CN106810614B - A kind of preparation process of nanocrystal cellulose - Google Patents
A kind of preparation process of nanocrystal cellulose Download PDFInfo
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- CN106810614B CN106810614B CN201710049562.9A CN201710049562A CN106810614B CN 106810614 B CN106810614 B CN 106810614B CN 201710049562 A CN201710049562 A CN 201710049562A CN 106810614 B CN106810614 B CN 106810614B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
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Abstract
A kind of preparation process of nanocrystal cellulose is related to cellulosic material field comprising: by cellulose wood pulp by being added to progress first gradient hydrolysis in hydrochloric acid solution after mechanical treatment, the degree of polymerization is hydrolyzed into less than 350, filtering cleaning is filtered dry；Filter cake is added to the hydrolysis that sulfuric acid solution carries out the second gradient again, is hydrolyzed into the degree of polymerization less than 100, filtering cleaning is dry, obtains nanocrystal cellulose.Use cellulose wood pulp for raw material, after carrying out first gradient hydrolysis by the hydrochloric acid of low concentration before sulphuric acid hydrolysis, the second gradient hydrolysis is carried out using sulfuric acid again, nanocrystal cellulose partial size obtained is small, centralized particle diameter, and purity and yield all have greatly improved.
Description
Technical field
The present invention relates to cellulosic material fields, and in particular to a kind of preparation process of nanocrystal cellulose.
Background technique
As energy crisis, problem of environmental pollution become increasingly conspicuous, environmental-friendly and reproducible material obtained widely
Research.Cellulose is the most abundant natural biodegradable polymer polymer on the earth, is a kind of with good biocompatibility
Environmentally friendly material.Nanocrystal cellulose (NCC) is the obtained minimal physical structural unit of cellulose after hydrolysis, directly
Diameter is less than 100nm, and having biggish draw ratio, high-specific surface area and high intensity, (its intensity is the 1/3 of carbon nanotube, is the 8 of steel
The nano material of low-density again), has broad application prospects.
The technique processed of nanocrystal cellulose generally includes acid-hydrolysis method, TEMPO oxidizing process and Mechanical Method and obtains.Wherein lead to
It is small to cross the nanocrystal cellulose partial size that TEMPO oxidizing process is prepared, and there is big draw ratio, enhances in cellulose compound
It shows good performance in terms of material, however TEMPO expensive reagents and is not easily recycled, it is at high cost, it should not be given birth on a large scale
It produces.In addition, cellulose fibre is separated into nano-scale by the effect that Mechanical Method mainly passes through power, usually high pressure homogenization method, ball
Mill method, polishing etc. are highly energy-consuming technique, inconvenient actual production.And acid-hydrolysis method prepares nano-cellulose and mainly passes through acid
Hydrolysis removes the amorphous region being more easily damaged and time crystalline region, keeps the complete crystalline structure in crystal region, has good toughness,
It is a kind of excellent reinforcing material.
Chinese patent application CN105625077A discloses a kind of preparation method of nano-cellulose, and method includes with quality
The sulfuric acid solution that score is 55% hydrolyzes absorbent cotton, 55-60 DEG C isothermal reaction 1.5-2 hour, add water cooling, pass through dialysis cleaning
To neutrality, freeze-drying.Since the distribution of lengths of absorbent cotton is very wide (several microns to several millimeters are differed), sulfuric acid water is directlyed adopt
Solution causes the amorphous region of few fibers and time crystalline region to be unable to fully destroy, and the crystal region excess destruction Cheng Danfen of few fibers
The glucose of son, the nanocrystal cellulose purity prepared by is low, yield is low, size distribution is wide.
Summary of the invention
The object of the present invention is to provide a kind of preparation process of nanocrystal cellulose, the preparation process is that more gradients are pure
Chemical hydrolysis, preparation-obtained nanocrystal cellulose purity is high, high income, partial size is small and size distribution is uniform, is applicable in
In the fields such as biological medicine and environment-friendly materials.
In order to reach the purpose of the present invention, technical scheme is as follows:
A kind of preparation process of nanocrystal cellulose comprising: cellulose wood pulp is added to after mechanical treatment
First gradient hydrolysis is carried out in hydrochloric acid solution, is hydrolyzed into the degree of polymerization less than 350, filtering cleaning is filtered dry；Filter cake is added again
The hydrolysis that the second gradient is carried out to sulfuric acid solution is hydrolyzed into the degree of polymerization less than 100, and filtering cleaning is dry, obtains nanocrystalline
Body cellulose.
The content of the chemical cellulose of the cellulose wood pulp is greater than 90wt%, and the cellulose wood pulp is by passing through Market Pulp
Mechanical treatment (such as slicer shearing) is the square less than 2cm × 2cm.
The concentration of the hydrochloric acid solution can be 0.1~5.0mol/L, preferably 0.5~3.0mol/L, in one embodiment,
The concentration of the hydrochloric acid solution can be 1.0mol/L.
The mass fraction of the sulfuric acid solution can be 30%~80%, in one embodiment, the matter of the sulfuric acid solution
Measuring score can be 45%.
The temperature of the hydrolysis of the first gradient can be 80~120 DEG C, preferably 100 DEG C, the water of the first gradient
The time for solving reaction can be 10~60 minutes.
The temperature of the hydrolysis of second gradient can be 40~80 DEG C, preferably 50 DEG C, the hydrolysis of second gradient
The time of reaction can be 10~60 minutes.
The hydrolysis of the first gradient and the hydrolysis of the second gradient carry out under stiring, using overhead stirrer
Stirring, revolving speed is about 100~500 revs/min.
The drying can be pneumatic conveying drying, fluidized drying, spray drying etc..
Compared with prior art, the present invention having the advantage that
The present inventor has found during the experiment, uses cellulose wood pulp for raw material, by lower dense before sulphuric acid hydrolysis
After the hydrochloric acid of degree carries out first step hydrolysis, then using sulfuric acid the second gradient hydrolysis of progress, nanocrystal cellulose obtained
Partial size is small, centralized particle diameter, and purity and yield all have greatly improved.
(1) the nanocrystal cellulose degree of polymerization prepared is down to 100 hereinafter, purity is high, partial size are 100 hereinafter, and granularity
Homogeneity is good.
(2) preparation process is simple, and low energy consumption, high income, can carry out continuous production.
Detailed description of the invention
Fig. 1 is: 1 laser particle analyzer grain size distribution of embodiment；
Fig. 2 is: 1 laser particle analyzer grain size distribution of comparative example；
Fig. 3 is: 1 atomic force microscopy surface aspect graph of embodiment；
Fig. 4 is: 1 atomic force microscopy surface aspect graph of comparative example.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, disclose further below some non-
Limitation embodiment further elaborates present invention work.
Detection method:
Configuration of surface:
Instrument: Bruker atomic force microscope, model: Dimension Icon, imaging system: ScanAsyst tests mould
Formula: tapping-mode.
Partial size (partial size described in the context of the invention is volume average particle size):
Instrument: HORIBA laser particle analyzer, model: LA-950, measuring method: wet process, decentralized medium: purified water.
The degree of polymerization:
Dry product 1.3g is taken, by testing under Chinese Pharmacopoeia the 4th (2015 editions) standard " microcrystalline cellulose " item.
Crystallinity:
Instrument: Bruker in situ X-ray diffraction diffractometer, model: D8Advance, voltage: 40kV, electric current: 30mA.
Embodiment 1
Slicer is added in Market Pulp (being rich in the slurry of chemical cellulose made of cellulose), is cut into 2cm × 2cm's
Square.100g cellulose paste is added to the hydrochloric acid solution of 900ml 1.0mol/L, it is anti-that first gradient hydrolysis is carried out at 100 DEG C
It answers, overhead stirrer stirs 20 minutes, 300 revs/min, after filtering washing, the cellulose cake that solid content is 40wt% is obtained,
The degree of polymerization is 320；Filter cake is added to the sulfuric acid solution of 1000ml 45wt%, carries out the second gradient hydrolysis at 50 DEG C, is reacted
Time 30 minutes, filtering washing, spray drying obtained nanocrystal cellulose, related physical characterization parameter for example table 1, Fig. 1,
Shown in Fig. 3.
Embodiment 2
Slicer is added in Market Pulp (being rich in the slurry of chemical cellulose made of cellulose), is cut into 2cm × 2cm's
Square.100g cellulose paste is added to the hydrochloric acid solution of 800ml 3.0mol/L, it is anti-that first gradient hydrolysis is carried out at 100 DEG C
It answers, overhead stirrer stirs 20 minutes, 300 revs/min, after filtering washing, the cellulose cake that solid content is 40wt% is obtained,
The degree of polymerization is 300；Filter cake is added to the sulfuric acid solution of 1000ml 30wt%, carries out the second gradient hydrolysis at 80 DEG C, is reacted
Time 30 minutes, filtering washing, spray drying obtained nanocrystal cellulose, related physical characterization parameter such as table 1.
Comparative example 1
Slicer is added in Market Pulp (being rich in the slurry of chemical cellulose made of cellulose), is cut into the side of 2cm*2cm
Block.100g cellulose paste is added to the sulfuric acid solution of 1000ml 55wt%, reaction, reaction time 30 is hydrolyzed at 60 DEG C
Minute, filtering washing, spray drying obtains nanocrystal cellulose, related physical characterization parameter such as table 1, Fig. 2, Fig. 4 institute
Show.
Table 1
| Characterization parameter | Embodiment 1 | Embodiment 2 | Comparative example 1 |
| Partial size (μm) | 89 | 96 | 232 |
| The degree of polymerization (DP) | 56 | 76 | 127 |
| Crystallinity (%) | 87 | 83 | 70 |
| Yield (%) | 50 | 47 | 20 |
Claims (8)
1. a kind of preparation process of nanocrystal cellulose, it is characterised in that comprising: which cellulose wood pulp is passed through mechanical treatment
After be added in hydrochloric acid solution progress first gradient hydrolysis, be hydrolyzed into the degree of polymerization less than 350, filtering cleaning is filtered dry；Again will
Filter cake is added to the hydrolysis that sulfuric acid solution carries out the second gradient, is hydrolyzed into the degree of polymerization less than 100, and filtering cleaning is dry, obtains
To nanocrystal cellulose；The concentration of the hydrochloric acid solution is 0.5~3.0mol/L, and the mass fraction of the sulfuric acid solution is
30%~80%.
2. a kind of preparation process of nanocrystal cellulose as described in claim 1, it is characterised in that the α of the cellulose wood pulp
The content of cellulose is greater than 90wt%, and the cellulose wood pulp is the side less than 2cm × 2cm through mechanical treatment by Market Pulp
Block.
3. a kind of preparation process of nanocrystal cellulose as described in claim 1, it is characterised in that the hydrochloric acid solution it is dense
Degree is 1.0mol/L.
4. a kind of preparation process of nanocrystal cellulose as described in claim 1, which is characterized in that the matter of the sulfuric acid solution
Measuring score is 30%~45%.
5. a kind of preparation process of nanocrystal cellulose as described in claim 1, it is characterised in that the water of the first gradient
The temperature of solution reaction is 80~120 DEG C, and the time of the hydrolysis of the first gradient is 10~60 minutes.
6. a kind of preparation process of nanocrystal cellulose as described in claim 1, it is characterised in that the water of second gradient
The temperature of solution reaction is 40~80 DEG C, and the time of the hydrolysis of second gradient is 10~60 minutes.
7. a kind of preparation process of nanocrystal cellulose as described in claim 1, it is characterised in that the water of the first gradient
The hydrolysis of solution reaction and the second gradient carries out under stiring, is stirred using overhead stirrer, and revolving speed is 100~500 revs/min
Clock.
8. a kind of preparation process of nanocrystal cellulose as described in claim 1, it is characterised in that the drying is dry for air-flow
Dry, fluidized drying or spray drying.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341663A (en) * | 2001-09-30 | 2002-03-27 | 中国科学院广州化学研究所 | Method for preparing nanocrystal cellulose by means of acid hydrolysis |
| CN103074794A (en) * | 2013-02-04 | 2013-05-01 | 上海同化新材料科技有限公司 | Method for preparing cellulose nanoparticles from waste cotton wool |
| CN105777913A (en) * | 2016-04-15 | 2016-07-20 | 青岛科技大学 | Efficient cellulose nanocrystalline preparing method |
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- 2017-01-21 CN CN201710049562.9A patent/CN106810614B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341663A (en) * | 2001-09-30 | 2002-03-27 | 中国科学院广州化学研究所 | Method for preparing nanocrystal cellulose by means of acid hydrolysis |
| CN103074794A (en) * | 2013-02-04 | 2013-05-01 | 上海同化新材料科技有限公司 | Method for preparing cellulose nanoparticles from waste cotton wool |
| CN105777913A (en) * | 2016-04-15 | 2016-07-20 | 青岛科技大学 | Efficient cellulose nanocrystalline preparing method |
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