CN110054808A - A kind of micro-nano cellulose compound, preparation method and purposes - Google Patents
A kind of micro-nano cellulose compound, preparation method and purposes Download PDFInfo
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- CN110054808A CN110054808A CN201810052985.0A CN201810052985A CN110054808A CN 110054808 A CN110054808 A CN 110054808A CN 201810052985 A CN201810052985 A CN 201810052985A CN 110054808 A CN110054808 A CN 110054808A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
Abstract
The present invention relates to a kind of micro-nano cellulose compound, the micro-nano cellulose compound includes micro-nano lignocellulose, and the grapheme material being dispersed in micro-nano lignocellulose；The micro-nano lignocellulose includes the lignin of 10~35wt%.The present invention utilizes the thin layer feature of grapheme material, mix it with the cellulosic material containing lignin, grapheme material intercalation to after in the cellulosic material containing lignin, remove to obtain micro-nano lignocellulose by collaboration lignin, the process does not need chemical reagent, easy to operate easily-controllable；In preparation method provided by the invention, graphene plays special adsorption, does not need the pre-treatment that the cellulosic material containing lignin is carried out to drop lignin, can directly remove to obtain micro-nano cellulose compound, environment friendly and pollution-free；In preparation method provided by the invention, micro-nano cellulose compound is prepared in such a way that mechanical pretreatment and high pressure homogenizer combine, blocking of the high pressure homogenizer in shattering process is can avoid, reduces abrasion.
Description
Technical field
This hair belongs to modifying nanometer cellulose field, and in particular to a kind of micro-nano cellulose compound, preparation method and
Purposes.
Background technique
With the continuous social and economic development, the problems such as non-renewable resources such as petroleum, coal are increasingly deficient, environmental pollution
It becomes increasingly conspicuous, application of the renewable resource in every field is increasingly taken seriously.Plant fiber material is most main on the earth
The biomass resource wanted, high-efficiency comprehensive utilization will occupy particularly important status in entire Biomass Industry.Plant fiber
Mainly it is made of cellulose, lignin and hemicellulose.Cellulose is to be widely present on the earth and reproducible resource.By natural
The nano-cellulose of cellulose preparation not only has huge specific surface area, high-hydrophilic, high Young's modulus, high intensity, good
Biodegradability and biocompatibility and stable chemical property, also have huge chemical modification potentiality, papermaking,
The fields such as adsorbent material, battery diaphragm and high-performance composite materials show huge application prospect.
Lignin is second renewable resource abundant in the world, is predominantly located between cellulose fibre, passes through to be formed
Intertexture net carrys out sclereid wall, plays resistance to compression.Lignin can be used as the use such as dispersing agent, adsorbent and reinforcing agent, have pole
Its extensive utility value.
The common preparation method of nano-cellulose has chemical method, Mechanical Method, bioanalysis and artificial synthesized method.Wherein Mechanical Method
It prepares that nano-cellulose effect on environment is small, and step is simple, is the preparation method for being suitble to large-scale commercial production.Due to hard
Lignin interweave among cellulose, can not simply direct mechanical stripping prepare nano-cellulose, prepare Nanowire at present
There are no obtained high lignin content nano-celluloses in the method for dimension element.There is still a need for first with acid, alkali pair in the prior art
Plant fiber carries out Removment of Lignin By Pretreatments and hemicellulose, then carries out mechanical stripping, complex steps, makes in preprocessing process
Acid, alkali or organic solvent still cause centainly to pollute to environment.
(such as high molecular polymer or it polymerize in addition, the micro-nano cellulose compound of prior art preparation and oily matter
Monomer) poor compatibility, exist to reunite with high molecular polymer compound tense and disperse non-uniform problem.
This field needs to develop a kind of micro-nano cellulose compound, can be well compatible with oil soluble material, and makes
Preparation Method is simple, will not generate pollution problem, and can directly be handled using the higher raw material of content of lignin as object.
Summary of the invention
The purpose of the present invention is to provide a kind of micro-nano cellulose compound, the micro-nano cellulose compound includes
Micro-nano lignocellulose, and the grapheme material being dispersed in micro-nano lignocellulose；
The micro-nano lignocellulose include 10~35wt% (such as 12wt%, 15wt%, 18wt%, 22wt%,
27wt%, 32wt% etc.) lignin.
Content of lignin is higher in micro-nano cellulose compound prepared by the present invention, and cellulose diameter has micro-nano meter ruler
It is very little, contain grapheme material simultaneously.In the micro-nano cellulose compound, the lignin of high-content improves micro nanometer fiber
The hydrophobicity of plain compound shows good dispersibility in non-aqueous solvent, while it is compound to improve micro-nano cellulose
The compatibility of object and polymer material, realizes not needing to be modified the cellulose of micro-or nano size is directly dispersed in polymerization
A possibility that in object material.
The micro-nano lignocellulose can be understood as containing 10~35wt% lignin, and diameter dimension is in 1nm
Cellulosic material within~1 μm.
Preferably, the content of the grapheme material be micro-nano lignocellulose 15wt% or less (such as
10wt%, 8wt%, 5wt%, 2wt%, 1wt% etc.), preferably 5wt% is hereinafter, further preferably 1wt% or less.
Preferably, the grapheme material with a thickness of≤20nm (such as 18nm, 15nm, 12nm, 8nm, 5nm etc.), it is excellent
Select 3~10nm.
Preferably, (such as 1.1 μm, 2 μm, 3 μm, 5 μm, 7 μm of length >=1 μm of the micro-nano cellulose compound
Deng), diameter be 4~200nm (such as 10nm, 50nm, 80nm, 150nm, 180nm etc.), draw ratio be 100~500 (such as
120,180,220,270,300,350,380,420,480 etc.).
The second object of the present invention is to a kind of preparation method of micro-nano cellulose compound as described in the first purpose is provided,
Described method includes following steps:
(1) cellulosic material containing lignin and grapheme material are dispersed in water, are uniformly mixed, are dispersed
Liquid；
(2) dispersion liquid is subjected to mechanical force prestripping, obtains prestripping product dispersion liquid；
(3) prestripping product dispersion liquid is subjected to high pressure homogenizer homogeneous, obtains micro-nano cellulose compound dispersion liquid.
In the preparation method of micro-nano cellulose compound provided by the invention, grapheme material is able to enter cellulose
Between lignin, weaken the interaction between lignin molecule, insertion cellulose silk interfascicular plays physical barrier peptizaiton, promotees
It is removed into cellulose, the directly mechanical stripping of the cellulosic material (content of lignin is higher) containing lignin is successfully obtained into micro-nano
Rice cellulose composite dispersion liquid.The addition of grapheme material avoid for destroy lignin interaction and apply high temperature,
The critical conditions such as high pressure, strong acid, highly basic and organic solvent.
The present invention prepares micro-nano cellulose compound in such a way that mechanical prestripping and high pressure homogenizer combine, and can keep away
Exempt to directly adopt blocking of the high pressure homogenizer in shattering process, reduces abrasion.
Preferably, the cellulosic material of the present invention containing lignin is that plant material extracts hemicellulose or portion completely
Divide the residue after extracting hemicellulose.
Preferably, the plant material includes forest, crops, any a kind or at least two kinds of of group in agriculture and forestry organic waste material
It closes；
Preferably, the cellulosic material containing lignin include furfural dregs, xylose residue, do not float wood pulp, do not float straw pulp,
Any a kind or at least two kinds of of combination in the agricultural wastes of stalk.
Preferably, in the cellulosic material containing lignin, content of lignin be 10~30wt% (such as
15wt%, 20wt%, 25wt% etc.), and the content of cellulose of the xylose residue 65% or more (such as 70wt%, 75wt%,
80wt% etc.).
Preferably, also contain hemicellulose in the cellulosic material containing lignin.
Preferably, in the cellulosic material containing lignin, hemicellulose level≤10wt% (such as 1wt%,
2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt% etc.).
In the prior art, the preparation process of nano-cellulose needs to carry out bleaching, so-called bleaching to raw material
It needs to remove the lignin in raw material using strong acid, highly basic or organic solvent etc..Micro-nano cellulose provided by the invention is compound
Object preparation method contains the cellulosic material of lignin using grapheme material intercalation, without using strong acid, highly basic and organic molten
Under the premise of agent, the removing that mechanical force is achieved that cellulosic material higher for content of lignin is only relied on, is obtained micro-
Nano-cellulose compound, it is environment friendly and pollution-free.
The grapheme material is by mechanically pulling off method, oxidation-reduction method, pyrolysis method, intercalation stripping method, chemical gaseous phase
Sedimentation, liquid phase stripping method or biomass by hydro-thermal carbonizatin method are prepared.
Preferably, the average platelet thickness of the grapheme material be≤20nm (such as 18nm, 14nm, 10nm, 5nm,
2nm etc.), preferably 3~10nm.
It is more advantageous to intercalation with a thickness of the grapheme material of 3~10nm and enters inside lignin molecule, realize micro-nano fibre
Tie up the removing of plain compound.
Preferably, in the dispersion liquid, the sum of the concentration of cellulosic material and grapheme material containing lignin is
0.1wt%-15wt% (such as 1wt%, 3wt%, 6wt%, 7wt%, 9wt%, 12wt% etc.), preferably 5wt%-7wt%.
Preferably, the additional amount of the grapheme material is the 10wt% or less (example of the cellulosic material containing lignin
Such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%), preferably 5wt% is hereinafter, into one
Walk preferred 1wt% or less.
Preferably, the mechanical force prestripping includes ultrasound removing, ball milling removing, mill removing, removing, grinding stripping is sanded
Any one from.
Preferably, the diameter for the product that the mechanical force prestripping obtains be 200~1500nm (such as 250nm, 300nm,
350nm、400nm、450nm、500nm、550nm、600nm、700nm、800nm、900nm、1000nm、1100nm、1200nm、
1300nm, 1400nm etc.).
Preferably, the pressure of step (3) described homogeneous be 50~150MPa (such as 70MPa, 90MPa, 110MPa,
120MPa, 140MPa etc.), preferably 60~80MPa.
Preferably, the cycle-index of the homogeneous be 3~10 times (such as 4 times, 5 times, 6 times, 7 times, 8 times, it is 9 inferior), it is excellent
It selects 3~7 times.
Preferably, step (4) are carried out after step (3): micro-nano cellulose compound dispersion liquid is post-processed, is obtained micro-
The compound powder of nano-cellulose.
Preferably, the post-processing includes washing, grinds, any a kind or at least two kinds of of combination in spray drying.
The three of the object of the invention are to provide a kind of purposes of micro-nano cellulose compound as described in the first purpose, described
Micro-nano cellulose compound is used for field of textiles, field of medicaments, high performance adjuvant field, adsorbent material field, food packaging
Field or field of compound material.
Compared with prior art, the invention has the following advantages:
(1) present invention utilizes the thin layer feature of grapheme material, mixes it with the cellulosic material containing lignin, stone
In black alkene material intercalation to the cellulosic material containing lignin, collaboration lignin is removed to obtain micro-nano lignocellulose,
The process does not need chemical reagent, easy to operate easily-controllable；
(2) in preparation method provided by the invention, graphene plays special adsorption, does not need the fibre that content of lignin is high
The pre-treatment that plain raw material carries out drop lignin is tieed up, can directly remove to obtain micro-nano lignocellulose, it is environment friendly and pollution-free；
(3) it in preparation method provided by the invention, is prepared in such a way that mechanical pretreatment and high pressure homogenizer combine micro-
Nano lignin cellulose can avoid blocking of the high pressure homogenizer in shattering process, reduce abrasion.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Those skilled in the art are not construed as to this hair it will be clearly understood that the described embodiments are merely helpful in understanding the present invention
Bright concrete restriction.
It in the art, illustratively include furfural dregs, xylose residue, not there are many cellulosic materials containing lignin
Wood pulp, the agricultural wastes for not floating straw pulp, stalk etc. are floated, but no matter which the cellulosic material containing lignin selects
Kind, composition is not much different, and for the present invention only using xylose residue as the raw material of following embodiment and comparative example, those skilled in the art can
The similar cellulose that other contain lignin is replaced with the content of the cellulose, lignin and the hemicellulose that limit according to it
Raw material.
Embodiment 1
A kind of preparation method of micro-nano cellulose compound, includes the following steps:
(1) 10g is extracted to the xylose residue (wood of cellulose, 28wt% containing 70wt% after hemicellulose by corncob
The hemicellulose of quality and 2wt%) and 0.5g graphene (lamella average thickness be 5nm) be dispersed in 200mL water, mixing is equal
It is even, obtain dispersion liquid；
(2) dispersion liquid is placed in ball mill and carries out prestripping, obtain prestripping product dispersion liquid (with removing product diameter
For 200~1500nm)；
(3) prestripping product dispersion liquid is placed in 130MPa recirculation gas stripper 3 circulations in high pressure homogenizer, obtaining diameter is
5~20nm, the nano-cellulose compound dispersion liquid that content of lignin is 28%；The concentration of the micro-nano cellulose dispersion liquid
For 4.8wt%, for the diameter of micro-nano cellulose within the scope of 3~7nm, the range of draw ratio is 230~260.
Embodiment 2
The difference from embodiment 1 is that etc. quality replacement xylose residue be by corn stover extract hemicellulose after xylose
Slag (hemicellulose of the lignin of cellulose, 25wt% containing 65wt%, 10wt%).
The concentration for the micro-nano cellulose dispersion liquid that embodiment 2 obtains is 4.8wt%, and the diameter of micro-nano cellulose exists
Within the scope of 20~40nm, the range of draw ratio is 340~380.
Embodiment 3
The difference from embodiment 1 is that etc. quality replacement xylose residue be by timber extract hemicellulose after xylose residue (contain
There are the hemicellulose of the cellulose of 65wt%, the lignin of 30wt%, 5wt%).
The concentration for the micro-nano cellulose dispersion liquid that embodiment 3 obtains is 4.5wt%, and the diameter of micro-nano cellulose exists
Within the scope of 10~20nm, the range of draw ratio is 240~250.
Embodiment 4~6
The difference from embodiment 1 is that lamella average thickness is the graphene of the graphene (embodiment 4) of 20nm, 3nm
The graphene (embodiment 6) of (embodiment 5), 10nm.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 4 obtains is 4.6wt%, and the diameter of micro-nano cellulose exists
Within the scope of 170~210nm, the range of draw ratio is 100~214.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 5 obtains is 4.75wt%, and the diameter of micro-nano cellulose is equal
Between 10~20nm, the range of draw ratio is 230~270.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 6 obtains is 4.68wt%, and the diameter of micro-nano cellulose is equal
Between 45~55nm, the range that draw ratio is is 150~210.
Embodiment 7~11
The difference from embodiment 1 is that grapheme material is incorporated as aoxidizing for 0.1g graphene (embodiment 7), 0.6g
Graphene (embodiment 8), 0.7g graphene (embodiment 9), 0.8g graphene (embodiment 10), 0.9g graphene oxide (are implemented
Example 11).
The concentration for the micro-nano cellulose dispersion liquid that embodiment 7 obtains is 4.5wt%, and the diameter of micro-nano cellulose is 3
Between~5nm, draw ratio is 260~270.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 8 obtains is 4.0wt%, and the diameter of micro-nano cellulose is 15
Between~25nm, draw ratio is 235~255.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 9 obtains is 3.8wt%, and the diameter of micro-nano cellulose is 45
Between~55nm, draw ratio is 230~250.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 10 obtains is 3.75wt%, and the diameter of micro-nano cellulose is
Between 90~98nm, draw ratio is 200~220.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 11 obtains is 3.5wt%, and the diameter of micro-nano cellulose is
Between 160~170nm, draw ratio is 170~190.
Embodiment 12
The difference from embodiment 1 is that high-pressure homogeneous condition are as follows: 150MPa recirculation gas stripper 5 circulations (embodiment 12)；
50MPa recirculation gas stripper 10 circulations (embodiment 13)；60MPa recirculation gas stripper 3 circulations (embodiment 14)；80MPa recirculation gas stripper 7
A circulation (embodiment 15).
The concentration for the micro-nano cellulose dispersion liquid that embodiment 12 obtains is 4.78wt%, and the diameter of micro-nano cellulose is
Between 3~5nm, draw ratio is 240~260.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 13 obtains is 4.6wt%, and the diameter of micro-nano cellulose is
13~19nm, draw ratio are 230~240.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 14 obtains is 4.55wt%, and the diameter of micro-nano cellulose is
45~55nm, draw ratio are 220~230.
The concentration for the micro-nano cellulose dispersion liquid that embodiment 15 obtains is 4.58wt%, and the diameter of micro-nano cellulose is
28~42nm, draw ratio are 210~225.
Embodiment 16
Step (4) are carried out embodiment 1 the step of after (3) to be spray-dried micro-nano cellulose dispersion liquid, are obtained micro-
Nano-cellulose powder.
The diameter range of the micro-nano cellulose is 13~17nm, and draw ratio range is 240~250.
Comparative example 1
A kind of preparation method of micro-nano cellulose compound, includes the following steps:
(1) xylose residue (lignin of cellulose, 28wt% containing 70wt% after hemicellulose will be extracted by corncob
With the hemicellulose of 2wt%) it is dispersed in 200mL water, it is uniformly mixed, obtains dispersion liquid；
(2) dispersion liquid is placed in ball mill and carries out prestripping, obtain prestripping product dispersion liquid；
(3) prestripping product dispersion liquid is placed in 130MPa recirculation gas stripper 3 circulations in high pressure homogenizer, obtains lignin
The micro-nano cellulose compound dispersion liquid that content is 28%；The concentration of the micro-nano cellulose dispersion liquid is 3.3wt%, is received
The diameter of rice cellulose is 1700~1900nm, and draw ratio is 8~12.
Comparative example 2
A kind of preparation method of micro-nano cellulose compound, includes the following steps:
(1) 10g is extracted to the xylose residue (wood of cellulose, 28wt% containing 70wt% after hemicellulose by corncob
The hemicellulose of quality and 2wt%) and 0.5g graphite (lamella average thickness is dispersed in 200mL water for 50nm), is uniformly mixed,
Obtain dispersion liquid；
(2) dispersion liquid is placed in ball mill and carries out prestripping, obtain prestripping product dispersion liquid；
(3) prestripping product dispersion liquid is placed in 130MPa recirculation gas stripper 3 circulations in high pressure homogenizer, obtains lignin
The micro-nano cellulose compound dispersion liquid that content is 28%；The concentration of the micro-nano cellulose dispersion liquid is 3.2wt%, micro-
The diameter range of nano-cellulose is 830~890nm, and draw ratio range is 25~35.
Comparative example 3
A kind of preparation method of micro-nano cellulose, includes the following steps:
(1) 10g bleaching wooden oar (hemicellulose of cellulose and 15wt% containing 85wt%) is dispersed in 200mL water
In, it is uniformly mixed, obtains dispersion liquid；
(2) dispersion liquid is placed in ball mill and carries out prestripping, obtain prestripping product dispersion liquid；
(3) prestripping product dispersion liquid is placed in 130MPa recirculation gas stripper 3 circulations in high pressure homogenizer, obtains Nanowire
Tie up plain dispersion liquid；The concentration of the nano-cellulose dispersion liquid is 4.5wt%, the diameter range of nano-cellulose is 30~
90nm, draw ratio range are 205~230.
It can be seen that in the system of aqueous solution from the result of embodiment and comparative example, not any to xylose residue progress
In the case where chemical treatment, using the means of mechanical pretreatment and high-pressure homogeneous combination, using the special adsorption of grapheme material,
Cellulose is removed, prepares the micro-nano cellulose compound with certain draw ratio (100~500), a diameter of 4
~200nm, preparation process is simple and easy to control, and any chemical reagents are not used in preparation process, environment friendly and pollution-free.
Performance test:
Compatibility experiments, test method are that the dispersion liquid for obtaining embodiment 1~15 and comparative example 1~3 is spray-dried, and are pressed
It is scattered in methylene chloride according to the ratio of powder concentration 0.1wt%, stands observation dispersion liquid and the time being layered occur.Test result
It is shown in Table 1:
Table 1
| Sample | Solution separation time | Sample | Solution separation time |
| Embodiment 1 | > 3 months | Embodiment 10 | 54 days |
| Embodiment 2 | > 3 months | Embodiment 11 | 35 days |
| Embodiment 3 | > 3 months | Embodiment 12 | > 3 months |
| Embodiment 4 | 28 days | Embodiment 13 | > 3 months |
| Embodiment 5 | > 3 months | Embodiment 14 | > 3 months |
| Embodiment 6 | > 3 months | Embodiment 15 | > 3 months |
| Embodiment 7 | > 3 months | Comparative example 1 | Instant precipitation |
| Embodiment 8 | > 3 months | Comparative example 2 | 2 hours |
| Embodiment 9 | > 3 months | Comparative example 3 | 3 days |
Can be seen that the micro-nano cellulose compound for preparing using xylose residue as raw material from the test result of table 1, it is having
Favorable dispersibility in solvent has good compatibility with organic solvent, and is capable of the stabilization of long period, therefore its energy
It is enough well compatible with the polymer or oiliness polymerized monomer of oiliness.When the thickness of grapheme material is in 3~10nm, the graphene
When the additional amount of material is the 10wt% or less of xylose residue, the micro-nano cellulose compound being prepared in organic solvent can
It is enough stabilized 3 months or more.
The Applicant declares that the present invention illustrates the process method of the present invention through the above embodiments, but the present invention not office
It is limited to above-mentioned processing step, that is, does not mean that the present invention must rely on the above process steps to be carried out.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of micro-nano cellulose compound, which is characterized in that the micro-nano cellulose compound includes micro-nano wooden
Cellulose fiber element, and the grapheme material being dispersed in micro-nano lignocellulose；
The micro-nano lignocellulose includes the lignin of 10~35wt%.
2. micro-nano cellulose compound as described in claim 1, which is characterized in that the content of the grapheme material is micro-
The 15wt% of nano lignin cellulose is hereinafter, it is preferred that 5wt% is hereinafter, further preferably 1wt% or less；
Preferably, the grapheme material with a thickness of≤20nm, preferably 3~10nm.
3. micro-nano cellulose compound as claimed in claim 1 or 2, which is characterized in that the micro-nano cellulose is compound
Length >=1 μm of object, diameter are 4~200nm, and draw ratio is 100~500.
4. a kind of preparation method of the micro-nano cellulose compound as described in one of claims 1 to 3, which is characterized in that institute
The method of stating includes the following steps:
(1) cellulosic material containing lignin and grapheme material are dispersed in water, are uniformly mixed, obtain dispersion liquid；
(2) dispersion liquid is subjected to mechanical force prestripping, obtains prestripping product dispersion liquid；
(3) prestripping product dispersion liquid is subjected to high pressure homogenizer homogeneous, obtains micro-nano cellulose compound dispersion liquid.
5. preparation method as claimed in claim 4, which is characterized in that the cellulosic material containing lignin is that plant is former
Material extracts the residue after hemicellulose or extracting section hemicellulose completely；
Preferably, the plant material includes forest, crops, any a kind or at least two kinds of of combination in agriculture and forestry organic waste material；
Preferably, the cellulosic material containing lignin includes furfural dregs, xylose residue, does not float wood pulp, do not float straw pulp, stalk
Agricultural wastes in any a kind or at least two kinds of of combination；
Preferably, in the cellulosic material containing lignin, content of lignin is 10~30wt%, and content of cellulose exists
65% or more；
Preferably, the cellulosic material containing lignin also contains hemicellulose；
Preferably, in the cellulosic material containing lignin, hemicellulose level≤10wt%.
6. preparation method as described in claim 4 or 5, which is characterized in that the grapheme material is by mechanically pulling off method, oxygen
Change reduction method, pyrolysis method, intercalation stripping method, chemical vapour deposition technique, liquid phase stripping method or the preparation of biomass by hydro-thermal carbonizatin method
It obtains；
Preferably, the average platelet thickness of the grapheme material is≤20nm, preferably 3~10nm.
7. the preparation method as described in one of claim 4~6, which is characterized in that in the dispersion liquid, the fibre containing lignin
The sum of the concentration for tieing up plain raw material and grapheme material is 0.1wt%-15wt%, preferably 5wt%-7wt%；
Preferably, the additional amount of the grapheme material be the cellulosic material containing lignin 10wt% hereinafter, it is preferred that
5wt% is hereinafter, further preferably 1wt% or less.
8. the preparation method as described in one of claim 4~7, which is characterized in that the mechanical force prestripping includes ultrasound stripping
From the removing of, ball milling, mill removing, removing, any one in grinding removing is sanded；
Preferably, the diameter for the product that the mechanical force prestripping obtains is in 200~1500nm；
Preferably, the pressure of the homogeneous is 50~150MPa, preferably 60~80MPa；
Preferably, the cycle-index of the homogeneous is 3~10 times, preferably 3~7 times.
9. the preparation method as described in one of claim 4~8, which is characterized in that carry out step (4) after step (3): will be micro-
The post-processing of nano-cellulose compound dispersion liquid, obtains the compound powder of micro-nano cellulose；
Preferably, the post-processing includes washing, grinds, any a kind or at least two kinds of of combination in spray drying.
10. a kind of purposes of the micro-nano cellulose compound as described in one of claims 1 to 3, which is characterized in that described micro-
Nano-cellulose compound is for field of textiles, field of medicaments, high performance adjuvant field, adsorbent material field, food packaging neck
Domain or field of compound material.
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| CN201810052985.0A CN110054808A (en) | 2018-01-19 | 2018-01-19 | A kind of micro-nano cellulose compound, preparation method and purposes |
| PCT/CN2019/071536 WO2019141140A1 (en) | 2018-01-19 | 2019-01-14 | Micro-nano lignocellulose, preparation method thereof and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606988A (en) * | 2019-10-15 | 2019-12-24 | 福州大学 | Lignin modified graphene material and preparation method and application thereof |
| CN112357918A (en) * | 2020-11-03 | 2021-02-12 | 中国林业科学研究院林产化学工业研究所 | Nano-diamond prepared by using plant fiber as raw material and method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360616A (en) * | 2013-07-10 | 2013-10-23 | 武汉纺织大学 | Method for preparing hybrid film through graphene/nano crystalline cellulose dispersion liquid |
| CN105899455A (en) * | 2013-11-22 | 2016-08-24 | 昆士兰大学 | Nanocellulose |
| CN106084300A (en) * | 2016-06-21 | 2016-11-09 | 华南理工大学 | A kind of redox graphene nanofibrils cellulose composite material thin film and preparation method thereof |
| CN106832426A (en) * | 2016-12-12 | 2017-06-13 | 山东圣泉新材料股份有限公司 | A kind of method for preparing nano-cellulose and gained nano-cellulose |
| CN106832425A (en) * | 2016-09-20 | 2017-06-13 | 济南圣泉集团股份有限公司 | High performance Graphene composite nano fiber element and preparation method thereof, application |
| CN107107661A (en) * | 2014-10-31 | 2017-08-29 | 阿普艾知识产权控股有限责任公司 | Automobile tire containing hydrophobic nano cellulose |
-
2018
- 2018-01-19 CN CN201810052985.0A patent/CN110054808A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360616A (en) * | 2013-07-10 | 2013-10-23 | 武汉纺织大学 | Method for preparing hybrid film through graphene/nano crystalline cellulose dispersion liquid |
| CN105899455A (en) * | 2013-11-22 | 2016-08-24 | 昆士兰大学 | Nanocellulose |
| CN107107661A (en) * | 2014-10-31 | 2017-08-29 | 阿普艾知识产权控股有限责任公司 | Automobile tire containing hydrophobic nano cellulose |
| CN106084300A (en) * | 2016-06-21 | 2016-11-09 | 华南理工大学 | A kind of redox graphene nanofibrils cellulose composite material thin film and preparation method thereof |
| CN106832425A (en) * | 2016-09-20 | 2017-06-13 | 济南圣泉集团股份有限公司 | High performance Graphene composite nano fiber element and preparation method thereof, application |
| CN106832426A (en) * | 2016-12-12 | 2017-06-13 | 山东圣泉新材料股份有限公司 | A kind of method for preparing nano-cellulose and gained nano-cellulose |
Non-Patent Citations (8)
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110606988A (en) * | 2019-10-15 | 2019-12-24 | 福州大学 | Lignin modified graphene material and preparation method and application thereof |
| CN112357918A (en) * | 2020-11-03 | 2021-02-12 | 中国林业科学研究院林产化学工业研究所 | Nano-diamond prepared by using plant fiber as raw material and method thereof |
| CN112357918B (en) * | 2020-11-03 | 2023-08-25 | 中国林业科学研究院林产化学工业研究所 | Nano diamond prepared from plant fiber and method thereof |
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