CN106893116A - A kind of preparation method of cellulose nano-fibrous biomass gel and aeroge - Google Patents
A kind of preparation method of cellulose nano-fibrous biomass gel and aeroge Download PDFInfo
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- CN106893116A CN106893116A CN201710103378.8A CN201710103378A CN106893116A CN 106893116 A CN106893116 A CN 106893116A CN 201710103378 A CN201710103378 A CN 201710103378A CN 106893116 A CN106893116 A CN 106893116A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0504—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/04—Oxycellulose; Hydrocellulose
Abstract
The present invention relates to a kind of cellulose nano-fibrous biomass gel and the preparation method of aeroge, comprise the following steps：（1）Cellulose is processed through TEMPO/NaBr/NaClO oxidation systems, oxycellulose is obtained；（2）Oxycellulose is obtained cellulose nano-fibrous dispersion liquid in the aqueous solution or weak alkaline aqueous solution through mechanical treatment；（3）Cellulose nano-fibrous dispersion liquid is obtained cellulose nano-fibrous biomass gel through acid coagulating bath or acid vapors bath treatment；（4）Cellulose nano-fibrous biomass gel is obtained cellulose nano-fibrous biogas gel through drying and dehydrating.A kind of preparation method of cellulose nano-fibrous biomass gel of the invention, simple and easy to control, low cost, environmental protection can prepare form is good, intensity is high, fiber content is low biomass gel and aeroge, and it has biocompatibility and nontoxic；The biomass gel with negative electricity characteristic and aeroge for wherein preparing have more preferable reactivity and bioactivity.
Description
Technical field
The present invention relates to the application field of cellulose, and in particular to a kind of cellulose nano-fibrous biomass gel and airsetting
The preparation method of glue.
Background technology
Cellulose is reserves a kind of natural biomass macromolecule the abundantest in nature.Cellulose is primarily present in plant
In the secondary wall of thing cell wall, such as in the biomass such as timber, bamboo wood, rice wheat straw, cotton.Cellulose is structural bio
Macromolecular is connected via strand, the high-crystallinity fiber with nanoscale scope is formed, according to its different biogenetic derivations, day
Right cellulose crystals fibre section is wide from 2nm to 20nm.Cellulose forms senior hierarchical structure in biomass, can be by
Isolated is nanofiber.Nano material has started one upsurge in new material research field with the development of nanometer technology, raw at present
Thing nano-fiber material technology has turned into the study hotspot of countries in the world key project and tip technology.Effectively utilize renewable agriculture
Woods development of resources new bio based high molecular new material is the important directions of biomass and the fusion of new material discipline intersection, to the mankind
Depending on unduly with important strategic importance to fossil resources such as oil is broken away from social development.
In recent years, Many researchers prepare high-performance fiber element gel rubber material, cellulose gel using cellulose nano-fibrous
Glue material has renewable natural polymer concurrently as the third generation gel after inorganic aerogels and synthetic polymer aeroge
And the plurality of advantages of high porosity nano-porous materials, and relative to intensity difference, frangible inorganic gel, natural polymer coagulates
Glue has the characteristics such as good toughness, easy processing, and its mechanical strength is far superior to inorganic silica gels, and cellulose gel turns into natural polymer
A focus in sub- investigation of materials and application.With going deep into for research, Recent study person lays particular emphasis on cellulose base gel force
The raising and functional exploitation of performance are learned, so as to greatly widened material be protected in biomedical, catalyst load and environment
The potential application of the numerous areas such as shield.There is great amount of hydroxy group on cellulose molecular chain, can be by forming intramolecular and intermolecular
Hydrogen bond carries out gelation, so as to the three-dimensional network being physical crosslinking.To extract cellulose nano-fibrous from native cellulose,
Including cellulose nanometer long fibre or nano whisker, it is directly dispersing in water and spontaneously forms gel.When cellulose nano-fibrous point
It is dispersed in water, three-dimensional network can be formed by interfibrous hydrogen bond and long stapled entanglement, so as to the gel stablized,
These fibers turn into the network skeleton of gel, improve the intensity and modulus of gel.
There are many reports on cellulose nano-fibrous based aquagel, Kentaro Abe etc. to be taken out with vacuum at present
The method of filter has prepared the cellulose nano-fibrous gel rubber material of solid content 10%；Dong H etc. are with calcium ion, iron ion etc.
The cellulose nano-fibrous gel rubber material of ionomer is prepared.It is fine that patent CN102671236B discloses a kind of nanometer bacteria
The preparation method of dimension element enhancing gel bionic meniscus composite, mainly using freeze-thaw method to prepare has
The fibre-reinforced polyvinyl alcohol hydrogel biomimetic prosthetic first quarter moon plate material of excellent mechanical performances；Patent CN103205015A is disclosed
A kind of transparent, flexible cellulose aerogels and preparation method thereof, mainly use ionic liquid aqueous solution or ionic liquid
Regenerated in the coagulating bath of alcoholic solution and a kind of transparent, flexible cellulose airsetting has been obtained through alcoholic solvent displacement or alcoholic solvent washing
Glue.But, including in the prior art, the preparation technology of cellulose nano-fibrous biomass gel is answered including above-mentioned patented technology
Research prepared by the physical gel under the conditions of miscellaneous and shortage low concentration (cellulose nano-fibrous concentration is low) and report.
The content of the invention
The first object of the present invention is to provide a kind of cellulose nano biological matter more simple and easy to control, inexpensive, environmentally friendly
The preparation method of gel.
The second object of the present invention is to provide a kind of cellulose nano biological matter more simple and easy to control, inexpensive, environmentally friendly
The preparation method of aeroge.
The first object of the present invention technical scheme is that：
A kind of preparation method of cellulose nano-fibrous biomass gel, comprises the following steps：
（1）Cellulose is processed through TEMPO/NaBr/NaClO oxidation systems, oxycellulose is obtained；
（2）The oxycellulose is obtained cellulose nano-fibrous point in the aqueous solution or weak alkaline aqueous solution through mechanical treatment
Dispersion liquid；
（3）The cellulose nano-fibrous dispersion liquid is obtained cellulose Nanowire through acid coagulating bath or acid vapors bath treatment
Dimension biomass gel.
In order to change the complicated technology that prior art prepares cellulose gel, complicated chemistry rambunctious, physics mistake are reduced
Journey, inventor employs a kind of preparation method more simple and easy to control, inexpensive, environmentally friendly, and inventor passes through 2,2,6,6- tetramethyls
Phenylpiperidines-nitrogen-oxide（TEMPO）The catalyst oxidation system treatment cellulose is obtained oxycellulose, then uses the oxidation
Cellulose prepares cellulose nano-fibrous dispersion liquid through mechanical treatments such as homogenate, ultrasonic waves, finally with the cellulose Nanowire
Dimension dispersion liquid can prepare cellulose nano-fibrous biomass gel through acid coagulating bath or acid vapors bath treatment.Entirely
Preparation process is relatively easy easily-controllable, and cost is lower, and need not use the volatile organic solvent of a large amount of poisonous and harmfuls.
As preferred, step（1）Specifically include：The cellulose of 1 mass parts is added to the water-soluble of 100 mass parts
Liquid, the NaClO for adding NaBr, 0.1-0.5 mass parts of 0.01-0.02 mass parts TEMPO, 0.05-0.2 mass parts mixes shape
Into oxidation reaction system, the pH of the oxidation reaction system is maintained into 9- to NaOH solution is added dropwise in the oxidation reaction system
11；When the oxidation reaction system no longer consumes NaOH, ethanol is added, pH is adjusted to 7 by acid adding, then is obtained through being centrifuged and washing
Oxycellulose.
Cellulose in oxidizing process along with the depolymerization of cellulose macromolecule chain, while the intensity of cellulose can be caused to damage
Lose.The oxidation of cellulose and palliating degradation degree are influenceed by many factors, such as oxidant, the consumption of oxidized thing and oxidation reaction
Condition etc., these factors determine the content of oxidation product；New functional group and its location in simultaneous oxidation product
Stability to cellulose glucoside bond has a significant impact.Additionally, side reaction, the decrystallizing of cellulose in oxidizing process
Also there is larger contact with the degraded of cellulose etc. some other factor.Therefore, in the oxidation reaction process of cellulose, rationally
Selective oxidation system is critically important with the degree of oxidation and palliating degradation degree for controlling cellulose.Inventor uses TEMPO/NaBr/
NaClO oxidation systems are aoxidized to the cellulose, strictly controlled oxidant, be oxidized the consumption and oxidation reaction bar of thing
Part etc., improves the yield of the oxycellulose while fibre strength is ensured.By the way that NaOH solution is added dropwise for the oxidation
Reaction system provides suitable pH.Inventor also judges the process of oxidation reaction by the consumption of NaOH, when oxidation system no longer
During consumption NaOH, inventor adds a small amount of ethanol, and pH is adjusted to 7, terminating reaction by acid adding.Inventor is finally by being centrifuged and wash
Wash, simply and easily remove supernatant and impurity, the water insoluble part for obtaining is the oxycellulose.
As preferred, step（2）Specifically include：By step（1）The obtained oxycellulose is carried out in being put into pure water
Mechanical treatment is obtained the cellulose nano-fibrous dispersion liquid；Or the oxycellulose is put into pure water and that NaOH is added dropwise is molten
Liquid regulation pH makes 7 ＜ pH≤10, then carries out mechanical treatment the cellulose nano-fibrous dispersion liquid is obtained.
In order that the cellulose nano-fibrous biomass gel for preparing is more homogeneous, oxycellulose described in inventor
It is dispersed in liquid by mechanical treatments such as homogenate ultrasounds and can be prepared by the cellulose nano-fibrous dispersion liquid.Hair
A person of good sense also by adjusting pH to 7-10, makes system be in weakly alkaline environment, so as to the cellulose with negative electricity characteristic is obtained
Nanofiber dispersion liquid, can be prepared special with negative electricity by the described cellulose nano-fibrous dispersion liquid with negative electricity characteristic
The cellulose nano-fibrous biomass gel and aeroge of property.After the oxycellulose is scattered in liquid, inventor is also
Can not on a small quantity have scattered large-size fiber by the way that removal is centrifuged, the supernatant after centrifugation is described cellulose nano-fibrous
Dispersion liquid.
As preferred, step（3）Specifically include：By step（2）The obtained cellulose nano-fibrous dispersion liquid is with dense
Spend for the acid solution of 3-7M carries out acid coagulating bath or acidic gas vapors bath treatment 0.1-12h is obtained cellulose nano-fibrous biomass
Gel.
Inventor is carrying out acid coagulating bath or acid steaming to the cellulose nano-fibrous dispersion liquid with the acid solution
Vapour bath treatment can be prepared by cellulose nano-fibrous biomass gel.Inventor also found, when described cellulose nano-fibrous point
The concentration of dispersion liquid（The mass fraction of fiber）During less than 0.6%, processed using the acid vapors and be advisable.Use TEMPO oxidation systems
The electrostatic repulsion that the carboxyl on the cellulose nano-fibrous surface for preparing is electrically charged causes dividing for cellulose nano-fibrous energy stabilization
It is dispersed in neutral or weak base aqueous phase system.When cellulose nano-fibrous dispersion liquid is after acid coagulating bath or steam bath are processed,
The stability of this electrostatic repulsion is destroyed.In acid condition, the electric charge of the carboxyl with negative electrical charge is neutralized, nanofiber
Between electrostatic repulsion disappear, be cross-linked with each other to form hydrogel between nanofiber.Particularly acid gas phase coagulating bath（Acid vapors
Bath）, it is to avoid the cellulose nano-fibrous dispersion liquid directly contact coagulating bath solution.Additionally, the method is easy to use, and
The selection that the acid coagulating bath or acidic gas vapors bathe used acid solution is various, and any volatile acid solution all may be used
To use.
Used as preferred, the cellulose is obtained by cellulosic material is preprocessed：By cellulosic material quality point
Number is submerged for the sodium chlorite solution of 0.3-0.7%, adds acetum and pH is adjusted into≤5, and 1- is processed at 60-80 DEG C
3h, is finally washed till the neutral prepared cellulose with pure water；The cellulosic material be microcrystalline cellulose, paper pulp, absorbent cotton with
And at least one from timber and straw in obtained cellulose.
Cellulose is primarily present in the secondary wall of plant cell walls, such as timber, bamboo wood, rice wheat straw, cotton etc.
In biomass.In order to reduce production cost, the high value added utilization of paper pulp, bamboo and wood material, stalk etc., the preferred paper of inventor are realized
Slurry, microcrystalline cellulose, absorbent cotton and obtained cellulose is cellulosic material, but paper pulp etc. from timber and straw
Cellulosic material containing a small amount of lignin often due to cannot directly carry out step（1）, step（2）, step（3）Prepare cellulose
Nanofiber biomass gel, therefore, inventor is pre-processed the cellulosic material, is obtained and be can be used to prepare cellulose
The cellulose of nanofiber biomass gel and aeroge.
As preferred, step（1）In, to NaOH solution is added dropwise in the oxidation reaction system by the oxidation reaction body
The pH of system maintains 10.
Oxidation reaction to the oxidation system has a direct impact, and inventor has found that pH is 10 reaction through repetition test
Under the conditions of, it is more beneficial for the preparation of the oxycellulose.
As preferred, concentration≤1% of the cellulose nano-fibrous dispersion liquid.
The cellulose nano-fibrous biomass gel and aeroge form prepared by guarantee be good, intensity it is high on the premise of
（Increase the cellulose nano-fibrous biomass gel and airsetting without materials such as any other macromolecular compounds simultaneously
The intensity of glue）, the content of cellulose in the cellulose nano-fibrous biomass gel and aeroge is reduced, it is a technology difficulty
Topic.Inventor's concentration（Cellulose mass fraction）≤ 1% described cellulose nano-fibrous dispersion liquid carries out the cellulose
The preparation of nanofiber biomass gel and aeroge.
Used as preferred, the acid solution is Volatile acid solutions.
The selection of the acid solution is to acid coagulating bath or acid vapors bath treatment and the final cellulose Nanowire
The shaping of dimension biogas gel and aeroge has a direct impact, and inventor is had found at the acid coagulating bath or acid vapors bath
Reason especially acid vapors bath treatment, is advisable with Volatile acid solutions.Acid coagulating bath or acidity are carried out using the acid solution
The time of steam bath treatment is too short to make the cellulose nano-fibrous biomass gel cannot effectively be molded, and process time is long
Production efficiency can then be reduced, increase production cost, inventor has found through repetition test, the acid coagulating bath treatment 0.1-6h is
Preferably, the acid vapors bath treatment 6-12h is advisable.
Used as preferred, the acid solution is hydrochloric acid or acetic acid.
The selection of the acid solution coagulating bath is processed and the final cellulose nano-fibrous biogas gel and
The shaping of aeroge has a direct impact, and inventor has found through repetition test, and the acid solution is advisable with acetic acid or hydrochloric acid.
The second object of the present invention technical scheme is that：
A kind of preparation method of cellulose nano-fibrous biogas gel, the cellulose nano-fibrous biomass gel is passed through
Drying and dehydrating is obtained cellulose nano-fibrous biogas gel.
The cellulose nano-fibrous biomass gel needs could to be finally obtained through drying and dehydrating cellulose nano-fibrous
Biogas gel, and inventor preferably uses freeze-drying or supercritical drying, and drying and dehydrating effect is good, preferably to make
Obtain cellulose nano-fibrous biogas gel.
In sum, the invention has the advantages that：
1st, the preparation method of a kind of cellulose nano-fibrous biomass gel of the invention and aeroge, method is simply and readily controlled
System, preparation cost is relatively low, and preparation process need not use the volatile organic solvent of a large amount of poisonous and harmfuls.
, a kind of cellulose nano-fibrous biomass gel of the invention and aeroge preparation method can prepare form
Good, the biomass gel and aeroge that intensity is high, fiber content is low, it has biocompatibility and nontoxic；Wherein prepare
What is obtained with the cellulose nano-fibrous biomass gel of negative electricity characteristic and aeroge there is more preferable reactivity and biology to live
Property.
, a kind of cellulose nano-fibrous biomass gel of the invention and aeroge preparation method, can be made with paper pulp etc.
It is cellulosic material, both reduces cost, the high value added utilization of paper pulp etc. is realized again.
Brief description of the drawings
Fig. 1 is the birefringence digital photograph of the cellulose nano-fibrous dispersion liquid；
Fig. 2 is the cellulose nano-fibrous transmission electron microscope picture;
Fig. 3 is the digital photograph of the cellulose nano-fibrous biomass gel;
Fig. 4 is the digital photograph of the cellulose nano-fibrous biogas gel；
Fig. 5 is the scanning electron microscope (SEM) photograph of the cellulose nano-fibrous biogas gel.
Specific embodiment
This specific embodiment is only explanation of the invention, and it is not limitation of the present invention, people in the art
Member can make the modification without creative contribution to the present embodiment as needed after this specification is read, but as long as at this
All protected by Patent Law in the right of invention.
The preparation of cellulose 1：Paper pulp is taken, is cleaned with distilled water to neutrality.Preparation mass fraction is 0.5% chlorous acid
Sodium solution, will completely be submerged in paper pulp addition sodium chlorite solution to paper pulp.Add to being soaked with the sodium chlorite solution of paper pulp
Plus acetum, the pH of system is adjusted to 3.Then processed 2 hours at whole system being placed in 70 DEG C, period is every 15-20 points
Clock carries out intermittent stirring.After the completion of, paper pulp is washed till neutrality with distilled water, cellulose 1 is obtained, it is placed in refrigerator and preserves stand-by.
The preparation of cellulose 2：Microcrystalline cellulose is taken, is cleaned with distilled water to neutrality.It is 0.2% to prepare mass fraction
Sodium chlorite solution, will completely be submerged in microcrystalline cellulose addition sodium chlorite solution to microcrystalline cellulose.To being soaked with crystallite
Acetum is added in the sodium chlorite solution of cellulose, the pH of system is adjusted to 5.Then locate at whole system being placed in 60 DEG C
Reason 3 hours, period carried out intermittent stirring every 15-20 minutes.After the completion of, paper pulp is washed till neutrality with distilled water, obtain fiber
Element 2, is placed in refrigerator and preserves stand-by.
The preparation of cellulose 3：Extracting degreasing cotton, is cleaned to neutrality with distilled water.It is 0.3% sub- chlorine to prepare mass fraction
Acid sodium solution, will completely be submerged in absorbent cotton addition sodium chlorite solution to absorbent cotton.To the sodium chlorite for being soaked with absorbent cotton
Acetum is added in solution, the pH of system is adjusted to 4.Then at whole system being placed in 75 DEG C process 1 hour, period every
Carry out intermittent stirring within 15-20 minutes.After the completion of, paper pulp is washed till neutrality with distilled water, cellulose 3 is obtained, it is placed in refrigerator and protects
Deposit stand-by.
The preparation of cellulose 4：Bagasse is taken, is cleaned with distilled water to neutrality.Preparation mass fraction is 0.7% chlorous acid
Sodium solution, will completely be submerged in bagasse addition sodium chlorite solution to bagasse.Add to being soaked with the sodium chlorite solution of bagasse
Plus acetum, the pH of system is adjusted to 1.Then processed 2.5 hours at whole system being placed in 80 DEG C, period is every 15-20
Minute carries out intermittent stirring.After the completion of, paper pulp is washed till neutrality with distilled water, cellulose 4 is obtained, it is placed in be preserved in refrigerator and treats
With.
The preparation of oxycellulose 1：Taking described in 1g cellulose 1 adds 100g water to stirring in beaker, adds
After 0.015gTEMPO, 0.1gNaBr stir, to adding 0.3gNaClO to start oxidation reaction in system, at room temperature to system
PH is maintained 10 by middle dropwise addition NaOH solution；When system no longer consumes NaOH, add a few drop ethanol, plus hydrochloric acid that pH is adjusted into 7
Carry out terminating reaction, then with centrifuge and cyclic washing, remove supernatant, it is fine that the water insoluble part for obtaining is oxidation
Dimension element 1.
The preparation of oxycellulose 2：Taking described in 1g cellulose 2 adds 100g water to stirring in beaker, adds
After 0.01gTEMPO, 0.05gNaBr stir, to adding 0.1gNaClO to start oxidation reaction in system, at room temperature to system
PH is maintained 11 by middle dropwise addition NaOH solution；When system no longer consumes NaOH, add a few drop ethanol, plus hydrochloric acid that pH is adjusted into 7
Carry out terminating reaction, then with centrifuge and cyclic washing, remove supernatant, it is fine that the water insoluble part for obtaining is oxidation
Dimension element 2.
The preparation of oxycellulose 3：Taking described in 1g cellulose 3 adds 100g water to stirring in beaker, adds
After 0.012gTEMPO, 0.08gNaBr stir, to adding 0.2gNaClO to start oxidation reaction in system, at room temperature to body
NaOH solution is added dropwise in system pH is maintained 9；When system no longer consumes NaOH, add a few drop ethanol, plus hydrochloric acid that pH is adjusted into 7
Carry out terminating reaction, then with centrifuge and cyclic washing, remove supernatant, it is fine that the water insoluble part for obtaining is oxidation
Dimension element 3.
The preparation of oxycellulose 4：Taking described in 1g cellulose 4 adds 100g water to stirring in beaker, adds
After 0.02gTEMPO, 0.2gNaBr stir, to adding 0.5gNaClO to start oxidation reaction in system, at room temperature to system
PH is maintained 10 by middle dropwise addition NaOH solution；When system no longer consumes NaOH, add a few drop ethanol, plus hydrochloric acid that pH is adjusted into 7
Carry out terminating reaction, then with centrifuge and cyclic washing, remove supernatant, it is fine that the water insoluble part for obtaining is oxidation
Dimension element 4.
The preparation of cellulose nano-fibrous dispersion liquid 1,3,4：The oxycellulose 1,3,4 is taken respectively is put into distillation in right amount
Carry out that homogenate is ultrasonically treated to make it be uniformly dispersed in water, then centrifuging and taking supernatant, the cellulose that concentration is 0.6% is obtained respectively and receives
Rice fiber dispersion 1, concentration is 0.8% cellulose nano-fibrous dispersion liquid 3, and concentration is cellulose nano-fibrous point of 0.5%
Dispersion liquid 4.
The preparation of cellulose nano-fibrous dispersion liquid 2：The oxycellulose 2 is put into distilled water in right amount carries out homogenate
Ultrasonically treated it is uniformly dispersed, prepared concentration is 0.3% cellulose nano-fibrous dispersion liquid 2.
The preparation of cellulose nano-fibrous dispersion liquid 5-7：Take that the oxycellulose 1 is appropriate to be put into distilled water simultaneously respectively
It is 8,9,10 NaOH solution to be added dropwise respectively and adjusts pH, then carries out that homogenate is ultrasonically treated to make it be uniformly dispersed, then centrifuging and taking supernatant, point
Not Zhi get concentration be 0.1% cellulose nano-fibrous dispersion liquid 5, concentration is 0.2% cellulose nano-fibrous dispersion liquid 6, dense
Spend the cellulose nano-fibrous dispersion liquid 7 for 1%.
Specific embodiment 1
The preparation of cellulose nano-fibrous biomass gel 1：Take cellulose nano-fibrous dispersion liquid 1 described in 20mL and be placed in coagulating basin
It is interior to carry out acid coagulating bath treatment with the hydrochloric acid solution that concentration is 5M, prepare that form is good, intensity is high, cellulose after treatment 3h
The low cellulose nano-fibrous biomass gel 1 of content.
The preparation of cellulose nano-fibrous biogas gel 1：The cellulose nano-fibrous biomass gel 1 is carried out
Freeze-drying, is obtained the cellulose nano-fibrous biogas gel 1 that form is good, intensity is high, content of cellulose is low.
Specific embodiment 2
The preparation of cellulose nano-fibrous biomass gel 2：Take cellulose nano-fibrous dispersion liquid 2 described in 20mL and be placed in 50mL burnings
In cup, separately take 250 mL beakers and pour into the hydrochloric acid solution that 20mL concentration is 7M, small beaker is positioned in large beaker and with fresh-keeping
Large beaker sealing is carried out acidic gas vapors bath treatment by film, and small beaker is taken out after treatment 6h, prepares that form is good, intensity is high, fibre
The low cellulose nano-fibrous biomass gel 2 of dimension cellulose content.
The preparation of cellulose nano-fibrous biogas gel 2：The cellulose nano-fibrous biomass gel 2 is carried out
Supercritical drying, is obtained the cellulose nano-fibrous biogas gel 2 that form is good, intensity is high, content of cellulose is low.
Specific embodiment 3
The preparation of cellulose nano-fibrous biomass gel 3：Take cellulose nano-fibrous dispersion liquid 3 described in 20mL and be placed in coagulating basin
It is interior to carry out acid coagulating bath treatment with the acetum that concentration is 3M, prepare that form is good, intensity is high, cellulose after treatment 6h
The low cellulose nano-fibrous biomass gel 3 of content.
The preparation of cellulose nano-fibrous biogas gel 3：The cellulose nano-fibrous biomass gel 3 is carried out
Freeze-drying, is obtained the cellulose nano-fibrous biogas gel 3 that form is good, intensity is high, content of cellulose is low.
Specific embodiment 4
The preparation of cellulose nano-fibrous biomass gel 4：Take cellulose nano-fibrous dispersion liquid 4 described in 20mL and be placed in coagulating basin
It is interior to carry out acid coagulating bath treatment with the hydrochloric acid solution that concentration is 7M, prepare that form is good, intensity is high, fiber after treatment 0.1h
The low cellulose nano-fibrous biomass gel 4 of cellulose content.
The preparation of cellulose nano-fibrous biogas gel 4：The cellulose nano-fibrous biomass gel 4 is carried out
Supercritical drying, is obtained the cellulose nano-fibrous biogas gel 4 that form is good, intensity is high, content of cellulose is low.
Specific embodiment 5
The preparation of cellulose nano-fibrous biomass gel 5：Take cellulose nano-fibrous dispersion liquid 2 described in 20mL and be placed in 50mL burnings
In cup, separately take 250 mL beakers and pour into the acetum that 20mL concentration is 5M, small beaker is positioned in large beaker and with fresh-keeping
Large beaker sealing is carried out acidic gas vapors bath treatment by film, and small beaker is taken out after treatment 10h, prepares that form is good, intensity is high, fibre
The low cellulose nano-fibrous biomass gel 5 of dimension cellulose content.
The preparation of cellulose nano-fibrous biogas gel 5：The cellulose nano-fibrous biomass gel 5 is carried out
Freeze-drying, is obtained the cellulose nano-fibrous biogas gel 5 that form is good, intensity is high, content of cellulose is low.
Specific embodiment 6
The preparation of cellulose nano-fibrous biomass gel 6：Take cellulose nano-fibrous dispersion liquid 6 described in 20mL and be placed in 50mL burnings
In cup, separately take 250 mL beakers and pour into the hydrochloric acid solution that 20mL concentration is 3M, small beaker is positioned in large beaker and with fresh-keeping
Large beaker sealing is carried out acidic gas vapors bath treatment by film, and small beaker is taken out after treatment 12h, prepares that form is good, intensity is high, fibre
The low cellulose nano-fibrous biomass gel 6 of dimension cellulose content.
The preparation of cellulose nano-fibrous biogas gel 6：The cellulose nano-fibrous biomass gel 6 is carried out
Supercritical drying, is obtained the cellulose nano-fibrous biogas gel 6 that form is good, intensity is high, content of cellulose is low.
Specific embodiment 7
The preparation of cellulose nano-fibrous biomass gel 7：Take cellulose nano-fibrous dispersion liquid 7 described in 20mL and be placed in 50mL burnings
In cup, separately take 250 mL beakers and pour into the acetum that 20mL concentration is 6M, small beaker is positioned in large beaker and with fresh-keeping
Large beaker sealing is carried out acidic gas vapors bath treatment by film, and small beaker is taken out after treatment 8h, prepares that form is good, intensity is high, fibre
The low cellulose nano-fibrous biomass gel 7 of dimension cellulose content.
The preparation of cellulose nano-fibrous biogas gel 7：The cellulose nano-fibrous biomass gel 7 is carried out
Freeze-drying, is obtained the cellulose nano-fibrous biogas gel 7 that form is good, intensity is high, content of cellulose is low.
Comparative example 1
Taking cellulose nano-fibrous dispersion liquid 6 described in 20mL and being placed in coagulating basin carries out coagulating bath treatment with ethanol solution, finally
The cellulose nano-fibrous biomass gel that form is good, intensity is high, content of cellulose is low cannot be obtained.
Comparative example 2
Using sulfuric acid substitute specific embodiment 7 in acetic acid, remaining using and the identical method of specific embodiment 7, finally cannot
Cellulose nano-fibrous biomass gel is obtained.
Comparative example 3
Paper pulp containing lignin is not pre-processed, remaining using and the identical method of specific embodiment 1, finally be obtained fiber
Plain nanofiber biomass gel 8, but inventor find the translucency of obtained cellulose nano-fibrous biomass gel 8 it is poor,
Intensity difference.
The cellulose nano-fibrous biomass gel 8 is carried out into freeze-drying, cellulose nano-fibrous biomass are obtained
Aeroge 8, but inventor has found that obtained cellulose nano-fibrous biogas gel Final 8 degree is poor.
Comparative example 4
Do not carry out step（1）Treatment, remaining using and the identical method of specific embodiment 1, cellulose cannot be finally obtained and receives
Rice fibrous biomass gel.
Comparative example 5
Do not carry out step（2）Treatment, remaining using and the identical method of specific embodiment 1, cellulose cannot be finally obtained and receives
Rice fibrous biomass gel.
In sum, specific embodiment 1-7 employs preparation method of the invention, all successfully prepared form it is good,
Intensity is high, fiber content is low cellulose nano-fibrous biomass gel and aeroge, wherein specific embodiment 5-7 are prepared
Cellulose nano-fibrous biomass gel and aeroge there is negative electricity characteristic.Comparative example 1-5 is as a result of unreasonable
Preparation method, it is impossible to successfully be obtained cellulose nano-fibrous biomass gel and aeroge or obtained cellulose nano-fibrous
Biomass gel and aeroge existing forms are poor, intensity difference the shortcomings of.
Claims (10)
1. a kind of preparation method of cellulose nano-fibrous biomass gel, it is characterised in that comprise the following steps：
（1）Cellulose is processed through TEMPO/NaBr/NaClO oxidation systems, oxycellulose is obtained；
（2）The oxycellulose is obtained cellulose nano-fibrous point in the aqueous solution or weak alkaline aqueous solution through mechanical treatment
Dispersion liquid；
（3）The cellulose nano-fibrous dispersion liquid is obtained cellulose Nanowire through acid coagulating bath or acid vapors bath treatment
Dimension biomass gel.
2. a kind of preparation method of cellulose nano-fibrous biomass gel according to claim 1, it is characterised in that step
Suddenly（1）Specifically include：The cellulose of 1 mass parts is added to the aqueous solution of 100 mass parts, 0.01-0.02 matter is added
The NaClO for measuring NaBr, 0.1-0.5 mass parts of part TEMPO, 0.05-0.2 mass parts mixes to form oxidation reaction system, to institute
The pH of the oxidation reaction system is maintained 9-11 by dropwise addition NaOH solution in stating oxidation reaction system；When the oxidation reaction body
When system no longer consumes NaOH, ethanol is added, pH is adjusted to 7 by acid adding, then oxycellulose is obtained through being centrifuged and washing.
3. a kind of preparation method of cellulose nano-fibrous biomass gel according to claim 1, it is characterised in that step
Suddenly（2）Specifically include：By step（1）The obtained oxycellulose is put into pure water and carries out mechanical treatment the fiber is obtained
Plain nanofiber dispersion liquid；Or the oxycellulose is put into pure water and NaOH solution is added dropwise make 7 ＜ pH≤10, then enter
Row mechanical treatment is obtained the cellulose nano-fibrous dispersion liquid.
4. a kind of preparation method of cellulose nano-fibrous biomass gel according to claim 1, it is characterised in that step
Suddenly（3）Specifically include：By step（2）The obtained cellulose nano-fibrous dispersion liquid is carried out with the acid solution that concentration is 3-7M
Acid coagulating bath or acidic gas vapors bath treatment 0.1-12h are obtained cellulose nano-fibrous biomass gel.
5. a kind of preparation method of cellulose nano-fibrous biomass gel according to claim 1 and 2, its feature exists
In the cellulose is obtained by cellulosic material is preprocessed：It is 0.3-0.7%'s by the cellulosic material mass fraction
Sodium chlorite solution is submerged, and adds acetum and pH is adjusted into≤5, and 1-3h is processed at 60-80 DEG C, is finally washed with pure water
The cellulose is obtained to neutral；The cellulosic material is microcrystalline cellulose, paper pulp, absorbent cotton and from timber and plant straw
At least one in stalk in obtained cellulose.
6. a kind of preparation method of cellulose nano-fibrous biomass gel according to claim 2, it is characterised in that step
Suddenly（1）In, the pH of the oxidation reaction system is maintained 10 to NaOH solution is added dropwise in the oxidation reaction system.
7. the preparation method of a kind of cellulose nano-fibrous biomass gel according to claim 3, it is characterised in that
Concentration≤1% of the cellulose nano-fibrous dispersion liquid.
8. a kind of preparation method of cellulose nano-fibrous biomass gel according to claim 4, it is characterised in that institute
Acid solution is stated for Volatile acid solutions.
9. a kind of preparation method of cellulose nano-fibrous biomass gel according to claim 8, it is characterised in that institute
Acid solution is stated for hydrochloric acid or acetic acid.
10. the preparation method of a kind of cellulose nano-fibrous biogas gel according to claim any one of 1-9, its
It is characterised by, the cellulose nano-fibrous biomass gel is obtained cellulose nano-fibrous biomass airsetting through drying and dehydrating
Glue.
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