CN105777913A - Efficient cellulose nanocrystalline preparing method - Google Patents
Efficient cellulose nanocrystalline preparing method Download PDFInfo
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- CN105777913A CN105777913A CN201610236962.6A CN201610236962A CN105777913A CN 105777913 A CN105777913 A CN 105777913A CN 201610236962 A CN201610236962 A CN 201610236962A CN 105777913 A CN105777913 A CN 105777913A
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 76
- 239000001913 cellulose Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 235000010980 cellulose Nutrition 0.000 claims description 71
- 239000002159 nanocrystal Substances 0.000 claims description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 4
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 4
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- -1 iron ion Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 229920001131 Pulp (paper) Polymers 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims 2
- 238000011026 diafiltration Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000006213 oxygenation reaction Methods 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 229920002749 Bacterial cellulose Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000005016 bacterial cellulose Substances 0.000 description 2
- 229910052927 chalcanthite Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008104 plant cellulose Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010018910 Haemolysis Diseases 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008588 hemolysis Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides an efficient and quick cellulose nanocrystalline preparing method.According to the method, a cellulose raw material is pretreated with aqueous alkali and then subjected to acidolysis, and inorganic salt containing metal ions is added during acidolysis to serve as a promoter to promote acidolysis reaction.Reaction condition is mild and easy to control, raw materials needed by reaction are simple and easy to obtain, and the method can be widely applied to preparation of cellulose nanocrystalline from various cellulose raw materials.
Description
[technical field]
The invention belongs to field of nano material preparation, fall within field of polymer technology, particularly to the preparation method of a kind of Cellulose nanocrystal.
[background technology]
Native cellulose is the biological material that in nature, amount is maximum, and its annual production can reach 1.5 × 1012Ton.The Cellulose nanocrystal that there is nano-scale by extracting cellulosic crystal region to obtain.Cellulose nanocrystal has numerous good characteristic, and as it has big draw ratio, length is from hundreds of nanometers to several microns not etc.；It has high mechanical strength, and its Young's modulus is similar to aramid fibre and higher than iron and steel, hot strength similar to aluminum；The Heat stability is good of Cellulose nanocrystal, thermal coefficient of expansion is typically in below 0.1ppm/K, it is possible to compare favourably with carbon fiber.Cellulose nanocrystal under certain condition can orientations, thus presenting the characteristic of liquid crystal.In addition; Cellulose nanocrystal also has biocompatibility, biodegradable, the surface that can react, high crystalline, low-density (less than inorfil), the advantage such as cheap; make it obtain in manufacture high-performance composite materials scientific domain to pay close attention to widely; particularly today earth resource day by day exhausted; environmental conservation is craved under day by day urgent background by people, and the research and development of Cellulose nanocrystal is had theoretical greatly and realistic meaning.
At present, the method for preparation Cellulose nanocrystal mainly has acid hydrolyzation, enzymatic isolation method and physical mechanical facture etc., and wherein enzymatic isolation method length complicated, consuming time, cost are high；Physicomechanical processes needs special installation and uses high pressure, and energy consumption is higher, the cellulose Nano Particle distribution width of preparation.The most frequently used at present is exactly the method for sulfuric acid solution, the method results from nineteen forty-seven the earliest, being utilized sulphuric acid hydrolysis timber and cotton-wool to prepare Cellulose nanocrystal suspension by Nickerson and Habrle, the method raw material is easy to get, and the Cellulose nanocrystal suspension stability of preparation is high.But the productivity that sulfuric acid solution prepares Cellulose nanocrystal needs to be improved further, the productivity of usual sulfuric acid solution method is lower than 30%, and Cellulose nanocrystal particle size distribution is relatively wide, gained is nanocrystalline from several nanometers to several microns, have a strong impact on its performance in follow-up use, it is therefore necessary to improve the method further and make its simple and effective more.In patent CN104711305A, enzymatic isolation method is adopted to prepare Cellulose nanocrystal Bacterial cellulose, productivity is up to 50-85%, this is higher up to more than 70% mainly due to the degree of crystallinity of Bacterial cellulose own, it is much higher than plant cellulose, so nanocrystalline productivity is also higher, but the method to be not particularly suited for utilizing plant cellulose to prepare nanocrystalline.Cellulosic material is all made directly process by the above-mentioned various methods of preparation Cellulose nanocrystal, there are no the step of pretreatment.This patent has been used for reference the biomass material such as straw, timber and has been produced the method adopting alkali process in cellulose process to remove hemicellulose therein and lignin, adopt and cellulosic material is carried out oxygenation pretreatment, the method simultaneously adding catalyst in preparation process, improve the productivity of Cellulose nanocrystal, shorten the response time simultaneously and make the nanocrystalline particle size distribution of gained more uniform.
[summary of the invention]
[solving the technical problem that]
It is an object of the invention to prepare the deficiency of Cellulose nanocrystal technology for existing sulfuric acid solution, it is provided that one preparation method easier, efficient so that the productivity of Cellulose nanocrystal significantly improves, and particle size distribution is more uniform.
[technical scheme]
The present invention by carrying out aqueous slkali pretreatment and adding metal ion in acid hemolysis process as promoter to cellulosic material, thus improving the productivity of Cellulose nanocrystal and improving particle size distribution.
The present invention is achieved by the following technical solutions:
(1) pretreatment: cellulosic material stirring is pulverized, uses aqueous slkali soaking 1-120h, it is preferable that 5-80 hour, more preferably 8-48 hour, then by deionized water filtering and washing to neutral；
(2) it is 45%-69% that the cellulose after being processed by (1) gained is dispersed in mass percentage concentration, it is preferable that 55-69%；More preferably in the aqueous sulfuric acid of 60-65%, being simultaneously introduced promoter, under Elevated Temperature Conditions, stirring above-mentioned reactant aqueous solution certain time obtains hydrolyzed solution；
(3) post processing: (2) gained hydrolyzed solution is added deionized water to terminate reaction, be centrifuged the hydrolyzed solution after dilution again separating, take upper strata suspension carry out dialysing, filter, ultrasound wave dispersion, obtain the rod-like fibre element nanocrystal suspension of stable dispersion.
In described step (1), cellulosic material is Plant fiber, paper pulp fiber, microcrystalline Cellulose and alpha-cellulose；Can certainly being natural fiber common in nature, the kind for fiber limit in the present invention.
In described step (1), aqueous slkali used by pretreatment is weight/mass percentage composition is 1%-10%, it is preferable that 3-8%, the more preferably sodium hydroxide of 4-6%, Lithium hydrate, potassium hydroxide or ammonia spirit.
In described step (1), cellulosic material is soaked in aqueous slkali, raw material and aqueous slkali
Amount ratio is 10-100g:1L.
In described step (1), the soak time of cellulosic material is 8-120 hour.
In described step (2), cellulose content in sulfuric acid solution is 10-80g/l.
In described step (2), temperature reaction is temperature required for 40-80 DEG C, and the response time is 20-200 minute.
Step (2) described promoter is the salt containing metal ion.
Described promoter is the salt containing iron ion, calcium ion, magnesium ion, aluminium ion or copper ion.
In described step (2), promoter used is the inorganic salt containing iron ion, calcium ion, magnesium ion, aluminium ion or copper ion.It is preferably one or more in ferrous chloride, ferric chloride, calcium chloride, magnesium sulfate, aluminum sulfate and copper sulfate.
In described step (2), promoter consumption is 1:100-10:100 with the mass ratio of cellulosic material.
When in described step (3), the hydrolyzed solution of dilution is centrifuged separating, centrifuge speed is 6000-10000rpm, and centrifugal number of times is 2-5 time.
[beneficial effect]
Due to the fact that and take technique scheme, have the advantage that
(1) present invention utilizes aqueous slkali to cellulosic swelling action, cellulosic material is soaked in aqueous slkali and carries out pretreatment, destroy the hydrogen bond between cellulosic molecule, make cellulose molecular structure loose, reaction accessibility improves, thus improve acidolysis reaction efficiency, reaction yield is made to significantly improve.
(2) inorganic salt of promoter is had no particular limits by the present invention, as long as it comprises following cation；Fe in the present invention2+、Fe3+、Ca2+、Mg2+、Al3+、Cu2+Deng metal ion with positive charge, the charge balance between cellulose hydrogen bond can be destroyed, contribute to the fracture of hydrogen bond, accelerate cellulosic hydrolysis, the present invention adopts the inorganic salt containing above-mentioned metal ion as promoter, shorten the response time, improve reaction efficiency and productivity, effectively improve the even particle size distribution of Cellulose nanocrystal.
(3) inorganic salt used in reaction uses mainly as promoter, and its consumption is few and is prone to remove by dialysis, and product is not affected.
(4) it is bar-shaped for adopting the Cellulose nanocrystal that the inventive method is prepared, mean diameter is about 100-200nm, particle size distribution is narrower compared to common sulfuric acid solution method, namely particle size distribution is evenly, the nanocrystalline particle size distribution index (PDI) of usual sulfuric acid solution method gained is about 2.0, and the nanocrystalline PDI of gained of the present invention is 1.0-1.6.The productivity of Cellulose nanocrystal is 70-90%.
(5) present invention prepares the reaction condition gentleness of Cellulose nanocrystal, easily controllable, reaction needed raw material is simple and easy to get, the method applied in the present invention can be widely applied to all kinds of cellulosic materials existed in prior art, including natural plant fibre, and the preparation Cellulose nanocrystal such as the higher paper cellulose of molecular weight and the higher microcrystalline Cellulose of degree of crystallinity, alpha-cellulose.
[accompanying drawing explanation]
Fig. 1 is the atomic force microscopy of the made Cellulose nanocrystal of the embodiment of the present invention 1
Fig. 2 is the grading curve of the made Cellulose nanocrystal of the embodiment of the present invention 1.
[detailed description of the invention]
Below in conjunction with embodiment, the present invention is further described, but protection scope of the present invention is not limited to that.
Embodiment 1.
5 grams of paper cellulose blenders are broken into flocculence, add the NaOH solution of 250ml, 4wt%, after soaking 24 hours, with deionized water by its filtering and washing to neutral, take this cellulose through oxygenation pretreatment, add 0.078 gram of CuSO4·5H2O, adds the sulphuric acid of 90 milliliters of 64wt%, after stirring 40min at 50 DEG C, add deionized water and terminate reaction, after solution left standstill, be centrifuged 10min with high speed centrifuge with the rotating speed of 8000rpm/min, then by washing of precipitate, again separate, until supernatant becomes cloudy.By ultrasonic for gained Cellulose nanocrystal suspension, obtaining stable Cellulose nanocrystal suspension, be about 160nm through measuring gained cellulose crystal grain footpath average-size, productivity is 77%, and PDI is 1.5.
Embodiment 2.
Raw materials used kind, consumption and technological process are with embodiment 1, the difference is that paper cellulose soak time in NaOH solution is extended to 72h, obtain stable Cellulose nanocrystal suspension, be about 150nm through measuring gained cellulose crystal grain footpath average-size, productivity is 81%, and PDI is 1.4.
Embodiment 3.
After 5g alpha-cellulose is soaked 48 hours by the NaOH solution of 250ml, 4wt%, with deionized water filtration washing to neutral, take this cellulose through oxygenation pretreatment, add 0.078 gram of CuSO4·5H2O, adds the sulphuric acid of 100 milliliters of 64wt%, after stirring 1.5h at 50 DEG C, add deionized water and terminate reaction, after solution left standstill, be centrifuged 10min with high speed centrifuge with the rotating speed of 8000rpm/min, then by washing of precipitate, again separate, until supernatant becomes cloudy.By ultrasonic for gained Cellulose nanocrystal suspension, obtaining stable Cellulose nanocrystal suspension, particle diameter average-size is about 200nm, and productivity is 83%, and PDI is 1.5.
Embodiment 4.
Replacing paper cellulose with microcrystalline Cellulose, repeat the proportioning in embodiment 1 and operation, obtain stable Cellulose nanocrystal suspension, particle diameter is 150nm, and productivity is 87%, and PDI is 1.4.
Embodiment 5.
5g paper cellulose blender is broken into flocculence, after soaking 24 hours by the NaOH solution of 250ml, 4wt%, with deionized water filtration washing to neutral, takes this 5 grams of celluloses through oxygenation pretreatment, add 0.085 gram of FeCl3·6H2O, adds the sulphuric acid of 90 milliliters of 64wt%, after stirring 40min at 50 DEG C, add deionized water and terminate reaction, after solution left standstill, be centrifuged 10min with high speed centrifuge with the rotating speed of 8000rpm/min, then by washing of precipitate, again separate, until supernatant becomes cloudy.By ultrasonic for gained Cellulose nanocrystal suspension, obtaining stable Cellulose nanocrystal suspension, particle diameter is 180nm, and productivity is 75%, and PDI is 1.5.
Embodiment 6.
Raw materials used kind, consumption and technological process are with embodiment 6, the difference is that with 0.078 gram of MgSO4As promoter, obtaining stable Cellulose nanocrystal suspension, particle diameter is 190nm, and productivity is 73%, and PDI is 1.6.
Comparative example 1.
Paper cellulose is repeated the proportioning in embodiment 1 and operation, but it is added without promoter, it is of a size of 260nm through acidolysis gained Cellulose nanocrystal, more than the nanocrystalline size of gained in embodiment 1, the productivity of Cellulose nanocrystal is 38% far below the productivity in embodiment 1, and its particle size distribution is also wider, PDI is 2.2.
Comparative example 2.
Paper cellulose is repeated the proportioning in embodiment 1 and operation, but do not carry out aqueous slkali pretreatment, be of a size of 350nm through acidolysis gained Cellulose nanocrystal, more than the nanocrystalline size of gained in embodiment 1, the productivity of Cellulose nanocrystal is 43% far below the productivity in embodiment 1, and PDI is 2.1.
Claims (10)
1. a Cellulose nanocrystal preparation method, it is characterised in that the method comprises the following steps:
(1) pretreatment: will wash after cellulosic material aqueous slkali soaking；
(2) being dispersed in the sulfuric acid solution that mass percentage concentration is 45%-69% by gained cellulose in step (1), be simultaneously introduced promoter, reacting by heating obtains cellulosic hydrolysate；
(3) post processing: separate after (2) gained cellulosic hydrolysate is terminated acidolysis reaction, take upper strata suspension diafiltration, dispersion, obtain Cellulose nanocrystal suspension.
2. the preparation method of Cellulose nanocrystal according to claim 1, it is characterised in that described cellulosic material is one or more in Plant fiber, paper pulp fiber, microcrystalline Cellulose or alpha-cellulose.
3. the preparation method of Cellulose nanocrystal according to claim 1 or claim 2, it is characterised in that: aqueous slkali used by step (1) pretreatment is weight/mass percentage composition is the sodium hydroxide of 1%-10%, Lithium hydrate, potassium hydroxide or ammonia spirit；The amount ratio of described cellulosic material and aqueous slkali is 10-100g:1L.
4. the preparation method of Cellulose nanocrystal according to claim 1 or claim 2, it is characterised in that: step (1) described soak time is 1-120 hour.
5. the preparation method of Cellulose nanocrystal according to claim 1, it is characterised in that: step (2) described cellulose content in sulfuric acid solution is 10-80g/l.
6. the preparation method of Cellulose nanocrystal according to claim 1, it is characterised in that: the reaction temperature of step (2) is 40-80 DEG C, and the response time is 20-200 minute.
7. the preparation method of Cellulose nanocrystal according to claim 1, it is characterised in that: step (2) described promoter is the salt containing metal cation.
8. the preparation method of Cellulose nanocrystal according to claim 7, it is characterised in that: described promoter is the salt containing iron ion, calcium ion, magnesium ion, aluminium ion or copper ion；The mass ratio of promoter and cellulosic material is 1:100-1:10.
9. the preparation method of Cellulose nanocrystal according to claim 8, it is characterised in that: step (2) described promoter is one or more in ferrous chloride, ferric chloride, calcium chloride, magnesium sulfate, aluminum sulfate or copper sulfate.
10. the preparation method of Cellulose nanocrystal according to claim 1, it is characterised in that: when the hydrolyzed solution of step (3) described dilution is centrifuged separating, centrifuge speed is 6000-10000rpm, and centrifugal number of times is 2-5 time.
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674357A (en) * | 2016-12-21 | 2017-05-17 | 广西大学 | Method for preparing nano cellulose in EmimOAc system |
| CN106800604A (en) * | 2016-12-21 | 2017-06-06 | 广西大学 | A kind of method that nano-cellulose is prepared in BmimCl systems |
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