 100w-200w, and the microwave time is 1-5min.
6. the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide according to claim 1 and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, it is characterized in that: in step (2), the water adding is 0.5-3 times of N-methyl morpholine oxide liquor capacity.
7. the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide according to claim 1 and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, it is characterized in that: in step (2), described magnetic graphite alkene is magnetic oxygenated Graphene.
8. the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide according to claim 1 and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, it is characterized in that: in step (2), described microwave treatment is closed processes in microwave synthesizer.
9. the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide according to claim 1 and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, it is characterized in that: in step (2), thermograde during described decompression distillation is 100-120 ℃ of decompression distillation 20min, 150-160 ℃ of decompression distillation 20min.
10. the Fourier Series expansion technique of the N-of utilization methyl morpholine oxide according to claim 1 and magnetic graphite alkene is prepared the method for nano micro crystal cellulose, it is characterized in that: in step (2), use bag filter dialysis except the impurity in sub-cloud.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103990471A (en) * | 2014-05-05 | 2014-08-20 | 江苏科技大学 | Preparation method of mulberry twig-based solid acid |
| CN109467608A (en) * | 2018-11-16 | 2019-03-15 | 江苏科技大学 | A kind of preparation method of the nano micro crystal cellulose of mulberry fiber source |
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| CN1171904A (en) * | 1996-07-31 | 1998-02-04 | 李庆 | Sausage with peanut |
| CN1267486A (en) * | 2000-02-01 | 2000-09-27 | 古盛龙 | Bone-glossy ganoderma beverage and its preparation |
| CN1171904C (en) * | 2000-07-18 | 2004-10-20 | 中国科学院广州化学研究所 | Nm-class microcrystal cellulose and its preparing process |
| CN102040663A (en) * | 2010-12-06 | 2011-05-04 | 东华大学 | Preparation method of narrow-distribution cellulose nanocrystalline |
| CN102505546A (en) * | 2011-10-01 | 2012-06-20 | 中国热带农业科学院农产品加工研究所 | Method for preparing nanocellulose by using homogeneous method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1171904A (en) * | 1996-07-31 | 1998-02-04 | 李庆 | Sausage with peanut |
| CN1267486A (en) * | 2000-02-01 | 2000-09-27 | 古盛龙 | Bone-glossy ganoderma beverage and its preparation |
| CN1171904C (en) * | 2000-07-18 | 2004-10-20 | 中国科学院广州化学研究所 | Nm-class microcrystal cellulose and its preparing process |
| CN102040663A (en) * | 2010-12-06 | 2011-05-04 | 东华大学 | Preparation method of narrow-distribution cellulose nanocrystalline |
| CN102505546A (en) * | 2011-10-01 | 2012-06-20 | 中国热带农业科学院农产品加工研究所 | Method for preparing nanocellulose by using homogeneous method |
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| CN103990471A (en) * | 2014-05-05 | 2014-08-20 | 江苏科技大学 | Preparation method of mulberry twig-based solid acid |
| CN103990471B (en) * | 2014-05-05 | 2016-05-18 | 江苏科技大学 | A kind of preparation method of ramulus mori based solid acid |
| CN109467608A (en) * | 2018-11-16 | 2019-03-15 | 江苏科技大学 | A kind of preparation method of the nano micro crystal cellulose of mulberry fiber source |
| CN109467608B (en) * | 2018-11-16 | 2020-11-06 | 江苏科技大学 | Preparation method of mulberry fiber-derived nano microcrystalline cellulose |
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