CN105131129B - A kind of preparation method of nano-cellulose - Google Patents
A kind of preparation method of nano-cellulose Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of nano-cellulose, belongs to Bio-Nano-Materials field.Solve the problems, such as that existing method can not thoroughly remove foreign ion, complex steps and high energy consumption.This method first prepares nano-cellulose suspension；Then alkalescence anion-exchange resin is put into ion interchange unit, active processing is carried out to alkalescence anion-exchange resin；Obtained nano-cellulose suspension is poured into from ion interchange unit is suitable for reading, alkalescence anion-exchange resin of the nano-cellulose suspension flow after activity is handled, outflow is exported below ion interchange unit, obtains treatment fluid I；With deionized water rinsing ion interchange unit, treatment fluid II is obtained；Obtained treatment fluid I and treatment fluid II are centrifuged, nano-cellulose precipitation is obtained, after freeze-dried, obtains nano-cellulose.Preparation method of the invention is simple, the time is short, saves cost, and without foreign ion is introduced, also without the size and property for changing nano-cellulose.
Description
Technical field
The invention belongs to biomass nano Material Field, and in particular to a kind of preparation method of nano-cellulose.
Technical background
As a kind of new nano meter biomaterial, nano-cellulose is increasingly subject to the extensive concern of all circles.Nanofiber
Element is defined as at least one-dimensional size and reaches 1~100nm, and the cellulose that can disperse to be formed stable suspension in water is brilliant
Body.Common nano-cellulose is broadly divided into the nano-cellulose of plant origin and the nano-cellulose of non-plant origin.It is inorganic
Acid hydrolyzed cellulose is the important channel for obtaining nano-cellulose.Mineral acid hydrolysis can remove the amorphous region of cellulose,
While reducing microcrystalline cellulose size, the nano-cellulose of high-crystallinity is obtained.Used in nano-cellulose preparation process
Inorganic acid has sulfuric acid, hydrochloric acid, phosphoric acid etc..Wherein sulfuric acid is the most commonly used, and also sulfuric acid and hydrochloric acid are coordinated and made by someone with certain proportion
With.Nineteen forty-seven Nickerson and Habrle are in document Ind Eng Chem Res, 39 (11) (1947), in pp.1507-1512
Using timber as raw material, using the method for hydrochloric acid and sulfuric acid mixed hydrolysis, nano-cellulose soliquid is prepared.Bondeson
Deng in document Cellulose, 2006,13 (2):One kind sour water solution Norway spruce wood pulp is described in 171-180, is prepared steady
The method of fixed nano-cellulose suspension.Gray is in Biomacromolecules, 2005,6 (2):1048-1054 and
Cellulose,2006,938:Describe the raw materials such as sulfuric acid solution cotton, wood pulp in the documents such as 26-32 in detail and obtain different qualities
Nano-cellulose method.
But the method that the inorganic acid hydrolyzation reported at present prepares nano-cellulose, dispel in nano-cellulose suspension
The process of residual acid, the problem of different be present, and the performance generation that the presence of residual acid can be to the nano-cellulose of preparation is important
Influence.Such as sulfonic presence in nano-cellulose, the heat endurance of nano-cellulose can be reduced.Usual method is to preparing
Obtained nano-cellulose suspension carries out low-temperature centrifugation washing repeatedly.Nanjing Forestry University is CN in application publication number
In 103172886A patent, there is provided the detailed step of this method：Suspension after acidolysis, being diluted with water makes hydrolysis
Stop.Part acid solution is centrifuged off, distillation water washing, centrifugation are repeated several times, and cellulose suspension is filled in bag filter and dialysed, extremely
PH value reaches neutral, to remove remaining acid solution.The centrifugal rotational speed that this processing mode needs is very high, and workload is big, and time-consuming,
High energy consumption.Guangzhou Inst of Chemistry, Chinese Academy of Sciences is in the patent that Authorization Notice No. is the C of CN 1141321, there is provided a kind of
With low concentration highly basic (such as sodium hydroxide) antacid method, this method is easy to operate, and cost is low.But the method can not be removed and received
Acid ion in rice cellulose, and introduce new foreign ion (such as sodium ion).Cause what acidolysis obtained to receive simultaneously
Rice cellulose I is changed into nano-cellulose II.Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences is in application publication number
In the A of CN 104448007 patent, there is provided a kind of method for replacing inorganic acid to prepare nano-cellulose with formic acid, the method solution
Determined inorganic liquid acid removal and recovery it is difficult the problem of.But the method needs to be evaporated under reduced pressure, high energy consumption, cost height.
In summary, the existing inorganic acid hydrolyzation of removal prepares residual sour method during nano-cellulose, is primarily present
The problems such as foreign ion, step are more, it is more to take, high energy consumption can not be thoroughly removed, so being badly in need of a kind of to the preparation of inorganic acid hydrolyzation
The method that the process of nano-cellulose optimizes.
The content of the invention
The invention aims to solve existing method can not thoroughly remove foreign ion, complex steps and high energy consumption
The problem of, and a kind of preparation method of nano-cellulose is provided.
The present invention provides a kind of preparation method of nano-cellulose, and this method includes：
Step 1：Prepare nano-cellulose suspension；
Step 2：Alkalescence anion-exchange resin is put into ion interchange unit, alkalescence anion-exchange resin is entered
Row activity processing；
Step 3：The nano-cellulose suspension that step 1 obtains is poured into from ion interchange unit is suitable for reading, nanofiber
Alkalescence anion-exchange resin of the plain suspension flow after activity is handled, outflow is exported below ion interchange unit, is obtained everywhere
Manage liquid I；
Step 4：With deionized water rinsing ion interchange unit, treatment fluid II is obtained；
Step 5：Treatment fluid II obtained by treatment fluid I and step 4 that step 3 obtains is centrifuged, obtains nanometer
Cellulose precipitates, after freeze-dried, obtain nano-cellulose.
Preferably, it is that cellulosic material is carried out into acid with inorganic acid that described step one, which prepares nano-cellulose suspension,
Obtained after solution.
Preferably, described cellulosic material is selected from microcrystalline cellulose, cotton, timber, bamboo wood, stalk, absorbent cotton, wood
One kind in slurry, straw pulp, bamboo pulp, wood-fibred or bamboo fibre etc..
Preferably, one or more of the described inorganic acid in sulfuric acid, hydrochloric acid or nitric acid.
Preferably, the alkali anion ion exchange resin be strong-base anion-exchange resin and alkalescent the moon from
Sub-exchange resin.
Preferably, described ion interchange unit is separatory funnel.
Preferably, the dosage of the alkalescence anion-exchange resin after described activity processing is every milliliter of nano-cellulose
Suspension uses the alkalescence anion-exchange resin after 1-10g activity processing.
Preferably, it is described that active processing is carried out to alkalescence anion-exchange resin, concretely comprise the following steps：
Step 1：By alkalescence anion-exchange resin immersion in deionized water, stir 3-60 minutes, be then filled in from
In sub- switch；
Step 2：Sodium chloride solution is poured into ion interchange unit, alkalescence anion-exchange resin is immersed in sodium chloride
In solution, after soaking 10-30 hours, liquid is released, then with deionized water rinsing alkalescence anion-exchange resin 2-4 times；
Step 3：Hydrochloric acid solution is poured into ion interchange unit, alkalescence anion-exchange resin is immersed in hydrochloric acid solution
In, after standing 1-4 hours, liquid is released, then with deionized water rinsing to neutrality；
Step 4：Sodium hydroxide solution is poured into ion interchange unit, alkali anion is exchanged and is immersed in sodium hydroxide
In solution, after standing 1-4 hours, liquid is released, then with deionized water, flushing to neutrality；
Step 5：Repeat step 3 and step 4,2-4 times, that is, obtain activated basic anion exchange resin.
Beneficial effects of the present invention
The invention provides a kind of preparation method of nano-cellulose, this method is dispelled using alkalescence anion-exchange resin
Except the method that acid hydrolyzation prepares nano-cellulose residual acid, this method makes full use of activated basic anion exchange resin to liquid
Middle SO4 2-、Cl-、NO3 -The absorption of plasma, and go out OH in dissociation in water-, realize that the nano-cellulose prepared to acid hydrolyzation hangs
Residual acid is dispelled in supernatant liquid, and alkalescence anion-exchange resin can reuse processing nano-cellulose suspension.With
Prior art compares, and the inventive method removes inorganic acid hydrolyzation using simple deacidite and prepares nanofiber
The method of residual acid during plain suspension, step is simple, reduces the time for preparing nano-cellulose, while reduce energy
Consumption, cost is saved, and without foreign ion is introduced, also without the size and property for changing nano-cellulose.
Brief description of the drawings
Fig. 1 is that the TEM for the nano-cellulose that nano-cellulose prepared by the embodiment of the present invention 1 is prepared with conventional method schemes
Piece.
Fig. 2 is the INFRARED SPECTRUM for the nano-cellulose that nano-cellulose prepared by the embodiment of the present invention 1 is prepared with conventional method
Figure.
Embodiment
Technical scheme is described in further detail below in conjunction with specific embodiments.Purpose is to make
Those skilled in the art are more clearly understood and recognized to the application.Following specific embodiment should not be in any degree
It is understood or is construed to the application claims are claimed the limitation of scope.
The present invention provides a kind of preparation method of nano-cellulose, and this method includes：
Step 1：Prepare nano-cellulose suspension；
Step 2：Alkalescence anion-exchange resin is put into ion interchange unit, alkalescence anion-exchange resin is entered
Row activity processing；
Step 3：The nano-cellulose suspension that step 1 obtains is poured into from ion interchange unit is suitable for reading, nanofiber
Alkalescence anion-exchange resin of the plain suspension flow after activity is handled, outflow is exported below ion interchange unit, is obtained everywhere
Manage liquid I；
Step 4：With deionized water rinsing ion interchange unit, treatment fluid II is obtained；
Step 5：Treatment fluid II obtained by treatment fluid I and step 4 that step 3 obtains is centrifuged, obtains nanometer
Cellulose precipitates, after freeze-dried, obtain nano-cellulose.
According to the present invention, the described method for preparing nano-cellulose suspension is to carry out cellulosic material with inorganic acid
Obtained after acidolysis, specific steps are preferably：Cellulosic material is put into inorganic acid solution, it is small that 3-6 is reacted at 45-60 DEG C
When, after reaction terminates, prevent it from continuing to hydrolyze, supernatant is removed after standing, add deionization by solution in deionized water
Water, repeat to stand process 3-5 times except supernatant, nano-cellulose suspension is obtained after finally adding deionized water；Described
Cellulosic material is preferably selected from microcrystalline cellulose, cotton, cotton linter, timber, bamboo wood, stalk, absorbent cotton, wood pulp, straw pulp, bamboo
One kind in slurry, wood-fibred or bamboo fibre etc., described inorganic acid are preferably selected from one kind or several in sulfuric acid, hydrochloric acid or nitric acid
Kind.
According to the present invention, alkalescence anion-exchange resin is put into ion interchange unit, alkali anion is exchanged and set
Fat carries out active processing；Described does not have particular/special requirement to ion interchange unit, can use any appearance with coutroi velocity device
The separatory funnel of device, preferably commercialization；Described alkali anion ion exchange resin preferably includes strong alkalinity anion exchange
Resin or weak-base anion-exchange resin, are not particularly limited, and can be any models being commercially available.It is more preferably strong
Alkaline #201 (resin processing plant of Nankai University), strong base 717, strong base 201*7 (Shanghai Resin Factory), Amerlite XE-98,
Amerlite IRA-400, Dowex 1, Dowex2, Lewatit MII, weak base 330 (Shanghai Resin Factory), weak base #301 (Nankai
Resin processing plant of university), Amerlite IR-4B, Dowex 3, Permutit W or Wofatit M, most preferably strong base #201
(resin processing plant of Nankai University), strong base 717, strong base 201*7 (Shanghai Resin Factory), Amerlite XE-98, Amerlite
IRA-400、Dowex 1、Dowex2、Lewatit MII。
Described carries out active processing to alkalescence anion-exchange resin, concretely comprises the following steps：
Step 1, by the alkalescence anion-exchange resin weighed immersion in deionized water, it is fully expanded, machinery
Stir 3-60 minutes after, remove the impurity of suspension and resin in small, broken bits, clean alkalescence anion-exchange resin be filled in from
In sub- switch；
Step 2, sodium chloride solution poured into ion interchange unit, alkalescence anion-exchange resin is immersed in sodium chloride
In solution, after soaking 10-30 hours, liquid is released, then with deionized water rinsing alkalescence anion-exchange resin 2-4 times；It is described
The mass concentration of sodium chloride solution be preferably 2%-10%；
Step 3, hydrochloric acid solution poured into ion interchange unit, alkalescence anion-exchange resin is immersed in hydrochloric acid solution
In, after standing 1-4 hours, liquid is released, then the alkalescence anion-exchange resin of above-mentioned processing is being exchanged into dress with deionized water
Middle flushing is put to neutrality, the mass fraction of described hydrochloric acid solution is preferably 2%-5%；
Step 4, sodium hydroxide solution are poured into ion interchange unit, alkalescence anion-exchange resin is immersed in hydroxide
In sodium solution, after standing 1-4 hours, liquid is released, then with deionized water by the alkalescence anion-exchange resin of above-mentioned processing
Rinsed in switch to neutrality, the mass fraction of described sodium hydroxide is preferably 2%-5%；
Step 5, repeat step 3 and step 4,2-4 times, that is, obtain activated basic anion exchange resin.
According to the present invention, obtained nano-cellulose suspension is slowly poured into from ion interchange unit is suitable for reading, nanometer
Cellulose suspension flows through the alkalescence anion-exchange resin after activity processing, and outflow is exported below ion interchange unit, is obtained
To treatment fluid I；The dosage of activated basic anion exchange resin is that every milliliter of nano-cellulose suspension is dried using 1-10g
Deacidite.
According to the present invention, with deionized water rinsing ion interchange unit, to wash out the nano-cellulose wherein remained, obtain
To treatment fluid II；
According to the present invention, obtained treatment fluid I and treatment fluid II are centrifuged, water unnecessary in treatment fluid is removed, obtains
Precipitated to nano-cellulose, after freeze-dried, obtain nano-cellulose.
According to the present invention, described activated basic anion exchange resin reuses after being handled, and continues to locate
Nano-cellulose suspension is managed, processing concretely comprises the following steps：
1st, the sodium chloride solution for being 2%-10% with mass concentration is poured into ion interchange unit, makes activated basic anion
Exchanger resin is immersed in sodium chloride solution, after soaking 10-30 hours, releases liquid, then with deionized water rinsing exchanger resin
2-4 times；
2nd, it is that 2%-5% sodium hydroxide solutions are poured into ion interchange unit by mass fraction, is immersed in exchanger resin
In sodium hydroxide solution, after standing 1-4 hours, liquid is released, is then exchanged the alkali ion of above-mentioned processing with deionized water
Resin is rinsed in switch to neutrality, as reusable deacidite.
With reference to embodiment, the present invention will be further described in detail.
Embodiment 1
(1) it is that 20 microns of micrometer fibers element is added in the 10ml sulfuric acid solutions prepared by 1g sizes, wherein sulfuric acid
Mass fraction is 64%, and stirred suspension is simultaneously heated to 45 DEG C, reaction 3 hours；After reaction terminates, solution is poured on going for 50ml
In ionized water, prevent it from continuing to hydrolyze, supernatant is removed after standing, add and obtain 60 milliliters of nano-celluloses after deionized water and hang
Supernatant liquid, repeat to stand process 3-5 time except supernatant, 60 milliliters of nano-celluloses suspensions are obtained after finally adding deionized water
Liquid；
(2) 600g strong-base anion-exchange resins 717 are put into 1000ml separatory funnel, to strong alkalinity anion
Exchanger resin 717 carries out active processing；
(3) by pending nano-cellulose suspension slowly from equipped with active strong-base anion-exchange resin 717
Separatory funnel it is suitable for reading be poured into, nano-cellulose suspension flow goes out after active strong-base anion-exchange resin 717 from below
Mouth outflow, obtains treatment fluid I；
(4) continue to be exchanged with 20% deionized water rinsing activity strong alkalinity anion of nano-cellulose suspension vol
Resin 717, to wash out the nano-cellulose wherein remained, obtain treatment fluid II；
(5) treatment fluid I and treatment fluid II are centrifuged, removes water unnecessary in treatment fluid, obtain nano-cellulose and sink
Form sediment, after freeze-dried, obtain white powder, as nano-cellulose.
The nano-cellulose that embodiment 1 is obtained and the nano-cellulose being prepared using conventional method are characterized,
Described conventional method is to obtain nano-cellulose suspension by sulphuric acid hydrolysis micrometer fibers element, specifically prepares nano-cellulose
The experiment condition of suspension and the experiment condition in embodiment 1 are completely the same, then successively centrifuge suspension, dialyse, freezing and do
It is dry to obtain nano-cellulose.
Nano-cellulose that the embodiment of the present invention 1 the obtains deacidification effect evidence consistent with the deacidification effect of conventional method,
It is that the pH value of dispersion liquid after the nano-cellulose being prepared by measuring above two method dissolves in water is carried out.
The specific implementation step for measuring nano-cellulose dispersion liquid pH value is as follows：
(1) received respectively by prepared by the 0.01g nano-celluloses being prepared by the embodiment of the present invention 1 and conventional method
Rice cellulose is placed in 40ml water, and ultrasound 15 minutes, obtain nano-cellulose dispersion liquid after stirring.
(2) pH value of nano-cellulose dispersion liquid prepared by above-mentioned (1) is measured respectively using PH testers, test result is shown in
Table one.
As a result show, nano-cellulose dispersion liquid pH value prepared by two methods approaches, difference 0.02.Consider instrument
The test error of device, it could be assumed that, nano-cellulose dispersion liquid prepared by the inventive method is prepared with conventional centrifugal dialysis
Nano-cellulose dispersion liquid acid content is consistent, that is, during preparing nano-cellulose, the inventive method except residual acid effect with
Traditional sour effect that residual is removed by centrifugation, dialysis is consistent.And do not have to the crystal habit and size of nano-cellulose
Influence.Fig. 1 is the TEM pictures for the nano-cellulose that nano-cellulose prepared by the embodiment of the present invention 1 is prepared with conventional method.From
Understood in figure, nano-cellulose size prepared by two kinds of different disposal methods is consistent, and length is 100-200 nanometers, a diameter of small
In 100 nanometers, and the nano-cellulose that above two different disposal method obtains is all bar-shaped.
The evidence that the structure of above two nano-cellulose is consistent is carried out using Fourier transform infrared (FT-IR)
's.The infrared spectrum for the nano-cellulose that Fig. 2 is prepared for nano-cellulose prepared by the embodiment of the present invention 1 with conventional method, Fig. 2
As can be seen that the inventive method nano-cellulose for handling to obtain and the nano-cellulose that is obtained by centrifugation, dialysis treatment
Each peak is in position and the intensity at peak is identical.
Using plasma emission spectrometer (ICP) is proved in the method for the embodiment of the present invention 1 and conventional method, sodium hydroxide
Nano-cellulose is prepared with method to compare without the new impurity of introducing.Wherein, in sodium hydroxide and the side of nano-cellulose is prepared
Method is to obtain nano-cellulose suspension by sulphuric acid hydrolysis micrometer fibers element, specifically prepare the reality of nano-cellulose suspension
Test condition and the experiment condition in embodiment 1 is completely the same, then instilled with sodium hydroxide solution in nano-cellulose suspension, extremely
Nano-cellulose suspension PH=7, nano-cellulose is obtained through freeze-drying after centrifugation.
(1) 0.01g is taken to be received by what the method for embodiment 1, conventional method and sodium hydroxide neutralization method were prepared respectively
Rice cellulose is placed in 40ml water, after stirring, ultrasound 15 minutes, after standing, takes 15ml supernatants；
(2) supernatant obtained respectively to three kinds of methods by ICP carries out elementary analysis.Test result is shown in Table 1.
As known from Table 1, the method neutralized using sodium hydroxide prepares nano-cellulose, introduces impurity-sodium element.And this
In the nano-cellulose that nano-cellulose and logical conventional method prepared by inventive method obtains, impurity element is not introduced.
Table 1
| Sulphur | Carbon | Other | PH | |
| The nano-cellulose that embodiment 1 obtains | Have | Have | Nothing | 6.78 |
| The nano-cellulose that conventional method obtains | Have | Have | Nothing | 6.76 |
| The nanofiber that sodium hydroxide neutralisation treatment obtains | Have | Have | Sodium | - |
Embodiment 2
(1) it is that 50 microns of micrometer fibers element is added in the 18ml sulfuric acid solutions prepared by 1g sizes, wherein sulfuric acid
Mass fraction is 64%, and stirred suspension is simultaneously heated to 45 DEG C, reaction 3 hours；After reaction terminates, solution is poured on going for 90ml
In ionized water, prevent it from continuing to hydrolyze, supernatant is removed after standing, 108 milliliters of nano-celluloses are obtained after adding deionized water
Suspension, repeat to stand process 3-5 time except supernatant, finally add and obtain 108ml nano-celluloses after deionized water and suspend
Liquid；
(2) in the separatory funnel for being put into 108g strong-base anion-exchange resins #201, alkali anion is exchanged and set
Fat carries out active processing；
(3) by pending nano-cellulose suspension slowly from equipped with active strong-base anion-exchange resin #201
Separatory funnel it is suitable for reading be poured into, nano-cellulose suspension flow is after active strong-base anion-exchange resin #201, from following
Outlet outflow, obtains treatment fluid I；
(4) continue to be exchanged with 20% deionized water rinsing activity strong alkalinity anion of nano-cellulose suspension vol
Resin #201, to wash out the nano-cellulose wherein remained, obtain treatment fluid II；
(5) treatment fluid I and treatment fluid II are centrifuged, removes water unnecessary in treatment fluid, obtain nano-cellulose and sink
Form sediment, after freeze-dried, obtain white powder, as nano-cellulose.
Embodiment 3
(1) cleaning and dried 10g cotton linters are added in the 85ml sulfuric acid solutions prepared, wherein the volume of sulfuric acid
Fraction is 30%, and stirred suspension is simultaneously heated to 60 DEG C, reaction 6 hours；Reaction terminate after, by solution be poured on 425ml go from
In sub- water, prevent it from continuing to hydrolyze, supernatant is removed after standing, add and obtain 510 milliliters of nano-celluloses after deionized water and hang
Supernatant liquid, repeat to stand process 3-5 time except supernatant, 510ml nano-cellulose suspension is obtained after finally adding deionized water
Liquid；
(2) 2500g strong-base anion-exchange resins 717 are put into separatory funnel, to alkalescence anion-exchange resin
Carry out active processing；
(3) by pending nano-cellulose suspension slowly from equipped with active strong-base anion-exchange resin 717
Separatory funnel it is suitable for reading be poured into, nano-cellulose suspension flow goes out after active strong-base anion-exchange resin 717 from below
Mouth outflow, obtains treatment fluid I；
(4) continue to be exchanged with 20% deionized water rinsing activity strong alkalinity anion of nano-cellulose suspension vol
Resin 717, to wash out the nano-cellulose wherein remained, obtain treatment fluid II；
(5) treatment fluid I and treatment fluid II are centrifuged, removes water unnecessary in treatment fluid, obtain nano-cellulose and sink
Form sediment, after freeze-dried, obtain white powder, as nano-cellulose.
Embodiment 4
(1) 2g bamboo pulps are added in the 100ml sulfuric acid solutions prepared, wherein the mass fraction of sulfuric acid is 46%, stirring
Suspension is simultaneously heated to 45 DEG C, reaction 4 hours；After reaction terminates, solution is poured in 500ml deionized waters, prevents its continuation
Hydrolyze, supernatant is removed after standing, 600 milliliters of nano-cellulose suspension are obtained after adding deionized water, repeat to stand except upper
The process of clear liquid 3-5 times, 600ml nano-cellulose suspension is obtained after finally adding deionized water；
(2) 1800g strong-base anion-exchange resins 717 are put into separatory funnel, to alkalescence anion-exchange resin
Carry out active processing；
(3) by pending nano-cellulose suspension slowly from equipped with active strong-base anion-exchange resin 717
Separatory funnel it is suitable for reading be poured into, nano-cellulose suspension flow goes out after active strong-base anion-exchange resin 717 from below
Mouth outflow, obtains treatment fluid I；
(4) continue to be exchanged with 20% deionized water rinsing activity strong alkalinity anion of nano-cellulose suspension vol
Resin 717, to wash out the nano-cellulose wherein remained, obtain treatment fluid II；
(5) treatment fluid I and treatment fluid II are centrifuged, removes water unnecessary in treatment fluid, obtain nano-cellulose and sink
Form sediment, after freeze-dried, obtain white powder, as nano-cellulose.
Claims (2)
1. a kind of preparation method of nano-cellulose, it is characterised in that this method includes：
Step 1：By 1g sizes it is that 20 microns of micrometer fibers element is added in the 10ml sulfuric acid solutions prepared, wherein sulfuric acid
Mass fraction is 64%, and stirred suspension is simultaneously heated to 45 DEG C, reaction 3 hours；After reaction terminates, solution is poured on going for 50ml
In ionized water, prevent it from continuing to hydrolyze, supernatant is removed after standing, add and obtain 60 milliliters of nano-celluloses after deionized water and hang
Supernatant liquid, repeat to stand process 3-5 time except supernatant, 60 milliliters of nano-celluloses suspensions are obtained after finally adding deionized water
Liquid；
Step 2：Alkalescence anion-exchange resin is put into ion interchange unit, alkalescence anion-exchange resin is lived
Property processing；
Step 3：The nano-cellulose suspension that step 1 obtains is poured into from ion interchange unit is suitable for reading, nano-cellulose hangs
Supernatant liquid flows through the alkalescence anion-exchange resin after activity processing, and outflow is exported below ion interchange unit, obtains treatment fluid
Ⅰ；
Step 4：With deionized water rinsing ion interchange unit, treatment fluid II is obtained；
Step 5：Treatment fluid II obtained by treatment fluid I and step 4 that step 3 obtains is centrifuged, obtains nanofiber
Element precipitation, after freeze-dried, obtains nano-cellulose；
The length of described nano-cellulose is 100-200 nanometers, a diameter of to be less than 100 nanometers；
The dosage of alkalescence anion-exchange resin after described activity processing uses 1- for every milliliter of nano-cellulose suspension
Alkalescence anion-exchange resin after 10g activity processing；
Described carries out active processing to alkalescence anion-exchange resin, concretely comprises the following steps：
Step 1：By alkalescence anion-exchange resin immersion in deionized water, 3-60 minutes are stirred, is then filled in ion friendship
In changing device；
Step 2：Sodium chloride solution is poured into ion interchange unit, alkalescence anion-exchange resin is immersed in sodium chloride solution
In, after soaking 10-30 hours, release liquid, then with deionized water rinsing alkalescence anion-exchange resin 2-4 times；
Step 3：Hydrochloric acid solution is poured into ion interchange unit, alkalescence anion-exchange resin is immersed in hydrochloric acid solution,
After standing 1-4 hours, liquid is released, then with deionized water rinsing to neutrality；
Step 4：Sodium hydroxide solution is poured into ion interchange unit, alkali anion is exchanged and is immersed in sodium hydroxide solution
In, after standing 1-4 hours, liquid is released, then with deionized water, flushing to neutrality；
Step 5：Repeat step 3 and step 4,2-4 times, that is, obtain activated basic anion exchange resin；
Described alkalescence anion-exchange resin is strong-base anion-exchange resin 717.
A kind of 2. preparation method of nano-cellulose according to claim 1, it is characterised in that described ion exchange dress
It is set to separatory funnel.
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| CN109970873B (en) * | 2019-04-03 | 2021-06-18 | 湖南九典宏阳制药有限公司 | Preparation method of pharmaceutical adjuvant grade microcrystalline cellulose |
| CN110284352A (en) * | 2019-05-29 | 2019-09-27 | 浙江金昌特种纸股份有限公司 | A kind of bamboo wood nano-cellulose preparation method of super clean |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740341A (en) * | 2005-09-15 | 2006-03-01 | 陈秀恋 | Decolour and refining apparatus for ion exchange method of sugar cane juice |
| CN101709336A (en) * | 2009-12-21 | 2010-05-19 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing high-concentration fructose syrup |
| CN101768221A (en) * | 2010-03-12 | 2010-07-07 | 福建农林大学 | Method for preparing nano-crystal cellulose II by using basic anion-exchange resin |
| CN101942102A (en) * | 2010-09-07 | 2011-01-12 | 东南大学 | Preparation method of powder nano cellulose |
| CN103172886A (en) * | 2013-03-14 | 2013-06-26 | 南京林业大学 | Method for quickly preparing colorful nanocrystalline cellulose film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1740341A (en) * | 2005-09-15 | 2006-03-01 | 陈秀恋 | Decolour and refining apparatus for ion exchange method of sugar cane juice |
| CN101709336A (en) * | 2009-12-21 | 2010-05-19 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing high-concentration fructose syrup |
| CN101768221A (en) * | 2010-03-12 | 2010-07-07 | 福建农林大学 | Method for preparing nano-crystal cellulose II by using basic anion-exchange resin |
| CN101942102A (en) * | 2010-09-07 | 2011-01-12 | 东南大学 | Preparation method of powder nano cellulose |
| CN103172886A (en) * | 2013-03-14 | 2013-06-26 | 南京林业大学 | Method for quickly preparing colorful nanocrystalline cellulose film |
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