CN106978651A - The manufacture method of biological nano fiber - Google Patents
The manufacture method of biological nano fiber Download PDFInfo
- Publication number
- CN106978651A CN106978651A CN201611008409.3A CN201611008409A CN106978651A CN 106978651 A CN106978651 A CN 106978651A CN 201611008409 A CN201611008409 A CN 201611008409A CN 106978651 A CN106978651 A CN 106978651A
- Authority
- CN
- China
- Prior art keywords
- fiber
- dispersion liquid
- processing
- microbubble
- biomass
- 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.)
- Pending
Links
Classifications
-
- 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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Disintegrating Or Milling (AREA)
- Artificial Filaments (AREA)
- Paper (AREA)
- Cosmetics (AREA)
Abstract
The manufacture method of the biological nano fiber of fiber separation processing is carried out the invention discloses a kind of dispersion liquid by biomass, fiber separation processing is the method that fiber separation processing is carried out under microbubble existence condition, or and is handled with the fiber separation processing carried out under the conditions of microbubble and the fiber separation that the dispersion liquid of the biomass containing microbubble is carried out into case of wet attrition.In fiber separation processing, the average grain diameter of the microbubble in the dispersion liquid of biomass is less than 50 μm., can be from the biogenic material containing biomass by the manufacture method of the present invention, low energy consumption, expeditiously acquisition nanofiber characteristic good, thin and biological nano fiber.
Description
Technical field
The present invention relates to a kind of manufacture method of biological nano fiber, more particularly to it is a kind of include employing low energy consumption,
The manufacture method of the biological nano fiber of the fiber separation process of efficient micro-nano bubble processing.
Background technology
Nanofiber refers to the fiber of a diameter of 1~1000nm, length for more than 100 times of diameter.With existing fiber phase
Than with excellent characteristic.Specifically, specific surface area is larger, excellent (the hypergeometric surface of adsorptivity, bonding force, molecular recognition
Product characteristic), fiber footpath be less than 400~700nm optical wavelength thus diffusing reflection it is less, it is transparent preferably (nano-scale characteristic), point
Sub- orientation is higher thus Strong degree, electrical conductivity, heat conductivity are excellent (molecules align characteristic).Therefore as a kind of new and energy
The material for playing property is used by extensive concern, and gradually.The raw material of nanofiber mainly has the inorganic material such as carbon, silicon
Material, nylon, terylene Polymer material.But, recently for the influence to environment, and resource abundance degree consideration, pass through
The material (biomass) of the biological sources such as cellulose, chitin rises come the research prosperity for obtaining biological nano fiber and being used
Come.In addition because manufacturing cost is higher, all the reduction of manufacturing cost is being pursued.
Biomass is former without worrying as a kind of recyclable resources because timber, the straw of its raw material can be cultivated
Material is exhausted, cellulose nano-fibrous as a kind of reinforcement material, compared with carbon fiber or glass fibre, with transparent excellent
Point, and in discarded burning, it is different from glass fibre, the advantage of combustion residue is not left.As cellulose nano-fibrous
The manufacture method of dispersion liquid, patent document 1 discloses one kind is in TEMPO (2,2,6,6- tetramethyl piperidine oxides) catalyst
In the presence of biomass is aoxidized, fiber is made by the mechanicalness fiber separation of spiral shape agitator or disc fiberizer etc.
The method of plain nanofiber.
There is abundant chitin, chitosan in the crustacean crust of shrimp crab etc., it is relevant to be made with crustacean crust
Research for the nanofiber of the biogenic material containing chitin of raw material also carries out (patent document 2).According to
Patent document 2, the nanofiber of the biogenic material containing chitin, by the biogenic material containing chitin is received
Around rice fiber and protein and ash content present in gap (mainly calcium carbonate) the deproteinized work that removes of matrix
Sequence is come with the fiber separation treatment process removed ash process and obtained chitin nano fiber is carried out into fiber separation (scattered)
Carry out.
In deproteinized process, using the alkali process method of the alkaline aqueous solution based on potassium hydroxide etc. and based on albumen
The enzyme process of the protein decomposition enzymes such as enzyme.In ash process is removed, using the acidic aqueous solution based on hydrochloric acid etc. acidic treatment and
Chelating method based on chelating agents such as ethylenediamine tetra-acetic acids.In fiber separation treatment process, by the first after deproteinized, dedusting processing
Shell element nanofiber is carried out after weak acid (pH3~4) processing, by stone mortar formula pulverizer, high pressure homogenizer, freezes reducing mechanism etc.
Carry out mechanical fiber separation processing.
In addition, in addition to the fiber hydrolization processing method in nanofiber disclosed in patent document 2, patent document 3 is public
A kind of dispersion liquid by polysaccharides such as cellulose, chitin, chitosans is opened by a pair of nozzles under 70~250MPa high pressures
Injection so that hit the case of wet attrition method crushed between injection stream mutually, patent document 4 discloses that a kind of point by biomass
Diffusing body carries out high-pressure injection under 100~240MPa, is allowed to strike the high-pressure injection hit and crushed on special hardware
Method.
But, in the processing of mechanicalness fiber hydrolization more than, load, energy loss to nanofiber all than larger,
May not necessarily low energy consumption obtain nanofiber characteristic at low cost (hypergeometric surface area characteristics, nano-scale characteristic, molecules align be special
Property) excellent, nanofiber.
In addition, patent document 5 discloses that a kind of substrate processing method using same, sprays on the surface of the plate-like substrate of semiconductor wafer etc.
On the treatment fluid containing microbubble, using the properties such as the physical impact, dissipated energy, electro sorb of microbubble to the substrate carry out
Cleaning.But, in patent document 5, it is therefore an objective to spray the treatment fluid containing microbubble on the surface of plate-like substrate, pass through its thing
Reason impact removes foreign matter present on substrate surface, to the fibre of the biological nano fiber in the raw body source of cellulose, chitin etc.
The fiber separation that the effect of microbubble in dimension separation, i.e. dispersion liquid (fiber-treating liquid) is carried out is not illustrated.
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-001728 publications
Patent document 2：No. 2010/073758 publication of International Publication
Patent document 3：Japanese Unexamined Patent Publication 2005-270891 publications
Patent document 4：Japanese Unexamined Patent Publication 2011-056456 publications
Patent document 5：Japanese Unexamined Patent Publication 2008-093577 publications
The content of the invention
The problem of the present invention is, from the biogenic material (biomass) containing cellulose or chitin, inexpensive, efficient
Ground obtain nanofiber characteristic (hypergeometric surface area characteristics, nano-scale characteristic, molecules align characteristic) it is excellent, thin and it is long,
The biological nano fiber of homogeneous.
The present inventor attentively studies for above problem, as a result finds, microbubble is due to voluntarily pressure effect and dissolubility
It is higher, performance is generated with free radical due to voluntarily fracturing effect, with the powered colloid surface electrical characteristic of negative potential,
Eye is in these characteristics of microbubble, by carrying out fiber separation under microbubble existence condition, can be from containing cellulose or first
In the biogenic material (biomass) of shell element, low energy consumption, at low cost acquisition nanofiber characteristic (hypergeometric surface area characteristics,
Nano-scale characteristic, molecules align characteristic) excellent, biological nano fiber.
It can specifically solve in the following manner.
Mode 1：A kind of manufacture method of biological nano fiber, is to carry out fiber separation processing to the dispersion liquid of biomass
The manufacture method of biological nano fiber, the fiber separation processing is in the microbubble produced by swirling flow micro bubble generation device
The fiber separation processing carried out under existence condition.
By carrying out fiber separation processing under microbubble existence condition, act on the microbubble of high concentration (highly dissoluble)
In on the biomass fiber for treating fiber separation processing, pass through its physical shock, the free radical pair that voluntarily fracturing effect is generated
Chemical reaction in biomass fiber and the current potential bounce-back based on colloidality surface electrical characteristic, to promote fiber separation,
Make to treat that the biomass fiber of fiber separation processing is separated into nano-scale rank, i.e. biological nano fibrosis and only needed to containing micro- gas
The dispersion liquid of bubble is stirred, therefore, with using grinder (stone mortar type pulverizer), high pressure homogenizer, super-pressure homogenizer, height
Pressure conflict type pulverizer, disc fiberizer, conical refiner, Soniprep, ball mill, freeze to crush etc. and utilize machinery
Property effect the fiber separation processing of case of wet attrition device compare, it is relatively low to the load of material, can be with low energy consumption, at low cost obtain
Take the biological nano fiber that fibre length is longer.
Mode 2：A kind of manufacture method of biological nano fiber, is to carry out fiber separation processing to the dispersion liquid of biomass
The manufacture method of biological nano fiber, micro- gas that the fiber separation is handled and is used in produced by swirling flow micro bubble generation device
The fiber separation processing carried out under bubble existence condition, and by the life containing the microbubble produced by swirling flow micro bubble generation device
The dispersion liquid of material carries out the fiber separation processing of case of wet attrition.
In grinder (stone mortar type pulverizer), high pressure homogenizer, super-pressure homogenizer, high pressure conflict type pulverizer, disk
Shape fiberizer, conical refiner, Soniprep, ball mill, the case of wet attrition acted on using mechanicalness such as freeze to crush
In fiber separation processing, using the dispersion liquid of the biomass containing microbubble, i.e., pass through wet type under conditions of microbubble presence
Crush and carry out fiber separation processing, the microbubble of high concentration is acted on the biomass fiber for treating fiber separation processing, by it
The free radical that physical shock, voluntarily fracturing effect are generated is for the chemical reaction of biomass fiber, based on colloidality surface
The current potential bounce-back of electrical characteristic, to promote fiber separation, makes the biomass fiber for treating fiber separation processing be separated into nano-scale
Rank, it is relatively low to the load of material compared with only carrying out the fiber separation of case of wet attrition by such synergy, can be with
Low energy consumption, the at low cost longer biological nano fiber of acquisition fibre length.
Mode 3：The manufacture method of biological nano fiber in mode 1 or mode 2 described in any one, in the micro- gas of swirling flow
It is soaked under the microbubble existence condition produced by generating apparatus and carries out fiber separation processing, wherein, the dispersion liquid of the biomass is
It is following any one：(a) carried out deproteinized processing and dedusting processing the biogenic material containing chitin dispersion liquid,
(b) carried out deproteinized processing, dedusting processing and deacetylation processing containing chitin biogenic material (shell gather
Sugar) dispersion liquid, (c) carried out delignification processing and go hemicellulose handle the biomass source material containing cellulose
Dispersion liquid.
It is used as the raw material of the biological nano fiber of biomass source, more using resourceful chitin, cellulose, preceding place
Reason method has also been established.
Mode 4：The manufacture method of biological nano fiber of the mode 1 into mode 3 described in any one, it is described for fiber
The concentration of the biomass dispersion liquid of separating treatment is 0.1~15 weight %.Micro- produced by swirling flow micro bubble generation device
In the fiber separation processing carried out under bubble existence condition, the concentration for the biomass dispersion liquid of fiber separation processing is preferably
0.1~15 weight %.
When the concentration of biomass dispersion liquid is more than 15 weight %, dispersion viscosity increase, swirling flow microbubble is filled
The diffusion in biomass dispersion liquid of microbubble produced by putting, it is impregnated with not enough fully, the fiber separation based on microbubble performance
Processing is not abundant enough.On the other hand, when biomass dispersion liquid concentration is less than 0.1 weight %, biological nano fiber manufacture efficiency
It can reduce.
Mode 5：The manufacture method of biological nano fiber of the mode 1 into mode 4 described in any one, in the fiber point
From in processing, the particle diameter of the microbubble produced by swirling flow micro bubble generation device in the dispersion liquid of the biomass is at 50 μm
Below.
By the size controlling of the microbubble produced by the swirling flow micro bubble generation device in biomass dispersion liquid at 50 μm
Below, it is preferably less than 40 μm, can so plays the performance of the microbubble handled for fiber separation (such as：Dissolubility, voluntarily
Fracturing effect, colloid effect).In addition, the performance of the performance of microbubble is not equal, according to the different meetings of the particle diameter of microbubble
It is different, so the particle diameter distribution of microbubble preferably covers certain scope.
Mode 6：The manufacture method of biological nano fiber of the mode 1 into mode 5 described in any one, the biological nano
The fiber footpath of fiber is 10~1000nm.
The characteristic (hypergeometric surface area characteristics, nano-scale characteristic, molecules align characteristic) of nanofiber is 10 in fiber footpath
It can be played during~1000nm.
Invention effect
The biological nano fiber obtained by the manufacture method of the present invention, is a kind of hypergeometric surface area characteristics, nanometer chi
Very little characteristic, molecules align characteristic good, the thin and biological nano fiber of long, homogeneous.By making in being handled in fiber separation
With microbubble, hypergeometric surface area characteristics, nano-scale characteristic, molecules align spy can be obtained with low energy consumption, low cost and efficiently
Property excellent, the thin and biological nano fiber of long, homogeneous.
The biological nano fiber obtained by the manufacture method of the present invention, due to its excellent characteristic, it is adaptable to many
Purposes.Than if any containing low thermal expansion, high photopermeability, lightweight and flexible higher biological nano fiber, (such as cellulose is received
Rice fiber, chitin nano fiber) film, thin plate, composite, and with uniform coating Forming ability and excellent viscous
The coating composition of conjunction property.
Brief description of the drawings
Fig. 1 is ideograph of the expression using an embodiment of the fiber separation process of the microbubble of the present invention.
Fig. 2 is the structure explanation figure of the micro bubble generation device used in fiber separation process of the present invention.
Fig. 3 for represent the present invention and enter with the fiber separation process using microbubble and by the dispersion liquid containing microbubble
The ideograph of one embodiment of the fiber separation processing of row case of wet attrition.
Fig. 4 is carried out for the rank of the fibre separation index of the biomass of the use microbubble of the present invention by the sedimentation of dispersion liquid
The picture of expression.
Fig. 5 be by the rank of the fibre separation index for the biomass for only carrying out wet attrition process with and with the biology of microbubble
The fibre separation index of matter is contrasted, the picture being indicated by the sedimentation of dispersion liquid.
Fig. 6 is that the rank of the fibre separation index of the present invention is passed through into the photo under sweep electron microscope (FE-SEM)
The picture that (50,000 times of multiplying power) is indicated.
Description of reference numerals
The 1 fiber separation treatment trough based on microbubble
2 micro bubble generation devices
The particle diameter distribution measurement apparatus of 3 microbubbles
4 pipelines
5 circulating pumps
6 case of wet attrition devices
7 conveyance conduits
10 micro bubble generation devices
11a, 11b liquid hand-hole
12 gas-liquid generation troughs
13 outer shell tanks
14 gas supply parts
15 short-circuit walls
16 gas discharge outlets
17 liquid supply ports
The side wall of 18 gas-liquid generation troughs
The inner face of 19 outer shell tanks
20 gaps
21 liquid supply units
Embodiment
Hereinafter, the mode for implementing the present invention is illustrated.But, however it is not limited to the embodiment described.
1. the fiber separation process in the presence of microbubble
(1) micro bubble generation device
Fig. 1 schematically shows an example of the fiber separation process under microbubble existence condition of the present invention.Such as
(a) shown in~(c), dispersion liquid, i.e. (a) that the biomass of biological source is carried out to the biomass of pre-treatment has been carried out at deproteinized
Reason and dedusting processing the biogenic material containing chitin dispersion liquid, (b) carried out deproteinized processing, dedusting processing with
And dispersion liquid, (c) of the biogenic material (chitosan) containing chitin of deacetylation processing have been carried out at delignification
Manage and go the dispersion liquid of the biogenic material containing cellulose of hemicellulose processing, put into the processing of microbubble fiber separation
In groove 1.Microbubble fiber separation treatment trough 1 is suitably stirred by agitating device (not shown).Microbubble occurs by microbubble
Device 2 is blown into microbubble fiber separation treatment trough 1.Micro bubble generation device has the spray that the microbubble generated is sprayed onto to outside
Outlet.Liquid and gas in micro bubble generation device 1 are provided by pipeline 4, circulating pump 5, and particle diameter is also sprayed simultaneously with the liquid
50 below μ micro-bubble.The particle diameter of microbubble is measured by microbubble particle diameter distribution measurement apparatus 3.
In micro bubble generation device, flowed in generation microbubble with liquid, be divided into convolution liquid flow type, static mixing
Formula, injecting type, cavitation corrosion formula, venturi type, also have centrifugal pump and swirling flow decline bubble generator combined type, utilize pressurization
The type of dissolution type microbubble genetic method.
On the micro bubble generation device in the present invention, with the convolution disclosed in Japanese Unexamined Patent Publication 2015-167946
It is specifically described exemplified by the structure of the micro-nano bubble generator of streaming.As described below, in Japanese Unexamined Patent Publication 2015-167946
The disclosed swirling flow nano-bubble generating apparatus that declines deviates the cylinder shaft core of gas-liquid generation trough 12 cylinder of outer shell tank 13
Shaft core, the reduction for the water-carrying capacity that gap 20 is supplied with liquid supply port 17 and narrow, will not so make liquid supply port 17
The water supplied flows back in outer shell tank in vain, because being injected into gas-liquid hair from liquid hand-hole 11a, 11b with uniform flow
In raw groove 12, it is possible to efficiently produce micro-nano bubble, be preferably adapted for the fiber separation of biological nano fiber.
Fig. 2 (a) is the stereogram of micro-nano bubble generator, and Fig. 2 (b) is is formed in liquid hand-hole 11a, 11b
Position by gas-liquid generation trough 12 along the sectional view blocked with the direction that direction of principal axis intersects vertically, Fig. 2 (c) is gas-liquid occurs
The sectional view that groove is axially blocked.
Micro-nano bubble generator 10 has gas-liquid generation trough 12, outer shell tank 13 and gas supply part 14.
Its structure is that the water of liquid is pressurizeed in advance and supplied from liquid supply unit 21, relative to these water, by gas
The air of body is pressurizeed and supplied from gas supply part 14 in advance, and the water for being mixed with air bubble is supplied into liquid supply port 17.
The inner face of gas-liquid generation trough 12 is drum, and the tangent to periphery direction of inner face is provided with 2 liquid for water filling
There is short-circuit wall 15 body hand-hole 11a, 11b, one end, and the other end has vapor-liquid outlet 16.Outer shell tank 13 covers gas-liquid generation trough 12
A part, gas-liquid is injected into by the mixed alveolate water supplied from liquid supply port 17 from liquid hand-hole 11a, 11b
In groove 12.
The gap that the side wall 18 formed outside the circumferencial direction of gas-liquid generation trough 12 and the inner face 19 of outer shell tank 13 are formed
20 be the stream of water, the cylinder shaft core of gas-liquid generation trough 12 is deviateed to the cylinder shaft core of outer shell tank 13, gap 20 is supplied with liquid
The reduction of the water-carrying capacity supplied to mouth 17 and narrow.
From outer shell tank 13 inject be mixed with the water of air bubble from liquid hand-hole 11a, 11b with substantially uniform flow in gas
The swirling flow being whirled up in liquid generation trough 12 along cylinder inner face, the shearing that air bubble contained in water is passed through into swirling flow
Power and micro-nano bubble, produce gas-liquid that the air of micro-nano bubble mixes with water and are discharged to by vapor-liquid outlet 16
(not shown) in tank.
In addition, the used gas for constituting microbubble of fiber separation processing in the present invention is not limited to air.Can also
It is the rare gas such as oxygen, ozone, nitrogen, carbon dioxide or helium, argon gas, neon.In addition, being mixed with the supply of the water of air bubble
Method is not limited to the method mixed after water and air is pressurizeed respectively.Water and air can also be carried out before the pressing
Pressurizeed again by water pump etc. after mixing.According to the method, air bubble can in advance be refined by the swirling flow of water pump,
The generation efficiency and quality of micro-nano bubble can be improved.
The fluid flow of the micro bubble generation device in fiber separation process in the present invention is 10~50L/min, preferably
For 20~40L/min, gas flow is 0.5~10L/min, preferably 1~5L/min.Gas flow is relative to fluid flow
It is 0.02~0.10, preferably 0.05~0.08 than (gas flow/fluid flow).Purpose is to continuously and efficiently produce
Microbubble below 50 μm of particle diameter.
(2) case of wet attrition device
Case of wet attrition can be used together in the fiber separation process of the present invention.Case of wet attrition mode, which is divided into, uses Media mills
Mode and using autogenous mill mode.The method of operation is divided into circular flow, bypass operation, batch type operation, can be by
Suitable mode is selected according to purpose.
The use of the mode of Media mills is to instigate crushing medium (such as ball, pearl) to collide to carry out fiber point by fiber separation thing
From mode.The mixed serum feeding of dispersion liquid containing microbubble and crushing medium is referred to as to the appearance of pulverizing chamber by water pump
In device, crushing medium is set to occur to collide and carry out fiber separation.
Workable Media mills are not particularly limited in the present invention.The production of " Getzmann " company can such as be included
" TORUSMILL ", ASHIZAWA Finetech companies production " Star Mill AMR1 ", AIMEX companies production " visco mill ",
SHINMARU ENTERPRISES companies production " dyno-mill ", Mitsubishi Heavy Industries Ltd's production " diamond fine pulverizer ", Kotobuki
Giken companies production " APEXi Mega ", shallow field ironworker company production " PICO MILL ", Eurotech companies production " OB ball mills ",
NIPPON COKE＆ENGINEERING companies produce " SC MILL " etc..
Mode based on autogenous mill refers to the mode that fiber separation is carried out without using crushing medium (such as ball, pearl).No
Directly to applying physical force by fiber separation thing, but by containing the shear stress produced in the dispersion liquid of fiber separation thing
Or cavitation corrosion etc. is enclosed in by the release effect around fiber separation thing to carry out the mode of fiber separation.It is divided into mixing treating liquid
High-speed stirred mode, high pressure and in the narrow swiftly flowing good pressure distribution mode of stream is applied to treatment fluid.To by fiber
The damage of isolate is smaller, is conducive to the improvement of the stability and rheological characteristic of fiber separation dispersion liquid.In addition, because not comprising powder
Broken medium, so being not only the quality of product, productivity ratio is also improved.
The autogenous mill that can be used in the present invention is not particularly limited.The production of PRIMIX companies can such as be included
" T.K.FILMIX ", Sugino Machine companies production " Ultimaizer ", Sugino Machine companies production " Star Burst
Mini ", M scientific ＆ technical corporation production " CLEAR SS5 ", " CLEARMIX W-MOTION ", Eurotech companies production " CAVITRON ",
The production of SHINMARU ENTERPRISES companies " IKA DR2000 ", IKA companies production " MHD2000/4PIOT ", Zeng Xing industry companies
Produce " Supermass colloider (MKCA6-2) " etc..
2. biomass and its pre-treatment
(1) biomass
The biomass starting material (biogenic material) of biological nano fiber for generating the present invention refers to, with fiber knot
The biogenic material and its derivative of structure.Specifically such as cellulose, chitin, chitosan etc..
The raw material of the biomass of the present invention can be any form such as fibrous, granular.If cellulose then has extensively
General plant material (such as rice straw, Ni shells, straw, corncob, timber, forest land waste material, the waste material of saw lumber factory, build timber,
Waste paper), if chitin then has shell-fish, insects or krill shell and crust etc..
(2) pre-treatment of biomass
In the manufacture method of the biological nano fiber of the present invention, enter preferably with efficiently to carry out fiber separation processing
The biogenic material of pre-treatment is gone, such as (a) has carried out the biology containing chitin of deproteinized processing and dedusting processing
Source material, (b) have carried out the biological source material containing chitin of deproteinized processing, dedusting processing and deacetylation processing
The biogenic material containing cellulose that material (chitosan), (c) have carried out delignification processing and gone hemicellulose to handle.Separately
Outside, the refined chitin, chitosan, crystallinity cellulose for the market sale for having carried out pre-treatment can be used.
(3) dispersion liquid of biomass
The dispersion liquid of biomass in the present invention refers to the gains after biomass is distributed in water.Work as biomass concentration
Belong to mobility dispersion liquid when relatively low, with biomass because of fiber separation micro- Fineization (nanofiber), viscosity uprises and is in
Existing pasty state.
Dispersion liquid concentration preferably 0.1~15 weight % of the biomass of the present invention.Reason is dense when biomass dispersion liquid
When degree is more than 15 weight %, the viscosity of dispersion liquid rises, and diffusion of the microbubble in biomass dispersion liquid is not abundant enough with being impregnated with,
Fiber separation processing based on microbubble performance is insufficient.In addition, when biomass dispersion liquid concentration is less than 0.1 weight %, it is raw
Thing nanofiber manufacture efficiency can be reduced., can be in micro- gas when the carry out dispersion liquid concentration handled with fiber separation increases
Steep while processing and use wet attrition process, to realize appropriate fiber separation processing.
Furthermore it is possible to the pH adjusting agents such as acid be added in the dispersion liquid of the present invention, to improve the dispersiveness of biomass.
(4) biomass nano fiber
In the present invention, nanofiber refers to the corpus fibrosum that fiber footpath is nano-scale.Pass through the nanofiber of the present invention
Manufacture method, will be separated between fiber after the fiber of 1 least unit, diameter reaches 10~50nm or so.Nanofiber
Diameter measured by electron microscope picture.
The fiber footpath of the biological nano fiber of the present invention is 10~1000nm, preferably 10~40nm, more preferably 15
~25nm.The biological nano fiber of the present invention can be shaped to as not knitting easily because aspect ratio (fiber length/fiber footpath) is larger
The interlaced film of the such nanofiber of cloth, flake.Cellulose nano-fibrous film, thin plate may be used as it is high thoroughly
The paper of lightness.If the film of chitin, chitosan nano fiber, thin slice, internal organs when artificial skin, operation are may be used as
The anti-limited step of adhesion.
In addition, the biological nano fiber of the present invention is mixed with other materials, composite can be formed after integration.Its
He can be properly selected material according to purposes or required physical characteristic of composite etc., and natural material, artificial material all may be used.
The mixing of biological nano fiber and other materials, integrated method can use method as known in the art, can do appropriate
Selection.
(5) other purposes
The nanofiber of biomass based on manufacture method of the present invention, can increase the specific surface area of matrix, so can
To improve the accessibility of the enzyme of its hydrolyzable.I.e., it is possible to efficiently extract solubilized sugar from cellulose and chitin
Glucose and 2-Acetamido-2-deoxy-D-glucose.Especially because during the process for extracting glucose from cellulose turns into biorefinery
Bottleneck, so the present invention's is effective using being sent to expectation.
Similarly, chitin, chitosan can also the solubilized sugar of high efficiency extraction 2-Acetamido-2-deoxy-D-glucose, aminoglucose
Sugar.When for chitosan, the chitosan oligomer of 6 sugar left and right has the bioactivity such as excellent antibiotic property, is gathered by improving shell
The ratio of sugared oligomer can improve the value of functional material.
In addition, 2-Acetamido-2-deoxy-D-glucose is the composition of hyaluronic acid, taste sweet tea, so the characteristics of there is easily intake.When
During for cellulose, by reducing fibre diameter so that weave in high-density between fiber, reaches the effect of increase intensity.
In addition, by increasing the space between fiber, it can be improved as the performance of heat-barrier material or filtering material.
As cosmetic material, the sense of touch lubricated very much is had using biological nano fiber, moisture-keeping function, shield can be played
Skin effect, antibacterial action, the effect enhanced metabolism.
Embodiment
Hereinafter, embodiment is shown to specifically describe the present invention in further detail, but is not to be construed as to present invention implementation
The limitation of example.In addition, embodiment, comparative example are as shown in table 1 below.
In table 1, embodiment 1-1~1-6 and comparative example 1-1 use the biogenic material for containing chitin as biology
Matter；Embodiment 2-1~2-3 and comparative example 2-1 use the biogenic material for containing chitosan as biomass；Embodiment 3-1
~embodiment 3-3 and comparative example 3-1 use the biogenic material for containing cellulose as biomass.
Table 1
<Embodiment 1-1>
Embodiment 1-1 is just illustrated from crab shell manufacture chitin nano fiber.
(1) deproteinized is handled
Crab shell (Canada's production, be purchased from Chkawai fertilizer, 100g) will be dried to be added in the 5% KOH aqueous solution, backflow 6 is small
When remove crab shell in protein.After the crab shell filtering after processing, cleaned with water to neutrality.
(2) dedusting is handled
The crab shell carried out after deproteinized processing is stirred 2 days at room temperature in 7% HCl/water solution, removed in crab shell
Ash content.Crab shell is filtered again and is cleaned using water to neutrality.
(3) depigmentaton is handled
The crab shell for the processing that deash is added to 1.7% NaClO20.3M sodium acetate buffers in,
Stirred 6 hours at 80 DEG C, remove pigment contained in crab shell.Crab shell is filtered again and is cleaned using water to neutrality.
(4) fiber separation is handled
The crab shell for having carried out depigmentaton processing is disperseed in water, after using domestic stirrer, dispersion liquid is crushed, addition
Acetic acid adjusts pH to 3~4, stirs 72 hours.The dispersion liquid (0.1wt%) that the crab shell of acetic acid processing will have been carried out is fed to tool
There is the fiber separation processing of the micro-nano bubble generator of Clothoid type (TriBiox Laboratories companies produce (TFBS-1))
In groove, it is stirred at room temperature 48 hours, fiber separation is into chitin nano fiber.Microbubble condition is：30L/ points of liquor charging flow,
2L/ points of air mass flow, the particle diameter of microbubble is 40 μm.
(5) dispersiveness is assessed
Chitin nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank A ".
(6) pattern is assessed
By fiber separation handle after chitin nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 4 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 1-2>
It is identical with embodiment 1-1 to (3) discoloration processing from the processing of (1) deproteinized.
(4) fiber separation is handled
The crab shell for having carried out depigmentaton processing is disperseed in water, after using family-use grinder, dispersion liquid is crushed, addition
Vinegar acid for adjusting pH is stirred 72 hours to 3~4.The dispersion liquid (1.0wt%) that the crab shell of acetic acid processing will have been carried out is fed to and had
The fiber separation treatment trough of the micro-nano bubble generator of Clothoid type (TriBiox Laboratories companies produce (TFBS-1))
In, it is stirred at room temperature 72 hours, fiber separation is into chitin nano fiber.Microbubble condition is：30L/ points of liquor charging flow, sky
2L/ points of throughput, the particle diameter of microbubble is 40 μm.
(5) dispersiveness is assessed
Chitin nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank B ".
(6) pattern is assessed
By fiber separation handle after chitin nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 3 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 1-3>
It is identical with embodiment 1-1 to (3) discoloration processing from the processing of (1) deproteinized.
(4) fiber separation is handled
The crab shell for having carried out depigmentaton processing is disperseed in water, after using family-use grinder, dispersion liquid is crushed, addition
Vinegar acid for adjusting pH is stirred 72 hours to 3~4.The dispersion liquid (3.0wt%) for the crab shell that peracetic acid processing will be carried out is fed to and had
The fiber separation treatment trough of the micro-nano bubble generator of Clothoid type (TriBiox Laboratories companies produce (TFBS-1)),
It is stirred at room temperature 72 hours, fiber separation is into chitin nano fiber.Microbubble condition is：30L/ points of liquor charging flow, air
2L/ points of flow, microbubble particle diameter is 40 μm.
(5) dispersiveness is assessed
Chitin nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank C ".
(6) pattern is assessed
By fiber separation handle after chitin nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 3 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 1-4>
It is identical with embodiment 1-1 to (3) discoloration processing from the processing of (1) deproteinized.
(4) fiber separation is handled
The crab shell for having carried out depigmentaton processing is disperseed in water, after using family-use grinder, dispersion liquid is crushed, addition
Vinegar acid for adjusting pH is stirred 72 hours to 3~4, and the dispersion liquid (3.0wt%) for the crab shell that will carry out peracetic acid processing, which is fed to, to be had
The fiber separation treatment trough of the micro-nano bubble generator of Clothoid type (TriBiox Laboratories companies produce (TFBS-1))
In, it is stirred at room temperature 72 hours, fiber separation is into chitin nano fiber.Microbubble condition is：30L/ points of liquor charging flow, sky
2L/ points of throughput, microbubble particle diameter is 40 μm.
Afterwards, the dispersion liquid containing microbubble is fed to online wet type autogenous mill (IKA companies production (MHD2000/
4PILOT)) carry out wet attrition process.Processing capacity is 0.1L/ points, and processing time is 3 hours.
(5) dispersiveness is assessed
Chitin nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank D ".
(6) pattern is assessed
By fiber separation handle after chitin nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 4 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 1-5>
It is identical with embodiment 1-1 to (3) discoloration processing from the processing of (1) deproteinized.
(4) fiber separation is handled
The crab shell for having carried out depigmentaton processing is disperseed in water, after using family-use grinder, dispersion liquid is crushed, addition
Vinegar acid for adjusting pH is stirred 72 hours to 3~4.The dispersion liquid (10wt%) for the crab shell that peracetic acid processing will be carried out is fed to and had
The fiber separation treatment trough of the micro-nano bubble generator of Clothoid type (TriBiox Laboratories companies produce (TFBS-1))
In, it is stirred at room temperature 84 hours, is separated into chitin nano fiber.Microbubble condition is：30L/ points of liquor charging flow, air stream
2L/ points are measured, the particle diameter of microbubble is 40 μm.
Afterwards, by the dispersion liquid containing microbubble feed online wet type ball mill (ASHIZAWA FINETECH companies
(Star Mill AMR1)), carry out wet attrition process.Processing capacity is that 0.1L/ divides, processing time is 3 hours.
(5) dispersiveness is assessed
Chitin nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank D ".
(6) pattern is assessed
By fiber separation handle after chitin nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 4 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 1-6>
It is identical with embodiment 1-1 to (3) discoloration processing from the processing of (1) deproteinized.
(4) fiber separation is handled
The crab shell for having carried out depigmentaton processing is disperseed in water, after using family-use grinder, dispersion liquid is crushed, addition
Vinegar acid for adjusting pH is stirred 72 hours to 3~4.The dispersion liquid (15wt%) for the crab shell that peracetic acid processing will be carried out is fed to and had
The micro-nano bubble generator of Clothoid type (TriBiox Laboratories companies produce TFBS-1)) fiber separation treatment trough
In, it is stirred at room temperature 72 hours, is separated into chitin nano fiber.Microbubble condition is：30L/ points of liquor charging flow, air stream
2L/ points are measured, the particle diameter of microbubble is 40 μm.
Afterwards, the dispersion liquid containing microbubble is fed into online wet type autogenous mill (IKA companies production (MHD2000/
4PILOT)), wet attrition process is carried out.Processing capacity is that 0.1L/ divides, processing time is 3 hours.
(5) dispersiveness is assessed
Chitin nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank D ".
(6) pattern is assessed
By fiber separation handle after chitin nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 4 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Comparative example 1-1>
It is identical with embodiment 1-1 to (3) discoloration processing from the processing of (1) deproteinized.
(4) fiber separation is handled
The crab shell for having carried out depigmentaton processing is disperseed in water, after using family-use grinder, dispersion liquid is crushed, addition
Vinegar acid for adjusting pH is stirred 72 hours to 3~4.Handled without microbubble, dispersion liquid is fed into online wet type autogenous mill
(Sugino Machine companies production Star Burst Mini), carries out wet attrition process.Processing capacity is 0.1L/ points, processing
Time is 3 hours.
(5) dispersiveness is assessed
Chitin nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank E ".Shown with contrasting " its transparency is higher compared with rank D ",
It may determine that obtained chitin nano fiber length is shorter.
(6) pattern is assessed
By fiber separation handle after chitin nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 3 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 2-1>
Embodiment 2-1 just manufactures chitosan nano fiber from shrimp shell and illustrated.
(1) deproteinized is handled
The shrimp shell (10g) of fresh ring shrimp is added in the 5% KOH aqueous solution, flowed back 6 hours, is removed in shrimp shell
Protein.After the shrimp shell filtering after processing, cleaned with water to neutrality.
(2) dedusting is handled
By shrimp shell under the 7%HCl aqueous solution, it is stirred at room temperature 2 days, removes the ash content among shrimp shell, filters shrimp shell simultaneously again
Cleaned with water to neutrality.
(3) decolorization
In 1.7% NaClO20.3M sodium acetate buffer in addition processing after shrimp shell, stir 6 at 80 DEG C
Hour, remove pigment contained in shrimp shell.Shrimp shell is filtered again and is cleaned with water to neutrality.
(4) processing of deacetylation
The sodium hydroxide that 40% is added in protein, ash content, the shrimp shell of pigment will be removed, returned while being constantly blown into nitrogen
Stream 6 hours, after deacetylation processing has been carried out, filters shrimp shell and is cleaned with water to neutrality again.
(5) fiber separation is handled
The shrimp shell for having carried out deacetylation processing is disperseed in water, will after dispersion liquid is crushed using domestic stirrer
Shrimp shell dispersion liquid (1.0wt%) is fed to (the TriBiox Laboratories productions of the micro-nano bubble generator of Clothoid type
(TFBS-1) in fiber separation treatment trough), it is stirred at room temperature 72 hours, fiber separation is into chitosan nano fiber.Micro- gas
Bubble condition is：30L/ points of liquor charging flow, 2L/ points of air mass flow, the particle diameter of microbubble is 40 μm.
(6) dispersiveness is assessed
Chitosan nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank B ".
(7) pattern is assessed
By fiber separation handle after chitosan nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 3 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 2-2>
Handle identical with embodiment 2-1 to (4) deacetylation decolorization from (1) deproteinized.
(5) fiber separation is handled
The shrimp shell for having carried out deacetylation processing is disperseed in water, will after dispersion liquid is crushed using domestic stirrer
The dispersion liquid (3.0wt%) of shrimp shell is fed to the micro-nano bubble generator of Clothoid type (TriBiox Laboratories
Company produces (TFBS-1)) fiber separation treatment trough in, be stirred at room temperature 72 hours, fiber separation is into chitosan Nanowire
Dimension.Microbubble condition is：30L/ points of liquor charging flow, 2L/ points of air mass flow, the particle diameter of microbubble is 40 μm.
Afterwards, the dispersion liquid containing microbubble is fed into online wet type autogenous mill (IKA companies production (MHD2000/
4PILOT)), wet attrition process is carried out.Processing capacity is that 0.1L/ divides, processing time is 0.5 hour.
(5) dispersiveness is assessed
Chitosan nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank D ".
(6) pattern is assessed
By fiber separation handle after chitosan nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 4 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 2-3>
Handle identical with embodiment 2-1 to (4) deacetylation decolorization from (1) deproteinized.
(5) fiber separation is handled
The shrimp shell for having carried out deacetylation processing is disperseed in water, will after dispersion liquid is crushed using domestic stirrer
The dispersion liquid (10wt%) of shrimp shell is fed to the micro-nano bubble generator of Clothoid type (TriBiox Laboratories public affairs
Department's production (TFBS-1)) fiber separation treatment trough in, be stirred at room temperature 84 hours, fiber separation is into chitosan nano fiber.
Microbubble condition is：30/L points of liquor charging flow, 2/L points of air mass flow, the particle diameter of microbubble is 40 μm.
Afterwards, the dispersion liquid containing microbubble is fed into online wet type autogenous mill (IKA companies production (MHD2000/
4PILOT)), wet attrition process is carried out.Processing capacity is that 0.1L/ divides, processing time is 0.5 hour.
(5) dispersiveness is assessed
Chitosan nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank D ".
(6) pattern is assessed
By fiber separation handle after chitosan nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 4 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Comparative example 2-1>
Handle identical with embodiment 2-1 to (4) deacetylation decolorization from (1) deproteinized.
(5) fiber separation processing disperses the shrimp shell for having carried out deacetylation processing in water, and dispersion liquid is used into family expenses
After mixer is crushed, prawn shell dispersion liquid (3.0wt%) is handled without microbubble, and dispersion liquid is supplied into online wet type without medium
Grinding machine (Sugino Machine companies production Star Burst Mini), carries out wet attrition process.Processing capacity be 0.1L/ point,
Processing time is 0.5 hour.
(5) dispersiveness is assessed
Chitosan chitin nano fiber dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index (sedimentation
Property, dispersiveness：Fibre separation index rank shown in Fig. 5) equivalent to " rank E ".With contrast display " its is transparent compared with rank D "
Degree is higher, it can be determined that the fibre length of obtained chitosan nano fiber is shorter.
(6) pattern is assessed
By fiber separation handle after chitosan nano fiber dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 3 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 3-1>
Embodiment 3-1 is just illustrated from cellulose powder manufacture is cellulose nano-fibrous.
(1) fiber separation is handled
Using cellulose powder (Nippon Paper company production KC Flock W-50) as dispersant, it is distributed to containing 0.02wt%
In the aqueous solution of Sodium Polyacrylate, after using domestic stirrer, dispersion liquid is crushed, by the dispersion liquid of cellulose powder
(1.0wt%) is fed to the micro-nano bubble generator of Clothoid type (TriBiox Laboratories companies production (TFBS-
1) in fiber separation treatment trough), it is stirred at room temperature 72 hours, fiber separation is into cellulose nano-fibrous.Microbubble condition
For：30L/ points of liquor charging flow, 2L/ points of air mass flow, 40 μm of the particle diameter of microbubble.
(2) dispersiveness is assessed
Cellulose nano-fibrous dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank B ".
(3) pattern is assessed
By fiber separation handle after cellulose nano-fibrous dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 3 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 3-2>
(1) fiber separation is handled
Using cellulose powder (Nippon Paper company production KC Flock W-50) as dispersant, it is distributed to containing 0.02wt%
In the aqueous solution of Sodium Polyacrylate, after using domestic stirrer, dispersion liquid is crushed, by the dispersion liquid of cellulose powder
(3.0wt%) is fed to the micro-nano bubble generator of Clothoid type (TriBiox Laboratories companies production (TFBS-
1) in fiber separation treatment trough), it is stirred at room temperature 72 hours, fiber separation is into cellulose nano-fibrous.Microbubble condition
For：30L/ points of liquor charging flow, 2L/ points of air mass flow, 40 μm of the particle diameter of microbubble.
Afterwards, the dispersion liquid containing microbubble is fed into online wet type autogenous mill (IKA companies production (MHD2000/
4PILOT)), wet attrition process is carried out.Processing capacity is that 0.1L/ divides, processing time is 0.5 hour.
(2) dispersiveness is assessed
Cellulose nano-fibrous dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank D ".
(3) pattern is assessed
By fiber separation handle after cellulose nano-fibrous dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 4 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Embodiment 3-3>
(1) fiber separation is handled
Using cellulose powder (Nippon Paper company production KC Flock W-50) as dispersant, it is distributed to containing 0.02wt%
In the aqueous solution of Sodium Polyacrylate, after using domestic stirrer, dispersion liquid is crushed, by the dispersion liquid of cellulose powder
(10wt%), which is fed, has the micro-nano bubble generator of Clothoid type (TriBiox Laboratories companies produce (TFBS-1))
Fiber separation treatment trough in, be stirred at room temperature 72 hours, fiber separation is into cellulose nano-fibrous.Microbubble condition is：
30L/ points of liquor charging flow, 2L/ points of air mass flow, 40 μm of the particle diameter of microbubble.
Afterwards, the dispersion liquid containing microbubble is fed into online wet type autogenous mill (IKA companies production (MHD2000/
4PILOT)), wet attrition process is carried out.Processing capacity is that 0.1L/ divides, processing time is 0.5 hour.
(2) dispersiveness is assessed
Cellulose nano-fibrous dispersion liquid after fiber separation is handled is placed 10 days.Fibre separation index is (settleability, scattered
Property：Fibre separation index rank shown in Fig. 4) equivalent to " rank D ".
(3) pattern is assessed
By fiber separation handle after cellulose nano-fibrous dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 4 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
<Comparative example 3-1>
(1) fiber separation is handled
Using cellulose powder (Nippon Paper company production KC Flock W-50) as dispersant, it is distributed to containing 0.02wt%
In the aqueous solution of Sodium Polyacrylate, after using domestic stirrer, dispersion liquid is crushed, to the dispersion liquid of cellulose powder
(3.0wt%) is handled without microbubble, and dispersion liquid is sent into online wet type autogenous mill, and (Sugino Machine companies produce
Star Burst Mini), carry out wet attrition process.Processing capacity is that 0.1L/ divides, processing time is 0.5 hour.
(2) dispersiveness is assessed
The plain nanofiber dispersion liquid of chitin fiber after fiber separation is handled is placed 10 days.Fibre separation index (sedimentation
Property, dispersiveness：Fibre separation index rank shown in Fig. 4) equivalent to " rank F ".With " though compared with rank E " transparency under
Drop, but with contrast display, " transparency is still higher compared with rank D ", it can be determined that obtained cellulose nano-fibrous fibre length
It is relatively short.
(3) pattern is assessed
By fiber separation handle after cellulose nano-fibrous dispersion liquid form dry coationg, it is micro- by scanning electron
Mirror (FE-SEM：JSM-6700F, JEOL) the formed envelope of observation.Fibre separation index (the observation of pattern：Fiber shown in Fig. 5
Separating degree rank) equivalent to " rank 3 ".Most of fiber width is in about below 20nm, and width is in the very elongated of 10nm or so
, the nanofiber of homogeneous it is more.
Industry applications
The present invention can be used in the field using biomass nano fiber.In addition, the present invention can also be used in composite wood
In the manufacture of material or cosmetics etc. and these field of use.
Claims (6)
1. a kind of manufacture method of biological nano fiber, is the biological nano that fiber separation processing is carried out to the dispersion liquid of biomass
The manufacture method of fiber, it is characterised in that：
The fiber separation processing is the fibre carried out under the microbubble existence condition produced by swirling flow micro bubble generation device
Tie up separating treatment.
2. a kind of manufacture method of biological nano fiber, is the biological nano that fiber separation processing is carried out to the dispersion liquid of biomass
The manufacture method of fiber, it is characterised in that：
The fiber separation handles and is used in what is carried out under the microbubble existence condition produced by swirling flow micro bubble generation device
Fiber separation processing, and the dispersion liquid progress of the biomass containing the microbubble produced by swirling flow micro bubble generation device is wet
Formula comminuted fibres separating treatment.
3. the manufacture method of the biological nano fiber described in claim 1 or 2, it is characterised in that：
Fiber separation processing is carried out under the microbubble existence condition produced by swirling flow micro bubble generation device, wherein, it is described
The dispersion liquid of biomass for it is following any one：(a) biology containing chitin of deproteinized processing and dedusting processing has been carried out
Dispersion liquid, (b) of source material have carried out the life containing chitin of deproteinized processing, dedusting processing and deacetylation processing
The biology containing cellulose that dispersion liquid, (c) of thing source material have carried out delignification processing and gone hemicellulose to handle comes
The dispersion liquid of source material.
4. the manufacture method of the biological nano fiber in claims 1 to 3 described in any one, it is characterised in that：
The concentration of the dispersion liquid of the biomass for fiber separation processing is 0.1~15 weight %.
5. the manufacture method of the biological nano fiber in Claims 1-4 described in any one, it is characterised in that：
It is micro- produced by the swirling flow micro bubble generation device in the dispersion liquid of the biomass in fiber separation processing
The particle diameter of bubble is below 50 μm.
6. the manufacture method of the biological nano fiber in claim 1 to 5 described in any one, it is characterised in that：
The fiber footpath of the biological nano fiber is 10~1000nm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015225332A JP5934974B1 (en) | 2015-11-18 | 2015-11-18 | Production method of bionanofiber |
| JP2015-225332 | 2015-11-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106978651A true CN106978651A (en) | 2017-07-25 |
Family
ID=56120552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611008409.3A Pending CN106978651A (en) | 2015-11-18 | 2016-11-16 | The manufacture method of biological nano fiber |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5934974B1 (en) |
| CN (1) | CN106978651A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108144465A (en) * | 2018-01-19 | 2018-06-12 | 济南上华科技有限公司 | It is a kind of based on the device that nanometer microvesicle is largely generated in water |
| JP7015201B2 (en) * | 2018-03-29 | 2022-02-02 | 大阪瓦斯株式会社 | Modified chitin nanofibers and their manufacturing methods |
| JP2021017460A (en) * | 2019-07-17 | 2021-02-15 | 甲陽ケミカル株式会社 | High-concentration dispersion of nanosized chitin |
| CN112523007A (en) * | 2020-11-30 | 2021-03-19 | 南京林业大学 | Method for preparing high-strength transparent chitin nanofiber gelatin composite membrane by mild method |
| WO2022244820A1 (en) * | 2021-05-18 | 2022-11-24 | 中越パルプ工業株式会社 | Hydrophobized cnf dispersion production method, and hydrophobized cnf oil-based component-containing body production method |
| CN114557453A (en) * | 2022-01-25 | 2022-05-31 | 广东省农业科学院蚕业与农产品加工研究所 | Shaddock peel modified fiber and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102852016A (en) * | 2012-06-29 | 2013-01-02 | 东北林业大学 | Process for preparing water-soluble cellulose through negative-pressure mass transfer and diffusion dialysis membrane separation technology |
| CN102877342A (en) * | 2012-09-14 | 2013-01-16 | 无锡市凯利药业有限公司 | Method for preparing cellulose nanocrystals |
| CN103387689A (en) * | 2013-08-19 | 2013-11-13 | 南京林业大学 | Method for preparing nanocellulose fiber optical transparent membrane material from peanut hulls |
| WO2014155102A1 (en) * | 2013-03-25 | 2014-10-02 | University College London | Method and apparatus for producing polymeric structures |
| CN103342825B (en) * | 2013-07-10 | 2015-02-25 | 南京林业大学 | Preparation method of chitin nano-fiber/polyving akohol composite membrane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5334055B2 (en) * | 2009-09-14 | 2013-11-06 | 独立行政法人産業技術総合研究所 | Production method of bionanofiber |
| JP2014018641A (en) * | 2012-07-21 | 2014-02-03 | Yamaguchi Kogyo:Kk | Air cleaner by cavitation bubbled water stream |
| JP5712322B1 (en) * | 2013-12-25 | 2015-05-07 | 中越パルプ工業株式会社 | Nano refined product manufacturing apparatus, nano refined product manufacturing method |
-
2015
- 2015-11-18 JP JP2015225332A patent/JP5934974B1/en active Active
-
2016
- 2016-11-16 CN CN201611008409.3A patent/CN106978651A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102852016A (en) * | 2012-06-29 | 2013-01-02 | 东北林业大学 | Process for preparing water-soluble cellulose through negative-pressure mass transfer and diffusion dialysis membrane separation technology |
| CN102877342A (en) * | 2012-09-14 | 2013-01-16 | 无锡市凯利药业有限公司 | Method for preparing cellulose nanocrystals |
| WO2014155102A1 (en) * | 2013-03-25 | 2014-10-02 | University College London | Method and apparatus for producing polymeric structures |
| CN103342825B (en) * | 2013-07-10 | 2015-02-25 | 南京林业大学 | Preparation method of chitin nano-fiber/polyving akohol composite membrane |
| CN103387689A (en) * | 2013-08-19 | 2013-11-13 | 南京林业大学 | Method for preparing nanocellulose fiber optical transparent membrane material from peanut hulls |
Non-Patent Citations (2)
| Title |
|---|
| 季祥等: "<<生物质能源及废物利用新技术>>", 31 December 2012, 吉林大学出版社 * |
| 张俐娜等: "<<基于生物质的环境友好材料>>", 30 June 2011, 化学工业出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5934974B1 (en) | 2016-06-15 |
| JP2017094218A (en) | 2017-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106978651A (en) | The manufacture method of biological nano fiber | |
| Zinge et al. | Nanocellulose based biodegradable polymers | |
| US11001644B2 (en) | Re-dispersed microfibrillated cellulose | |
| JP5334055B2 (en) | Production method of bionanofiber | |
| US9149064B2 (en) | Method of producing nanofibrillar cellulose with high absorptivity to fat and cholate | |
| JP6363340B2 (en) | Emulsions containing nano-sized fibrous polysaccharides, materials and methods for producing them | |
| CN104684935B (en) | Anti-cracking agent for water-borne acrylic paint and coating compositions | |
| SE530720C2 (en) | Pre-treatment of chips with high-defibration | |
| CN111465620B (en) | Carboxymethylated cellulose nanofibers | |
| Jongaroontaprangsee et al. | Production of nanocellulose from lime residues using chemical-free technology | |
| KR20200012103A (en) | An apparatus and method for mass producting nanocellulose fiber | |
| KR101973758B1 (en) | Preparing method of cellulose nanofiber using electron beam irradiation and cellulose nanofiber therefrom | |
| KR102109355B1 (en) | Preparing method of redispersible cellulose nanofiber, redispersible cellulose nanofiber therefrom, and dispersion method of redispersible cellulose nanofiber | |
| JP2010188288A (en) | Biomass crushing method, biomass crusher, and method of manufacturing sugars | |
| CN103518017A (en) | Method for producing cellulose-containing mass for producing composite material | |
| CN102159637A (en) | Cellulose-containing mass | |
| JP2019131772A (en) | Method for producing biomass nanofiber dry body and method for producing biomass nanofiber resin composite | |
| KR102305296B1 (en) | Microplastic replaceable natural particles and preparation method thereof | |
| US20190308167A1 (en) | Process for Converting Banana Tree Stalk Into Fibers for Absorption of Hydrocarbons and Corresponding System and Product | |
| JP6165103B2 (en) | Method for producing fish scale-derived collagen dispersion and fish scale-derived collagen dispersion | |
| CN109881521A (en) | A kind of nano-cellulose, Preparation method and use | |
| JPH04281017A (en) | Natural fiber material opened to submicron unit, its production and production device therefor | |
| JP7449323B2 (en) | Fibrous cellulose composite resin | |
| JP7440574B2 (en) | Fibrous cellulose composite resin | |
| Rashida | Microfibrillated Cellulose from Coloured Cotton Textile Waste |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170725 |
|
| WD01 | Invention patent application deemed withdrawn after publication |