CN1141321C - Method for preparing nanocrystal cellulose by means of acid hydrolysis - Google Patents
Method for preparing nanocrystal cellulose by means of acid hydrolysis Download PDFInfo
- Publication number
- CN1141321C CN1141321C CNB011297174A CN01129717A CN1141321C CN 1141321 C CN1141321 C CN 1141321C CN B011297174 A CNB011297174 A CN B011297174A CN 01129717 A CN01129717 A CN 01129717A CN 1141321 C CN1141321 C CN 1141321C
- Authority
- CN
- China
- Prior art keywords
- ncc
- hydrolysis
- cellulose
- nanocrystal cellulose
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920002678 cellulose Polymers 0.000 title claims abstract description 37
- 239000001913 cellulose Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 19
- 238000005903 acid hydrolysis reaction Methods 0.000 title claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000007062 hydrolysis Effects 0.000 claims abstract description 29
- 239000000835 fiber Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 229920000742 Cotton Polymers 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- 238000010129 solution processing Methods 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 7
- 239000001117 sulphuric acid Substances 0.000 abstract description 4
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 4
- 229920003043 Cellulose fiber Polymers 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- 235000010980 cellulose Nutrition 0.000 description 22
- 239000000243 solution Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- 229940083608 sodium hydroxide Drugs 0.000 description 8
- 241000212978 Amorpha <angiosperm> Species 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 229920002301 cellulose acetate Polymers 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000008030 elimination Effects 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- -1 sulfuric acid ester Chemical class 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GOYYUYNOGNSLTE-UHFFFAOYSA-N copper;2-azanidylethylazanide Chemical compound [Cu+2].[NH-]CC[NH-].[NH-]CC[NH-] GOYYUYNOGNSLTE-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 240000008564 Boehmeria nivea Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000035614 depigmentation Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention belongs to a method for preparing nanocrystal cellulose (NCC) by acid hydrolysis The present invention provides a method for preparing NCC by using inorganic acid to hydrolyze cellulose fiber, which is characterized in that under the condition of the continuous vibration of ultrasonic waves, a nanocrystal cellulose I(NCC-I) product is obtained by using indoor-temperature strong acid hydrolysis with a one-step method, wherein the hydrolysis conditions comprise: the concentration of sulphuric acid is from 45 to 60%, the temperature is from 0 to 38 DEG C, and the hydrolysis time is from 2 to 24 hours; then the nanocrystal cellulose I(NCC-I) obtained by hydrolysis is treated by low-concentration strong alkali to prepare nanocrystal cellulose II(NCC-II).
Description
The present invention relates to method with preparing nanocrystal cellulose by means of acid hydrolysis (NCC).
Nanocrystal cellulose is one of basal component that constitutes cellulosic fibre.Usually the basic structure of the cellulosic fibre of saying: unit fibril and little fibril all belong to the NCC scope.Little fibril is made of the unit fibril, and many unit fibril set constitute little fibril.And the unit fibril is made up of many cellulose macromolecule chains, constitutes crystallizing field and pars amorpha between molecular chain and the molecular chain.Remove pars amorpha or the incomplete zone of crystallization by method for hydrolysis, obtain containing the many component NCC of crystallising part, its particle diameter is in nano-scale (1-100nm) scope, contain unit fibril and little fibrillar fragment, although molecular weight is little, still keeping cellulosic chemical ingredients and physical structure.NCC has the high chemically reactive of nanoparticle, is easy to work with sodium hydroxide; Also carry out easily esterification, etherification reaction and and other chemical reagent react, wide application prospect arranged in that medical science and other are industrial.But at present the method for preparing Microcrystalline Cellulose with acid hydrolysis needs to heat more, and what have also will carry out pre-treatment to fiber.
The invention provides and a kind ofly prepare nanocrystal cellulose I (NCC-I) and further make the method for nano-crystal cellulose II (NCC-II) with alkaline purification with the mineral acid hydrolysis cellulosic fibre, be characterized under ultrasonic wave (32kHz) vibration, room temperature strong acid one one-step hydrolysis method and make NCC-I, again with alkali lye handle NCC-II.
The method that the acid hydrolysis cellulosic fibre that the present invention relates to makes NCC is to use earlier the mineral acid hydrolysis cellulosic fibre, obtain the about 30nm of particle diameter, the NCC-I of degree of crystallinity about 80%, its preparation condition is: be the sulfuric acid of 45-60% with volumetric concentration, under 0-38 ℃, ultrasonic continuous vibration hydrolysis 2-24 hour, the product that hydrolysis obtains separates de-salted water, washing with acetone and dehydration, room temperature vacuum drying through deionization washing, alkali neutralization, filter membrane, obtains the NCC-I powder.Optimum hydrolysising condition is a sulfuric acid volumetric concentration 55%, 25 ℃ of hydrolysis temperatures, and hydrolysis time 2.5 hours, ultrasonic wave is 32kHz, handled fiber can be a cotton fibre, cellulosic fibres such as flaxen fiber or refining wood pulp come unstuck.
After the NCC-I of above-mentioned gained concentrated through neutralizing, the sodium hydroxide solution that is made into volumetric concentration 1% was handled 20min at least, and under ultrasonic vibration, 25 ℃ of constant temperature obtained NCC-II through 2.5 hours.
Hydrolysing agent sulfuric acid, sour dense 45-60%, temperature 0-38 ℃, 2-24h, optimum hydrolysising condition are 55% sulfuric acid, 25 ℃, 2.5h.Hydrolysis is with cotton or linters, also can be with the vegetable fibres such as keen-witted and capable ramie, kendir or refining wood pulp that come unstuck.Different fibers can be selected different hydrolysis acid concentration and time for use, all can obtain the NCC-I of particle diameter 10-30nm.During acid hydrolysis at room temperature, fiber need not to handle through prehydrolysis or other organic solvent, directly fiber is soaked among the acid solution, with the continuous vibration of ultrasonic wave chain.Action of ultrasonic waves is to quicken hydrolysis and fibrous particle division.2.5h after just obtain NCC-I.When sulfuric acid concentration＜45%, what obtain is not nanoparticle, and particle size exceeds nanometer range; When sulfuric acid concentration＞60%, hydrolysis time is long, as＞24h, cellulosic fibre is glucose and fiber polysaccharide with complete hydrolysis, can not get NCC-I, this moment, cellulosic crystalline texture was all destroyed.Outside the hydrolysis deacidification concentration affects, temperature is also very important, and when acid concentration was 55%, hydrolysis temperature surpassed 38 ℃, and fiber is also fallen by complete hydrolysis.
Separating through sulfuric acid chamber warm water with cotton fibre, mainly is to interrupt the cellulose macromolecule chain, reduces molecular weight, the pars amorpha is destroyed, and then destroyed defective crystallizing field.Cellulose macromolecule chain sharply fracture in beginning 5 minutes, and form cellulose sulfuric acid ester if stop hydrolysis this moment, will can not get NCC-I and obtain cellulose sulfuric acid ester.When cotton fibre continued hydrolysis, owing to be subjected to the effect of sulfuric acid catalysis and water, formed cellulose sulfuric acid ester was hydrolyzed, and cellulose molecular chain continues fracture, and the pars amorpha continues to decompose, and finally obtains NCC-I.
During the sulphuric acid hydrolysis cellulosic fibre, the degree of crystallinity of fiber also changes.About 75%, the NCC-I degree of crystallinity that obtains after hydrolysis is 75%-83% without the hot cotton fibre degree of crystallinity of one-tenth of hydrolysis.By convention, hydrolysis is except that destroying the Mierocrystalline cellulose pars amorpha, and the district also produces destruction to defective partial crystallization, and fibre crystallinity should descend.Experiment shows that vitriol oil hydrolysis cotton fibre post crystallization degree does not only have decline, raises on the contrary.Major cause is that hydrolytic process is with pars amorpha dissolving in the fiber, the defective crystallizing field of small part is also dissolved, and that remaining is the high NCC-I of crystalline content, and its degree of crystallinity will improve, because hydrolysis is cost with the sacrificial fiber pars amorpha, so hydrolysis yield only about 10%.On the other hand, hydrolysis howsoever, the degree of crystallinity of the NCC-I of gained can not improve yet, and can not get the degree of crystallinity of picture inorganic crystal compound more than 98%.This is because cellulosic molecule is a natural product, formed lattice particle is also not exclusively regular in growing process, defectiveness also, in big lattice, also be impregnated with the small amount of amorphous district, be subjected to the parcel of peripheral lattice, the accessibility of hydrolysing agent can not arrive at intracell, therefore, the degree of crystallinity of NCC-I all rests on the certain level, does not reach complete crystallization.
Room temperature sulphuric acid hydrolysis cotton fibre, behind 2.5h, the solution light brown that is translucent scrapes off the impurity that float on the upper strata this moment, pours in a large amount of distilled water, reduces acidity, reduces the heat that produces because of Dilution of sulphuric acid simultaneously, stops hydrolysis reaction at once.With nylon cloth elimination impurity, obtain oyster white and contain NCC-I suspension, leave standstill 6h, under the acid solution effect, NCC-I is loose aggregate and is sunken under the liquid, the upper strata acid solution of inclining, be neutralized to pH=7 with dilute sodium hydroxide aqueous solution, because salting out, NCC-I still can be sunken to liquid bottom.The upper strata saline solution that inclines, the saline solution that will contain NCC-I moves in the cellulose acetate filter membrane that the aperture is 0.22 μ m and filters, and vacuum filtration adds distilled water wash till salt-free.Although NCC-I particle diameter ratio filter membrane aperture is little, because mutual bridging action between the particle only has small amount of N CC-I to leach, major part is retained on the filter membrane.The also available polysulfone membrane of used filter membrane or other anti-general acid, alkali film.NCC-I after desalination removes the acetone solvend with washing with acetone again, displaces moisture, avoid in drying process, producing agglomeration because of the water effect makes NCC-I, again through room temperature vacuum-drying, pulverize, sieve, the NCC-I powder.
Through the NCC-I that purification obtains, wherein C, H, O element ratio meet the cellulose chemistry component proportions with ultimate analysis; Measuring product with X-ray diffraction is the cellulose I crystalline structure, and degree of crystallinity is 75%-80%; Can observe NCC-I granular size and shape with transmission electron microscope (TEM) or atomic force microscope (AFM), be generally 30nm; Do electron beam diffraction with TEM and show that product has single crystal structure; It is the Mierocrystalline cellulose characteristic infrared spectrum that infrared spectrum energy is measured NCC-I.Through above-mentioned sign, can determine that product is the NCC-I nanoparticle.Measure the NCC-I molecular weight in the 2300-9000 scope with the cupriethylene diamine solution viscosimetry.GPC can measure NCC-I molecular weight and distribution thereof.
Prepare NCC-II from NCC-I, except that with the sodium-hydroxide treatment, inorganic strong alkalis such as available hydrogen potassium oxide, yellow soda ash also, alkali is dense about 1%, can obtain NCC-II more than the room temperature treatment 20min.Product obtains the NCC-II powder through operations such as dealkalize, neutralization, washing, filter membrane separation, washing with acetone and precipitation, low-temperature vacuum drying, pulverizing.The purpose of membrane sepn is removed outside the impurity such as depigmentation, mainly is desalination and dehydration.Because the NCC-II particle is minimum, general filter method can not separate nanoparticle.The aperture of film is 0.22 μ m, and NCC-II can see through filter membrane and discharge because interparticle function served as bridge is difficult for seeing through filter membrane, and water and molecules of salt are littler, holds back down the NCC-II particle.Used filter membrane is wanted anti-general soda acid, cellulose acetate filter membrane commonly used or polysulfones filter membrane.
Reunion is the characteristics of nano particle, and the gordian technique of preparation nano particle is to solve agglomeration traits between particle.In case the nano particle tight agglomeration is difficult to its redispersion is become nano particle with the common mechanical method.Therefore, preparation NCC-II powder is when concentrating NCC-II to 5% solid content with membrane sepn, must be with washing with acetone and dehydration, flush away pigment and impurity be the more important thing is dehydration on the one hand, elimination makes cellulose particulates not produce reunion because of the hydrogen bond that water molecules forms the cellulose particles intergranular.
NCC-II through aforesaid method makes can determine that with the survey of element determination method C, H, O content ratio the NCC-II chemical ingredients is a cellulose components; Measuring NCC-II with X-ray diffraction is the cellulose II crystalline structure, can also measure grain size in the particle simultaneously; Can observe NCC-II granular size and shape with transmission electron microscope (TEM) or atomic force microscope (AFM), be generally 30-50nm; Infrared measurement NCC-II is the Mierocrystalline cellulose characteristic infrared spectrum.Through above-mentioned sign, can determine that product is the NCC-II nanoparticle.Measure the NCC-II molecular weight with cupriethylene diamine solution with viscosimetry.
Acid hydrolysis cellulosic fibre provided by the present invention prepares the method for NCC-I, compare with acid hydrolysis process of the prior art, having can be at room temperature, do not need pre-treatment with acid hydrolysis, under ultrasonic vibration, one step directly obtained NCC-I, and under the more and more wider situation of the application of nanoparticle, this method has more significance; With low concentration alkali NCC-I is converted into NCC-II, can saves the alkali consumption, reduce environmental pollution, to research Mierocrystalline cellulose crystalline texture, academicly highly significant, the NCC-II that obtains is used for cellulose ester, etherification reaction and other reaction and also has theory and practical significance.
Embodiment 1: get the 500g refined cotton linter and be dipped in 25 ℃, in 55% aqueous sulfuric acid of 5000mL, vibrate 2.5h with ultrasonic continuous, scrape off the impurity that floats on liquid level, pour in the 10000mL distilled water at once, stop hydrolysis reaction,, leave standstill 6h with nylon filter cloth impurity screening, the upper strata of inclining contains the acid solution body, with ceramic post sintering funnel elimination acid solution, add the distilled water diluting sample, be neutralized to pH=7 with 0.05% aqueous sodium hydroxide solution, NCC-I settles out, the supernatant liquid that inclines moves in the 0.22 μ m cellulose acetate filter membrane of aperture and filters, and adds deionized water wash till salt-free, again through washing with acetone and dehydration, room temperature vacuum-drying, pulverize, sieve and obtain the NCC powder.
Embodiment 2: replace linters with the keen-witted and capable ramee that comes unstuck, repeat embodiment 1 proportioning and operation, also obtain the NCC-I powder of the about 30nm of particle diameter.
Embodiment 3: repeat embodiment 1 proportioning and operation with refining wood pulp, also obtain the NCC-I powder that particle diameter is about 30nm.
Embodiment 4: get embodiment 1 gained NCC-I, supernatant liquid inclines, aqueous sodium hydroxide solution with 0.05% is neutralized to pH=7, this moment NCC-I be loose aggregating state and since salting out be sunken under the liquid, with the most of salt solution of No. 2 ceramic post sintering funnel eliminations, get the about 5%NCC-I colloid of solids content.Mix with aqueous sodium hydroxide solution again, mixed sodium hydroxide volumetric concentration is 1%, soak more than the 20nim, get NCC-II, again through neutralizing, wash, separating salt solution with aperture 0.22 μ m cellulose acetate filter membrane, take out filter cake, washing with acetone and dehydration, room temperature vacuum-drying, pulverize, sieving obtains the about 30nmNCC-II powder of particle diameter.
Embodiment 5: replace linters with the keen-witted and capable ramee that comes unstuck, repeat embodiment 4 proportionings and operation, also obtain the NCC-II powder.
Embodiment 6: repeat embodiment 4 proportionings and operation with refining wood pulp, also obtain the NCC-II powder.
Claims (7)
1, a kind of method of preparing nanocrystal cellulose by means of acid hydrolysis, this method is to use the mineral acid hydrolysis cellulosic fibre, obtain the nanocrystal cellulose I of particle diameter 30mm, degree of crystallinity 80%, it is characterized in that preparing is to be the sulfuric acid of 45%-60% with volumetric concentration, 0-38 ℃, under ultrasonic continuous vibration, obtained nanocrystal cellulose I product in hydrolysis 2-24 hour, separate de-salted water, washing with acetone and dehydration through washing, neutralization, filter membrane, room temperature vacuum-drying obtains nanocrystal cellulose I powder.
2,, it is characterized in that described cellulosic fibre is a cotton fibre, flaxen fiber or refining timber pulp fibres come unstuck according to the method described in the claim 1.
3, according to the method described in the claim 1, it is characterized in that described preparation condition is: sulfuric acid volumetric concentration 55%, 25 ℃ of hydrolysis temperatures, hydrolysis time 2.5 hours.
4,, it is characterized in that described ultrasonic wave is 32KHz according to the method described in the claim 1.
5, a kind of preparation method of nano-crystal cellulose II, be the nanocrystal cellulose I of gained in the claim 1 to be concentrated the back through neutralizing handle, it is characterized in that with the sodium hydroxide solution processing nanocrystal cellulose I product of volumetric concentration 1% 20min and making at least with chemical reagent.
6,, it is characterized in that described chemical treatment reagent is potassium hydroxide or yellow soda ash according to the method described in the claim 5.
7, according to the method described in the claim 5, it is characterized in that the nano-crystal cellulose II product, through neutralization, deionized water wash, filter membrane separation, washing with acetone and dehydration, room temperature vacuum-drying, pulverize and obtain the nano-crystal cellulose II powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011297174A CN1141321C (en) | 2001-09-30 | 2001-09-30 | Method for preparing nanocrystal cellulose by means of acid hydrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011297174A CN1141321C (en) | 2001-09-30 | 2001-09-30 | Method for preparing nanocrystal cellulose by means of acid hydrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1341663A CN1341663A (en) | 2002-03-27 |
| CN1141321C true CN1141321C (en) | 2004-03-10 |
Family
ID=4669389
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011297174A Expired - Lifetime CN1141321C (en) | 2001-09-30 | 2001-09-30 | Method for preparing nanocrystal cellulose by means of acid hydrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1141321C (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070352B (en) * | 2007-03-27 | 2011-05-11 | 鲁东大学 | Method for preparing sheet-like microcrystal cellulose and modification processing method |
| EP2344689B1 (en) * | 2008-10-14 | 2014-04-23 | SAPPI Netherlands Services B.V. | Process for the manufacture of cellulose-based fibres and the fibres thus obtained |
| JP5717646B2 (en) * | 2008-12-11 | 2015-05-13 | エフピーイノベイションズ | Redispersible dry nanocrystalline cellulose |
| BRPI1011265A2 (en) * | 2009-05-06 | 2019-09-24 | Fpinnovations | pulp, method and process for producing pulp, and process for producing pulp materials. |
| EP2464599B1 (en) * | 2009-08-11 | 2016-09-07 | FPInnovations | Fractionation of a waste liquor stream from nanocrystalline cellulose production |
| CN101768221B (en) * | 2010-03-12 | 2012-02-29 | 福建农林大学 | Method for preparing nano-crystal cellulose II by using basic anion-exchange resin |
| CN101864606B (en) * | 2010-06-30 | 2011-09-07 | 东北林业大学 | Preparation method of biomass cellulose nanofibers with high length-diameter ratio |
| CN102080342B (en) * | 2010-11-25 | 2013-04-24 | 山东轻工业学院 | Anionic organic particles and preparation and application thereof |
| CN102080343B (en) * | 2010-11-25 | 2013-05-29 | 山东轻工业学院 | Application of anion nano microcrystalline cellulose as paper reinforcer |
| CN102080341B (en) * | 2010-11-25 | 2013-04-24 | 山东轻工业学院 | Cationic organic particles and preparation and application thereof |
| CN102040663B (en) * | 2010-12-06 | 2012-08-29 | 东华大学 | Preparation method of narrow-distribution cellulose nanocrystalline |
| CN102311505B (en) * | 2011-07-18 | 2012-12-05 | 东华大学 | Method for preparing cellulose nanospheres based on waste dissolvable fibers |
| FI126118B (en) * | 2012-02-10 | 2016-06-30 | Upm Kymmene Corp | Cellulose pulp pretreatment method |
| CN102585017B (en) * | 2012-03-27 | 2013-12-11 | 东华大学 | Preparation method of nanoscale solidago canadensis L. microcrystalline cellulose |
| WO2014029001A1 (en) * | 2012-08-21 | 2014-02-27 | Noram Engineering And Constructors Ltd. | Purification process for partly-hydrolyzed cellulose |
| US20140155301A1 (en) * | 2012-11-30 | 2014-06-05 | Api Intellectual Property Holdings, Llc | Processes and apparatus for producing nanocellulose, and compositions and products produced therefrom |
| CN103304824A (en) * | 2013-06-15 | 2013-09-18 | 浙江理工大学 | Preparation method of high-concentration nano microcrystalline cellulose gel |
| CN104288842A (en) * | 2013-07-19 | 2015-01-21 | 中国国旅贸易有限责任公司 | Injectable bone joint lubricating material and preparation method thereof |
| CN104342850B (en) * | 2013-08-08 | 2017-03-15 | 北京纳迅科技股份有限公司 | polyimide film containing nanocrystal cellulose and preparation method thereof |
| CN104629276B (en) * | 2013-11-12 | 2017-01-11 | 珠海市红旌发展有限公司 | Preparation method for nanocrystal cellulose composite material, product and application thereof |
| CN104381591A (en) * | 2013-12-19 | 2015-03-04 | 珠海市红旌发展有限公司 | Feed containing nanocrystalline cellulose |
| KR102358824B1 (en) * | 2014-01-29 | 2022-02-07 | 이섬 리서치 디벨러프먼트 컴파니 오브 더 히브루 유니버시티 오브 예루살렘 엘티디. | Porous nanocrystalline cellulose structures |
| US9499637B2 (en) * | 2014-06-23 | 2016-11-22 | Api Intellectual Property Holdings, Llc | Nanocellulose compositions and processes to produce same |
| CN104448007A (en) * | 2014-11-14 | 2015-03-25 | 中国科学院青岛生物能源与过程研究所 | Method for preparing nano-cellulose |
| CN104887583B (en) * | 2015-06-15 | 2017-11-24 | 天津科技大学 | A kind of preparation method of cellulose base Polyphenols natural anti-oxidation compound |
| CN105670005B (en) * | 2016-03-25 | 2017-12-19 | 西南交通大学 | A kind of process that Cellulose nanocrystal dispersion liquid is prepared based on controllable dissolving |
| CN106380613B (en) * | 2016-09-28 | 2019-01-22 | 武汉纺织大学 | A kind of preparation method of ramie core Cellulose nanocrystal self-assembled structures color film |
| CN106810614B (en) * | 2017-01-21 | 2019-04-12 | 深圳市优普惠药品股份有限公司 | A kind of preparation process of nanocrystal cellulose |
| CN108084278A (en) * | 2018-01-02 | 2018-05-29 | 青岛大学 | A kind of preparation method of small size Cellulose nanocrystal |
| CN109208366B (en) * | 2018-09-06 | 2021-05-25 | 刘永红 | Preparation method and application of micro-nano cellulose |
| CN109438580B (en) * | 2018-11-27 | 2021-04-27 | 陕西科技大学 | Method for preparing nano cellulose crystal from ultralow acid hydrolysis fiber |
| CN109608555A (en) * | 2018-12-25 | 2019-04-12 | 天津科技大学 | A kind of method that ultrasonic wave assist acid hydrolysis microcrystalline cellulose prepares nanofiber crystalline substance |
| CN110183538A (en) * | 2019-06-21 | 2019-08-30 | 大连工业大学 | A kind of method of the slightly sour preparation Cellulose nanocrystal body of promotion system altogether of inorganic fused salt- |
| CN114345129A (en) * | 2022-02-14 | 2022-04-15 | 天津如米新材料有限公司 | Cellulose nanocrystalline separation and purification method based on microfiltration separation and direct deacidification |
-
2001
- 2001-09-30 CN CNB011297174A patent/CN1141321C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1341663A (en) | 2002-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1141321C (en) | Method for preparing nanocrystal cellulose by means of acid hydrolysis | |
| Mohamed et al. | Physicochemical characterization of cellulose nanocrystal and nanoporous self-assembled CNC membrane derived from Ceiba pentandra | |
| Kunusa et al. | FTIR, XRD and SEM analysis of microcrystalline cellulose (MCC) fibers from corncorbs in alkaline treatment | |
| KR102682506B1 (en) | Chemical Formula Manufacturing Method of Cellulose Fiber | |
| Biswal et al. | Exploring the adsorption efficiency of a novel cellulosic material for removal of food dye from water | |
| CN102803296B (en) | Crystal Sulfocellulose II and prepare this crystal Sulfocellulose II by cellulosic sulphuric acid hydrolysis | |
| CN103342826B (en) | Preparation method of chitin nano-fiber/montmorillonite composite membrane material | |
| abualnoun Ajeel et al. | Extraction of high purity amorphous silica from rice husk by chemical process | |
| CN111087491B (en) | Method for preparing hemicellulose, carboxylated cellulose nano crystal, fibril and citrate multi-component product from fiber by using citric acid | |
| CN101730751A (en) | Process for production of monosaccharide and process for production of ethanol both utilizing cellulose-based substance | |
| CN108264569B (en) | Cellulose II type nanocrystalline particles and preparation method and application thereof | |
| WO2011114005A1 (en) | Process for preparing micro-and nanocrystalline cellulose | |
| CN103572394B (en) | A kind of preparation method cellulose nano-fibrous simply and rapidly | |
| CN110485188A (en) | A kind of wood fibre synchronization prepares the method and its application of high pure cellulose and lignin nanoparticle | |
| EP2632957A1 (en) | Process for the derivatization of cellulose | |
| CN113145080A (en) | Preparation method of TEMPO oxidized holocellulose-chitosan adsorption material, prepared adsorption material and application | |
| JP5822101B2 (en) | Method for producing cellulose solution, method for producing cellulose precipitate, and method for saccharification of cellulose | |
| Le et al. | Effect of HCl-Alcoholic treatment on the modification of jackfruit (Artocarpus heterophyllus Lam) seed starch | |
| CN1278933C (en) | Method for preparing silicon dioxide aerogel by normal pressure drying method using rice hull ash as raw material | |
| He et al. | Isolation and characterization of cellulose nanocrystals from Chinese medicine residues | |
| Bakar et al. | Extraction of silica from rice straw using alkaline hydrolysis pretreatment | |
| CN113388130A (en) | Method for preparing stable pickering emulsion by utilizing bagasse nanocellulose | |
| CN102718874B (en) | Method for preparing methyl cellulose ether with arundodomax dissolving pulp serving as raw material | |
| Naseem et al. | Green and efficient synthesis of cellulose nanocrystals from Hamelia patens leftover via hydrolysis of microwave assisted-ionic liquid (MWAIL) pretreated microcrystalline cellulose | |
| CN105131129B (en) | A kind of preparation method of nano-cellulose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| DD01 | Delivery of document by public notice |
Addressee: Dong Mei Document name: Notification that Application Deemed not to be Proposed |
|
| ASS | Succession or assignment of patent right |
Owner name: CHINA INTERNATIONAL TOURISM + TRADE CO., LTD. Free format text: FORMER OWNER: GUANGZHOU INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20121212 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 510650 GUANGZHOU, GUANGDONG PROVINCE TO: 100022 CHAOYANG, BEIJING |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20121212 Address after: 100022 A1901-1903, general international center, 3 East Li, Yongan, Chaoyang District, Beijing Patentee after: China International Tourism & Trade Co., Ltd. Address before: 510650 Guangdong city of Guangzhou province Tianhe District Wushan happy home Patentee before: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences |
|
| ASS | Succession or assignment of patent right |
Owner name: ZHUHAI HONGJING DEVELOPMENT CO., LTD. Free format text: FORMER OWNER: CHINA INTERNATIONAL TOURISM + TRADE CO., LTD. Effective date: 20141231 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 100022 CHAOYANG, BEIJING TO: 102299 CHANGPING, BEIJING |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20141231 Address after: 102299 Beijing city Changping District Nan Shao Zhen Xing Chang Road No. 1 Science Park East Building 5 layer 1 Patentee after: ZHUHAI HONGJING DEVELOPMENT CO., LTD. Address before: 100022 A1901-1903, general international center, 3 East Li, Yongan, Chaoyang District, Beijing Patentee before: China International Tourism & Trade Co., Ltd. |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20020327 Assignee: BEIJING NAXUN TECHNOLOGY CO., LTD. Assignor: ZHUHAI HONGJING DEVELOPMENT CO., LTD. Contract record no.: 2015990000770 Denomination of invention: Method for preparing nanocrystal cellulose by means of acid hydrolysis Granted publication date: 20040310 License type: Common License Record date: 20150827 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| EM01 | Change of recordation of patent licensing contract |
Change date: 20160202 Contract record no.: 2015990000770 Assignee after: Beijing Nano Ace Technology Co., Ltd. Assignee before: BEIJING NAXUN TECHNOLOGY CO., LTD. |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040310 |
|
| CX01 | Expiry of patent term |