CN108178802A - A kind of preparation method based on nitric acid, the oxycellulose nanofibrils of hydrogen peroxide - Google Patents
A kind of preparation method based on nitric acid, the oxycellulose nanofibrils of hydrogen peroxide Download PDFInfo
- Publication number
- CN108178802A CN108178802A CN201810173515.XA CN201810173515A CN108178802A CN 108178802 A CN108178802 A CN 108178802A CN 201810173515 A CN201810173515 A CN 201810173515A CN 108178802 A CN108178802 A CN 108178802A
- Authority
- CN
- China
- Prior art keywords
- nitric acid
- hydrogen peroxide
- preparation
- nanofibrils
- oxycellulose
- 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.)
- Granted
Links
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
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a kind of preparation method based on nitric acid, the oxycellulose nanofibrils of hydrogen peroxide, this method is based on nitric acid hydrolyzation system, introduces hydrogen peroxide oxidation reagent, specifically includes following operating procedure：Biomass material, the nitric acid of a concentration of 1~8mol/L, the hydrogen peroxide that mass concentration is 30% are mixed, it is stirred to react under the conditions of 20~80 DEG C 6~96 hours, then it adds in absolute ethyl alcohol and terminates reaction, solution stand is layered again, outwell supernatant liquor, retain lower sediment thing, lower sediment thing is cleaned, then is handled through high pressure homogenizer to obtain oxycellulose nanofibrils with absolute ethyl alcohol, the second alcohol and water that volumetric concentration is 50% successively.The method of the present invention simple process, the chemical species of use are few, are easy to get cheap, oxycellulose nanofibrils obtained are with a wide range of applications in fields such as water process, water-oil separating, nanocomposites.
Description
Technical field
The invention belongs to nano-cellulose manufacturing technology fields, particularly a kind of that oxidized fibre is directly prepared from biomass
The method of plain nanofibrils.
Background technology
Nano-cellulose not only has that native cellulose is renewable, the characteristics such as biodegradable, also with bigger serface,
The advantages that high-hydrophilic, high transparency, high intensity, high Young's modulus, low thermal coefficient of expansion, it is compound to form various functions for it
Material provides possibility, has broad application prospects.Biomass, which has, to be derived from a wealth of sources, is rich reserves, renewable and to ring
The advantage of border close friend.From biomass, the biomass resource of variform is obtained, is particularly grasped in nano-scale range
Vertical, design and assembling native cellulose become the hot subject of this field current research.
Preparation about nano-cellulose includes：(1) preparation of nano micro crystal cellulose (NCC).By strong acid or cellulose
The amorphous region of cellulose is removed in enzyme hydrolysis, retains fine and close crystal region and obtains, in the NCC (diameters 5 of needle-like whisker structure
~70nm, 100~400nm of length), the crystallinity of NCC is very high (60%~90%).However, the hydrolysis of high intensity can lead to fibre
The a large amount of degradations of dimension element, product yield is low, to the more demanding of equipment.(2) preparation of crinosity Cellulose nanocrystal (HC-NC), by
Chemical reagent cut-out amorphous region and obtain, crystal region is similar to NCC (5~10nm of diameter, 100~200nm of length), both ends
There are many polymeric chains (being about 100nm) for amorphous region.(3) preparation of fento cellulose (MFC).MFC also known as receives
Rice filament fibers are plain, cellulose nano-fibrous, and in filamentous, 5~60nm of diameter, 1000~10000nm of length have flexible
Property, molecular structure is alternately made of crystal region and amorphous region.There are following defects for this method：(1) MFC is generally by Mechanical Method
It prepares (for example, high pressure homogenization method), first passes through Chemical Pretreatment and cellulose is extracted from raw material, then utilize the machinery of high intensity
External force (such as high-pressure homogeneous, high shear, microjet, grinding) makes cellulose that cut-out and fibrillating effect separation occur.High pressure
For homogeneous method preparation process generally to the less pollution of environment, but to equipment requirement height, energy consumption is huge.(2) MFC is aoxidized by TEMPO
Prepared by method, utilize the hydroxyl by C6 positions on glucose unit of TEMPO (piperidine nitroxide free-radical)-NaBr-NaClO selectivity
Base is oxidized to carboxyl, and the electrostatic repulsion using filament surface carboxylic ions promotes filament to detach.Other preparation Nanowires
The method of dimension element is such as etherified, aoxidizes, being esterified, carboxy methylation, and principle is similar with TEMPO oxidizing process.Its reaction condition is mild, behaviour
Make simple, the method to be commonly used at present.The deficiency of these methods be need to pre-process raw material (including boiling,
Multistage bleaching etc.), whole process can consume the resources such as a large amount of electricity, heat, chemical reagent and water.(3) MFC is by electrostatic spinning legal system
It is standby, by the cellulose solution of concentration by the needle-shaped syringe of metal, and steadily squeeze under the inducing action of high-voltage electrostatic field and
Prepare nano-cellulose.The nanofiber that electrostatic spinning obtains, surface is smooth, and diameter is evenly distributed, the fibre of indefinite length
The plain nanofiber of dimension.The process of Electrospun nano-fibers one energy-intensive of element, and the dissolving of cellulose is difficult.(4)
The preparation of Nano bacteria cellulose (BNC).BNC is to carry out biopolymerization generation to glucose in the presence of biology enzyme by bacterium
, crystallinity is higher than plant cellulose, indefinite length, and there is 20~100nm of diameter high tensile strength and excellent in shape to tie up
Hold ability.Bacterium method can regulate and control to be prepared structure, crystal form, particle diameter distribution of cellulose etc., in addition this method energy consumption it is relatively low,
It is pollution-free.But domestic research is still within the primary stage, there are low output, of high cost, the production cycle is longer, processing technology
The problems such as being difficult to, it is difficult to realize large-scale industrialization.
Oxycellulose nanofibrils draw ratio is big, good dispersion, and is important natural with functional groups such as carboxyls
Cellulose derivative.Oxycellulose nanofibrils are current most common methods by the preparation of TEMPO oxidizing process, utilize TEMPO
The hydroxyl by C6 positions on glucose unit of (piperidine nitroxide free-radical)-NaBr-NaClO selectivity is oxidized to carboxyl, profit
Filament is promoted to detach with the electrostatic repulsion of filament surface carboxylic ions.The other method for preparing nano-cellulose such as ethers
Change, oxidation, esterification, carboxy methylation etc., principle is similar with TEMPO oxidizing process.The deficiency of these methods be need to raw material into
(including boiling, multistage bleaching etc.), whole process can consume the resources such as a large amount of electricity, heat, chemical reagent and water, and high for row pretreatment
Leading to natural microfibril structure in the preprocessing process of intensity, the degree of polymerization of cellulose is significantly by different degrees of broken outer
Decline.
Invention content
The technical problems to be solved by the invention are to provide a kind of oxycellulose nanofibrils based on nitric acid, hydrogen peroxide
Preparation method, this method based on nitric acid hydrolyze, introduce hydrogen peroxide oxidation reagent, can be prepared directly from biomass oxidation fibre
The plain nanofibrils of dimension.
The present invention solves above-mentioned technical problem with following technical solution：
A kind of preparation method based on nitric acid, the oxycellulose nanofibrils of hydrogen peroxide of the present invention, it includes following behaviour
Make step：Biomass material, the nitric acid of a concentration of 1~8mol/L, the hydrogen peroxide that mass concentration is 30% are mixed, 20~80
It is stirred to react under the conditions of DEG C 6~96 hours, then adds in absolute ethyl alcohol and terminate reaction, then solution stand is layered, outwell upper strata
Clear liquid retains lower sediment thing, is successively cleaned lower sediment thing with absolute ethyl alcohol, the second alcohol and water that volumetric concentration is 50%,
It handles to obtain oxycellulose nanofibrils through high pressure homogenizer again.
The proportioning of biomass material of the present invention, nitric acid and hydrogen peroxide is：10g biomass materials:150ml nitric acid：15
~50ml hydrogen peroxide.
Biomass material of the present invention includes bagasse, giantreed piece, eucalyptus skin graft.
Relative to the prior art, the method for the present invention has the advantages that：
(1) preparation process of the present invention is simple, does not need to the pretreatment of high intensity, is suitable for scale industrial production；
(2) the raw materials used in the present invention includes available all biomass, such as bagasse, presses bark, bamboo, also includes
The biomass such as unemployed weeds, shrub；
(3) chemical species of the present invention are few, and it is cheap to be easy to get；
(4) the oxycellulose nanofibrils obtained by the present invention are in necks such as water process, water-oil separating, nanocomposites
Domain is with a wide range of applications.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
10g bagasse, the nitric acid of a concentration of 4mol/L of 150ml, the hydrogen peroxide that 45ml mass concentrations are 30% are added to
In the three-necked flask of 500ml, 48h is stirred to react under the conditions of 50 DEG C, absolute ethyl alcohol is added in and terminates reaction, solution is moved into
Static layering in the graduated cylinder of 500ml outwells supernatant liquor, retains lower sediment thing, is with absolute ethyl alcohol, volumetric concentration successively
50% ethyl alcohol, water clean lower sediment thing, handle to obtain oxycellulose nanofibrils through high pressure homogenizer.
The obtained diameter of oxycellulose nanofibrils is in the range of 5~50nm, carboxyl-content 1.036mmol/g.
Embodiment 2
10g giantreeds piece, the nitric acid of a concentration of 8mol/L of 150ml, the hydrogen peroxide that 15ml mass concentrations are 30% are added to
In the three-necked flask of 500ml, 6h is stirred to react under the conditions of 80 DEG C, absolute ethyl alcohol is added in and terminates reaction, solution is moved into 500ml
Graduated cylinder in static layering, outwell supernatant liquor, retain lower sediment thing, be successively 50% with absolute ethyl alcohol, volumetric concentration
Ethyl alcohol, water clean lower sediment thing, handle to obtain oxycellulose nanofibrils through high pressure homogenizer.
The obtained diameter of oxycellulose nanofibrils is in the range of 20~80nm, carboxyl-content 0.791mmol/g.
Embodiment 3
10g eucalyptus skin graft, the nitric acid of a concentration of 1mol/L of 150ml, the hydrogen peroxide that 50ml mass concentrations are 30% are added in
Into the three-necked flask of 500ml, 96h is stirred to react under the conditions of 20 DEG C, absolute ethyl alcohol is added in and terminates reaction, solution is moved into
Static layering in the graduated cylinder of 500ml outwells supernatant liquor, retains lower sediment thing, is with absolute ethyl alcohol, volumetric concentration successively
50% ethyl alcohol, water clean lower sediment thing, handle to obtain oxycellulose nanofibrils through high pressure homogenizer.
The obtained diameter of oxycellulose nanofibrils is in the range of 10~50nm, carboxyl-content 1.275mmol/g.
Claims (3)
1. a kind of preparation method based on nitric acid, the oxycellulose nanofibrils of hydrogen peroxide, which is characterized in that it includes as follows
Operating procedure：Biomass material, the nitric acid of a concentration of 1~8mol/L, the hydrogen peroxide that mass concentration is 30% are mixed, 20~
It is stirred to react under the conditions of 80 DEG C 6~96 hours, then adds in absolute ethyl alcohol and terminate reaction, then solution stand is layered, outwell
Layer clear liquid, retains lower sediment thing, is successively washed lower sediment thing with absolute ethyl alcohol, the second alcohol and water that volumetric concentration is 50%
Only, then through high pressure homogenizer handle to obtain oxycellulose nanofibrils.
2. the preparation method based on nitric acid, the oxycellulose nanofibrils of hydrogen peroxide, feature exist according to claim 1
In the proportioning of the biomass material, nitric acid and hydrogen peroxide is：10g biomass materials:150ml nitric acid：15~50ml dioxygens
Water.
3. the preparation method according to claim 1 or claim 2 based on nitric acid, the oxycellulose nanofibrils of hydrogen peroxide, special
Sign is that the biomass material includes bagasse, giantreed piece, eucalyptus skin graft, weeds, shrub.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810173515.XA CN108178802B (en) | 2018-03-02 | 2018-03-02 | Preparation method of oxidized cellulose nanofibrils based on nitric acid and hydrogen peroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810173515.XA CN108178802B (en) | 2018-03-02 | 2018-03-02 | Preparation method of oxidized cellulose nanofibrils based on nitric acid and hydrogen peroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108178802A true CN108178802A (en) | 2018-06-19 |
| CN108178802B CN108178802B (en) | 2020-04-10 |
Family
ID=62553080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810173515.XA Active CN108178802B (en) | 2018-03-02 | 2018-03-02 | Preparation method of oxidized cellulose nanofibrils based on nitric acid and hydrogen peroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108178802B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625143A (en) * | 2020-12-18 | 2021-04-09 | 浙江理工大学 | Preparation method of antibacterial nanocellulose |
| WO2021152958A1 (en) * | 2020-01-31 | 2021-08-05 | ユニ・チャーム株式会社 | Method for producing pulp fiber for carboxylated cellulose nanofibrillation use, and pulp fiber for carboxylated cellulose nanofibrillation use |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10259504A1 (en) * | 2002-12-19 | 2004-07-08 | Beisel, Günther | Production of a spongy material containing an orally ingestible product, useful for delayed and sustained release of drugs, dietary supplements or foods, comprises oxidizing a polymer in aqueous solution |
| CN104098704A (en) * | 2013-04-15 | 2014-10-15 | 金东纸业（江苏）股份有限公司 | Preparation method for paper pulp containing multiple functional groups |
| CN106592311A (en) * | 2016-12-13 | 2017-04-26 | 华南理工大学 | Preparation method of nanofibril cellulose |
| CN107236049A (en) * | 2017-06-29 | 2017-10-10 | 东北农业大学 | A kind of nano-cellulose and preparation method thereof |
-
2018
- 2018-03-02 CN CN201810173515.XA patent/CN108178802B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10259504A1 (en) * | 2002-12-19 | 2004-07-08 | Beisel, Günther | Production of a spongy material containing an orally ingestible product, useful for delayed and sustained release of drugs, dietary supplements or foods, comprises oxidizing a polymer in aqueous solution |
| CN104098704A (en) * | 2013-04-15 | 2014-10-15 | 金东纸业（江苏）股份有限公司 | Preparation method for paper pulp containing multiple functional groups |
| CN106592311A (en) * | 2016-12-13 | 2017-04-26 | 华南理工大学 | Preparation method of nanofibril cellulose |
| CN107236049A (en) * | 2017-06-29 | 2017-10-10 | 东北农业大学 | A kind of nano-cellulose and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021152958A1 (en) * | 2020-01-31 | 2021-08-05 | ユニ・チャーム株式会社 | Method for producing pulp fiber for carboxylated cellulose nanofibrillation use, and pulp fiber for carboxylated cellulose nanofibrillation use |
| CN115038837A (en) * | 2020-01-31 | 2022-09-09 | 尤妮佳股份有限公司 | Method for producing pulp fiber for carboxylated cellulose nanofibers and pulp fiber for carboxylated cellulose nanofibers |
| CN115038837B (en) * | 2020-01-31 | 2023-11-10 | 尤妮佳股份有限公司 | Method for producing pulp fiber for carboxylation cellulose nanofibers and pulp fiber for carboxylation cellulose nanofibers |
| JP7458802B2 (en) | 2020-01-31 | 2024-04-01 | ユニ・チャーム株式会社 | Method for producing pulp fibers for carboxylated cellulose nanofibers, and pulp fibers for carboxylated cellulose nanofibers |
| CN112625143A (en) * | 2020-12-18 | 2021-04-09 | 浙江理工大学 | Preparation method of antibacterial nanocellulose |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108178802B (en) | 2020-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Reuse of waste cotton cloth for the extraction of cellulose nanocrystals | |
| Isogai et al. | TEMPO-oxidized cellulose nanofibers | |
| CN103061174B (en) | The method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment | |
| CN103102419B (en) | Method for preparing nano microcrystalline cellulose by hydrolyzing phyllostachys edulis fiber with cellulase | |
| Xu et al. | Preparation and characterization of spherical cellulose nanocrystals with high purity by the composite enzymolysis of pulp fibers | |
| CN105568730A (en) | Method for preparing renewable nano-celluloses | |
| CN105566502B (en) | The preparation method of the renewable nano-cellulose film of water resistance | |
| CN107287956B (en) | Method for preparing nano-cellulose by combining enzyme pretreatment with mechanical grinding | |
| CN107236049A (en) | A kind of nano-cellulose and preparation method thereof | |
| CN103643577B (en) | A kind of method utilizing garlic skin to prepare nano-cellulose whisker | |
| CN106893116A (en) | A kind of preparation method of cellulose nano-fibrous biomass gel and aeroge | |
| CN106939443B (en) | A kind of reed stem cellulose nano wire and preparation method thereof | |
| CN106758492A (en) | A kind of many site oxidizing process prepare method and its application of nano-cellulose | |
| CN103755817B (en) | A kind of preparation method of nano micro crystal cellulose | |
| CN108221438A (en) | A kind of preparation method of bleached eucalyptus pulp nano-cellulose | |
| Cheng et al. | Comparative study on properties of nanocellulose derived from sustainable biomass resources | |
| Zhang et al. | Separation cellulose nanocrystals from microcrystalline cellulose using hydrated deep eutectic solvent and high shear force | |
| CN108178802A (en) | A kind of preparation method based on nitric acid, the oxycellulose nanofibrils of hydrogen peroxide | |
| CN109468871A (en) | The wooden nano-cellulose and its method of a kind of preparation of straw and application | |
| CN105884908B (en) | A kind of preparation method of carboxylated cellulose element nanoparticle | |
| CN108314742A (en) | A kind of preparation method based on nitric acid, the oxycellulose nanofibrils of nitrite | |
| Abdul Razab et al. | Isolation and characterization of cellulose nanofibrils from banana pseudostem, oil palm trunk, and kenaf bast fibers using chemicals and high-intensity ultrasonication | |
| CN109608555A (en) | A kind of method that ultrasonic wave assist acid hydrolysis microcrystalline cellulose prepares nanofiber crystalline substance | |
| CN109208366A (en) | A kind of preparation method and application of micro-nano cellulose | |
| CN108166090A (en) | A kind of preparation method based on phosphoric acid, the oxycellulose nanofibrils of hydrogen peroxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |