CN106521714B - The method that carbon fiber is prepared using crop material - Google Patents
The method that carbon fiber is prepared using crop material Download PDFInfo
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- CN106521714B CN106521714B CN201610852635.3A CN201610852635A CN106521714B CN 106521714 B CN106521714 B CN 106521714B CN 201610852635 A CN201610852635 A CN 201610852635A CN 106521714 B CN106521714 B CN 106521714B
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- 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
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
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Abstract
The invention discloses a kind of methods preparing carbon fiber using crop material, belong to stalk comprehensive utilization technical field.The present invention prepares high-purity fiber pulp by stalk first, viscose rayon prepared by fiber pulp, by viscose rayon prepares carbon fiber again, has obtained the high-quality carbon fiber product of high quality.Gained carbon fiber purity of the invention is high, 95% or more phosphorus content, tensile strength 3.4GPa or more.The problem of more carbon fiber impurity, poor tensile strength are prepared using stalk the present invention overcomes the prior art.Present invention process clear route, technical equipment are ripe, are easy to industrialized production.
Description
Technical field
The present invention relates to stalk comprehensive utilization technical field, more particularly to a kind of side preparing carbon fiber using crop material
Method.
Background technology
Carbon fiber is a kind of new fiber materials, and phosphorus content both has the intrinsic intrinsic property of carbon material 90% or more,
Soft processability with fibrous material again, and possess superhigh intensity, high temperature resistant, corrosion-resistant, conductive, heat transfer and thermally expand
A series of excellent properties such as coefficient is small.Currently, carbon fiber has been widely used in the numerous areas such as civilian, military project.
It should say, carbon fiber is the most significant end of stalk fibre application technology, because it represents stalk fibre from separation, essence
The big collection of the systems technologies such as refining, spinning, viscose glue to oxidation, charing, graphitization.
By development for many years, the raw material for producing carbon fiber at present mainly has viscose rayon, pitch and polyacrylonitrile
（PAN）；The latter two are petrochemical materials, and viscose rayon is to pass through a series of complex with timber, cotton natural fiber pulps
What technique was prepared.Requirement of the viscose rayon to pulp is very high, including to alpha-cellulose in pulp（Content, polymerization
Degree）, whiteness, impurity（Hemicellulose, lignin, ash grade）Require.
It China every year can more than 900,000,000 tons of harvesting crops stalk.Stalk described here, including wheat, corn, rice, cotton, height
Remaining stem after the herbage harvestings seed such as the crops such as fine strain of millet, crudefiber crop, soybean, peanut, potato, melon and clover, prairie milk vetch, leaf,
Skin（Shell）, climing rattan（Seedling）Deng and sugarcane（Slag）, corncob, reed etc..
How using so abundant stalk resource preparing market, there is an urgent need for, added value high carbon fibers againThis project
Interest and the concern of domestic and international many professional persons are caused.Chinese patent（CN 104131364 A）Disclose a kind of agriculture
The processes such as the production method of crop material activated carbon fiber, including melting reels off raw silk from cocoons, is oxidation-stabilized, anoxybiotic charing；The technology does not have
Separation, refining stalk cellulose, i.e., prepare viscose rayon not over stalk cellulose, then prepare carbon fiber by viscose rayon
Dimension, but stalk powder is directly heated and is reeled off raw silk from cocoons；Because impurity composition is too many, the tensile strength for the carbon fiber which finally prepares
Only 1GPa or so limits the application range of carbon fiber product.
Invention content
In order to make up for the deficiencies of the prior art, the present invention provides a kind of simple for process, gained carbon fiber purity height, stretchings
The big method that carbon fiber is prepared using crop material of intensity.
The technical scheme is that：
A method of carbon fiber, including step are prepared using crop material：
A prepares fiber pulp
A1）Stalk through impurity elimination, dedusting, rub silk, segment, cleaning after in merging steam explosion separator, stalk quality 1-20 is added
Water again, it is 5-25% that alkali to lye mass concentration, which is added, and water vapour to temperature is passed through into steam explosion separator and rises to 60-95 DEG C
Afterwards, stop water flowing steam；It is passed through inert gas into steam explosion separator, air in steam explosion separator is emptied, is sealed；Then between
Having a rest property is passed through water vapour and inert gas into steam explosion separator, to maintain temperature in steam explosion separator to be 80-110 DEG C, press
Power is 0.5-2MPa, and heat-insulation pressure keeping spurts after 20-180 minutes；
A2）To spurt slurry move to grinding mill in grind, after grinding, cross 30-50 mesh sieve, screen out short in slurries
Small fiber；
A3）It is separated by solid-liquid separation, obtains filter residue one and filtrate one；
A4）Filter residue one is washed several times using dilute hot alkaline solution, is separated by solid-liquid separation, is obtained filter residue two and filtrate two；
A5）Filter residue two is placed in enzymatic vessel, the water of the 1-10 times of quality of filter residue two is added, and compound protease is added, enzyme
Solution 10-80 minutes；Normal temperature type alpha-amylase is then added, digests 10-80 minutes；It then passes to steam and is warming up to 60-70 DEG C, protect
It is 2-20 minutes warm, the activity of inactivator；The compound protease is by having the alkali protease of endopeptidase activity and having end peptide
The Proteinase K of enzymatic activity forms；The normal temperature type alpha-amylase is by microwave induced gained variation bacillus licheniformis secretion gained
The preference temperature of alpha-amylase, the normal temperature type alpha-amylase is 22-35 DEG C；
A6）Mixture in enzymatic vessel is placed in bleaching tank, the mass fraction that hydrogen peroxide is added to hydrogen peroxide is 0.1%-
0.5%, keep the temperature 10-120 minutes at 50-80 DEG C；
A7）Hydrogen peroxide is continuously added, until the mass fraction of hydrogen peroxide is 2%-5%, carries out bleaching；
A8）It is separated by solid-liquid separation, obtains filter residue three and filtrate three；Filter residue three obtains filter residue four after alcohol is washed and is washed；
A9）Filter residue four is through drying, crushing to get fiber pulp finished product.
The preparation of B viscose rayons
B1）It uses mass fraction to impregnate the fiber pulp finished product for the potassium hydroxide solution of 10%-15%, cellulose is made to turn
Turn to alkali cellulose；
B2）It is separated by solid-liquid separation, obtains blocky alkali cellulose, crush the alkali cellulose that the bulk alkali cellulose obtains loose state；
B3）The alkali cellulose of loose state comes into full contact with oxygen, carries out burin-in process；
B4）Carbon disulfide is added, the alkali cellulose after aging carries out yellow processing, obtains cellulose xanthate；
B5）The potassium hydroxide of mass fraction 3%-20% is added into the alkali cellulose after yellow, cellulose xanthate hydrolyzes,
Degree of esterification reduces；Filtering, to remove bubble and impurity, obtains viscose glue；
B6）The viscose glue forms thread by spinneret orifice and enters the coagulating bath containing acid, and alkali is neutralized, and thread is frozen into silk
Item, cellulose xanthate disintegrating and regeneration are cellulose hydrate, are configured to cellulose strand；
B7）The cellulose strand is through washing, caustic wash desulfuration, to get viscose final product after drying.
The preparation of C viscose-based carbon fibers
The viscose final product pre-oxidizes 0.5-3 hours in 200-300 DEG C of pre-oxidation furnace, then respectively in 200-
800 DEG C of retort low-temperature carbonizations 1-10 minutes, in 1000-3000 DEG C of retort high temperature carbonization 0.2-10 minutes, in 2000-4000
DEG C graphitizing furnace high temperature handles 5-50 seconds to get viscose-based carbon fiber.
Preferably, step A3）Gained filtrate one is used to prepare lignin and hemicellulose.
Preferably, step A4）In, the hot alkaline solution be mass fraction be 1%-10% potassium hydroxide solution,
Sodium hydroxide solution or calcium hydroxide solution.
Preferably, step A5）In, the obtaining step of the microwave induced gained variation bacillus licheniformis is specific
For：The culture solution of bacillus licheniformis is placed in microwave generator, setting microwave power is 850-950W, and pulse frequency is
2300MHz, microwave treatment 20s, cooling 20s are 25-35 times reciprocal according to this；Culture solution after microwave treatment is coated on solid training
It supports on base, cultivate 1-2 days under the conditions of 30 DEG C, by screening the ground that alpha-amylase activity is high under four plants of room temperature in the bacterium colony that survives
The dissociant of clothing bacillus.
Further, the dissociant for selecting the highest bacillus licheniformis of alpha-amylase activity under room temperature expands culture,
To obtain the normal temperature type alpha-amylase.
Preferably, step A5）In, have the alkali protease and tool of endopeptidase activity in the compound protease
The ratio of the active Proteinase K of standby peptide ending enzyme is 1:1-3；The addition of the compound protease meets every kilogram of butt filter residue two
The addition of 400-800U, the normal temperature type alpha-amylase meet every kilogram of two 300-700U of butt filter residue.
Preferably, step A8））In, it uses volume fraction to be washed several times for 95% ethyl alcohol alcohol, finally washes.
Preferably, step B4）The addition of middle carbon disulfide is alpha-cellulose butt quality in fiber pulp
25%-50%。
Preferably, step B6）In, in the coagulating bath containing acid, acid is the sulfuric acid that mass fraction is 1%-10%.
Preferably, step B7）In, the caustic wash desulfuration uses mass fraction for the potassium hydroxide solution of 1%-10%
Desulfurization.
Beneficial effects of the present invention are：
The present invention prepares high-purity fiber pulp by stalk first, viscose rayon is prepared by fiber pulp, again by viscose glue fibre
Dimension prepares carbon fiber, has obtained the high-quality carbon fiber product of high quality.Gained carbon fiber purity of the invention is high, phosphorus content 95% with
On, tensile strength 3.4GPa or more.
Present invention process clear route, technical equipment are ripe, are easy to industrialized production.
Specific implementation mode
Embodiment 1
A method of carbon fiber, including step are prepared using crop material：
A prepares fiber pulp
A1）Wheat stalk is through impurity elimination, dedusting, segment（3-4cm）, after cleaning in merging steam explosion separator, stalk matter is added
The water of 10 times of amount, it is 16% that potassium hydroxide to lye mass concentration, which is added, and water vapour to temperature is passed through into steam explosion separator and is risen to
After 90 DEG C, stop water flowing steam；It is passed through inert gas into steam explosion separator, air in steam explosion separator is emptied, is sealed；So
It is intermittent afterwards that water vapour and inert gas are passed through into steam explosion separator, to maintain temperature in steam explosion separator to be 105 DEG C, press
Power is 1.5MPa, and heat-insulation pressure keeping spurts after 80 minutes.
In the step steam explosion separation process, the components such as lignin, hemicellulose, ash content, resinae dissolve in lye；It adopts
With relatively low boiling temperature（It is passed through hot steam realization）Avoid decomposition reaction, dehydration of the cellulosic molecule in digestion process（It is burnt
Change）Reaction, peeling reaction etc., the higher pressure inside the tank of use（It is realized by being passed through inert gas）It ensure that lye to raw cell
Effective infiltration between wall, in addition, using inert environments（It is passed through inert gas realization）Avoid the oxidation of cellulosic molecule group
Reaction, acetyl esterification reaction etc., to ensure the integrality of cellulose.
A2）It slurry will be spurted will move in mill and grind 20 minutes, and after grinding, cross 40 mesh sieve, screen out in slurries
Small short fibers.The step Mechanical Method continues to crack the part chemical bond between macromolecular, contributes to the enzymolysis of next step.
A3）It is separated by solid-liquid separation, obtains filter residue one and filtrate one；Filter residue one is the slurry containing cellulose, and filtrate one is half fiber
Tie up the inorganic salts such as element, lignin, ash content be siliceous.
A4）Filter residue one uses mass fraction to be washed 3 times for 8% dilute hot alkaline solution, is separated by solid-liquid separation, obtains filter residue two and filtrate
Two.The hemicellulose, lignin, ash that the step dissolves cellulose surface remaining using thermokalite grade.
A5）Filter residue two is placed in enzymatic vessel, the water of 26 times of quality of filter residue is added, and compound protease is added（500U/
Kilogram butt filter residue two）, digest 40 minutes；Normal temperature type alpha-amylase is then added（400U/ kilograms of butt filter residue two）, enzymolysis 30
Minute；It then passes to steam and is warming up to 65 DEG C, keep the temperature 10 minutes, the activity of inactivator.
Wherein, compound protease is by having the alkali protease of endopeptidase activity and having the active Proteinase K of peptide ending enzyme
It forms, the alkali protease for having endopeptidase activity in compound protease is with the ratio for having the active Proteinase K of peptide ending enzyme
1: 1；The compound protease can effectively hydrolyzing protein at normal temperatures.
Normal temperature type alpha-amylase is by microwave induced gained variation bacillus licheniformis secretion gained alpha-amylase；It is microwave induced
Gained variation bacillus licheniformis obtaining step be specially：The culture solution of bacillus licheniformis is placed in microwave generator, if
It is 900W, pulse frequency 2300MHz, microwave treatment 20s to set microwave power, cooling 20s, reciprocal 30 times according to this；At microwave
Culture solution after reason is coated on solid medium, is cultivated 1-2 days under the conditions of 30 DEG C, by screening four plants in the bacterium colony that survives
The dissociant of the high bacillus licheniformis of alpha-amylase activity under room temperature.Select the highest lichens of alpha-amylase activity under room temperature
The dissociant of bacillus expands culture, to obtain normal temperature type alpha-amylase；Normal temperature type alpha-amylase is in 22-35 DEG C of temperature
Under expeditiously hydrolyze starch, it is not necessary to as the thermal-stable α-amylase mostly used greatly at present needs high temperature（80-90℃）Condition, because
And reduce energy consumption and also reduce requirement to equipment, while greatly reducing the generation of side reaction.
It herein can be mildly by protein, Starch Hydrolysis at the peptides of small molecule, amino acid, maltose, Portugal with enzyme process
Grape sugar etc. enters in filtrate, to success deproteination matter and starch；To ensure the purity of cellulose.
A6）Mixture in enzymatic vessel is placed in bleaching tank, the mass fraction that hydrogen peroxide is added to hydrogen peroxide is 0.3%,
70 minutes are kept the temperature at 60 DEG C.The step is not intended to bleach, but is dissolved under alkaline condition with hydrogen peroxide and remain in fibre
The hemicellulose and lignin for tieing up pulp surface, are further purified fiber pulp.
A7）Hydrogen peroxide is continuously added, until the mass fraction of hydrogen peroxide is 2.5%, carries out bleaching.
A8）It is separated by solid-liquid separation, obtains filter residue three and filtrate three；Filter residue three is washed 2 times by 95% ethyl alcohol, is finally washed, is obtained filter residue
Four.The recyclable recycling of ethyl alcohol in this step.
Filter residue three is with cellulose fiber pulp crude product as main component.Ethyl alcohol removing remains in fiber pulp surface
Lignin and dissolution lipoid material.
A9）Filter residue four is spray-dried（Temperature is less than 120 DEG C）, slight crush to get fiber pulp finished product.After testing,
Fiber pulp alpha-cellulose content prepared by the present embodiment wheat stalk is 97.4%, and the cellulosic molecule degree of polymerization is 587.
Filtrate one prepares the products such as lignin, hemicellulose in step A, and for waste water in addition to the reuse of part, remaining prepares liquid
Fertilizer.
The preparation of B viscose rayons
B1）It uses mass fraction to impregnate the fiber pulp finished product for 12% potassium hydroxide solution, cellulose is made to be converted into
Alkali cellulose.
The mass fraction that the step generally uses in replacing usual viscose rayon to prepare with the potassium hydroxide of mass fraction 12%
18% sodium hydroxide, the fiber pulp degree of purity that on the one hand prepared by the present invention are very high, it is not necessary to use higher concentration lye de- again
Except impurity such as hemicelluloses remaining in fiber pulp, the presence of another aspect sodium ion can significantly affect carbon fiber in subsequent technique
The tensile strength of dimension and the difficulty for increasing wastewater treatment；The waste water containing potassium ion does not need water process but through adjusting in the present invention
The preparation of liquid fertilizer is used directly for after matching.
B2）It is separated by solid-liquid separation, obtains blocky alkali cellulose, crush the alkali cellulose that the bulk alkali cellulose obtains loose state；
B3）The alkali cellulose of loose state comes into full contact with oxygen, carries out burin-in process；
B4）The carbon disulfide of alpha-cellulose butt quality 31% in fiber pulp is added, the alkali cellulose after aging carries out yellow
Change is handled, and obtains cellulose xanthate；
B5）10% potassium hydroxide, cellulose xanthate hydrolysis, degree of esterification drop are added into the alkali cellulose after yellow
It is low；Filtering, to remove bubble and impurity, obtains viscose glue；
B6）The viscose glue forms thread by spinneret orifice and enters the coagulating bath containing acid, and alkali is neutralized, and thread is frozen into silk
Item, cellulose xanthate disintegrating and regeneration are cellulose hydrate, are configured to cellulose strand；In coagulating bath wherein containing acid, acid is
The sulfuric acid of mass fraction 5%.
B7）The cellulose strand use after washing mass fraction for 5% potassium hydroxide solution desulfurization, after dry, i.e.,
Obtain viscose final product.After testing, the viscose rayon line density that prepared by wheat stalk is 3.67dtex, dry break strength is
4.12cN/dtex, water free breaking elongation rate are 14.7%.
Viscose rayon is prepared by the fiber pulp of wheat stalk using wet spinning technology.It is viscous by being prepared into for fiber pulp
The production of glue fiber, whole process prepare next step carbon fiber and the Waste water reuse of high intensity without using sodium salt
It is significant.
The preparation of C viscose-based carbon fibers
The viscose final product pre-oxidizes 1 hour in 260 DEG C of pre-oxidation furnaces, then low in 500 DEG C of retorts respectively
Temperature charing 5 minutes handles 20 seconds to get viscous in 2000 DEG C of retort high temperature carbonizations 5 minutes, in 3000 DEG C of graphitizing furnace high temperatures
Matrix carbon fiber.
Charing and graphitizing process carry out in an inert atmosphere, and feed inlet, discharge port are sealed using nitrogen.
After testing, the performance indicator of viscose-based carbon fiber obtained by the present embodiment is as follows：
Fibre diameter（μm） 5.8
Tensile strength（GPa） 3.4
Elasticity modulus（GPa） 80.7
Fiber total recovery（%） 38.2
Fibre density（g/m3） 1.75
Phosphorus content（%） 95.2.
Embodiment 2
A method of carbon fiber, including step are prepared using crop material：
A prepares fiber pulp
A1）Reed is through impurity elimination, dedusting, segment（3cm）, after cleaning in merging steam explosion separator, 8 times of reed quality is added
Water, it is 18% that potassium hydroxide to lye mass concentration, which is added, is passed through into steam explosion separator after water vapour to temperature rises to 85 DEG C,
Stop water flowing steam；It is passed through inert gas, such as nitrogen into steam explosion separator, air in steam explosion separator is emptied, seals；So
It is intermittent afterwards that water vapour and inert gas are passed through into steam explosion separator, to maintain temperature in steam explosion separator to be 105 DEG C, press
Power is 1.6MPa, and heat-insulation pressure keeping spurts after 100 minutes.
In the step steam explosion separation process, the components such as lignin, hemicellulose, ash content, resinae dissolve in lye；It adopts
With relatively low boiling temperature（It is passed through hot steam realization）Avoid decomposition reaction, dehydration of the cellulosic molecule in digestion process（It is burnt
Change）Reaction, peeling reaction etc., the higher pressure inside the tank of use（It is realized by being passed through inert gas）It ensure that lye to raw cell
Effective infiltration between wall, in addition, using inert environments（It is passed through inert gas realization）Avoid the oxidation of cellulosic molecule group
Reaction, acetyl esterification reaction etc., to ensure the integrality of cellulose.
A2）It slurry will be spurted will move in colloid mill and grind 25 minutes, and after grinding, cross 45 mesh sieve, screen out in slurries
Small short fibers.The step Mechanical Method continues to crack the part chemical bond between macromolecular, contributes to the enzymolysis of next step.
A3）It is separated by solid-liquid separation, obtains filter residue one and filtrate one；Filter residue one is the slurry containing cellulose, and filtrate one is half fiber
Tie up the inorganic salts such as element, lignin, ash content be siliceous.
A4）Filter residue one uses mass fraction to be washed 5 times for 7% dilute hot alkaline solution, is separated by solid-liquid separation, obtains filter residue two and filtrate
Two.The hemicellulose, lignin, ash that the step dissolves cellulose surface remaining using thermokalite grade.
A5）Filter residue two is placed in enzymatic vessel, the water of 23 times of quality of filter residue is added, and compound protease is added（550U/
Kilogram butt filter residue two）, digest 30 minutes；Normal temperature type alpha-amylase is then added（450U/ kilograms of butt filter residue two）, enzymolysis 20
Minute；It then passes to steam and is warming up to 65 DEG C, keep the temperature 15 minutes, the activity of inactivator.
Wherein, compound protease is by having the alkali protease of endopeptidase activity and having the active Proteinase K of peptide ending enzyme
It forms, the alkali protease for having endopeptidase activity in compound protease is with the ratio for having the active Proteinase K of peptide ending enzyme
1: 2；The compound protease can effectively hydrolyzing protein at normal temperatures.
Normal temperature type alpha-amylase is by microwave induced gained variation bacillus licheniformis secretion gained alpha-amylase；It is microwave induced
Gained variation bacillus licheniformis obtaining step be specially：The culture solution of bacillus licheniformis is placed in microwave generator, if
It is 900W, pulse frequency 2300MHz, microwave treatment 20s to set microwave power, cooling 20s, reciprocal 30 times according to this；At microwave
Culture solution after reason is coated on solid medium, is cultivated 1-2 days under the conditions of 30 DEG C, by screening four plants in the bacterium colony that survives
The dissociant of the high bacillus licheniformis of alpha-amylase activity under room temperature.Select the highest lichens of alpha-amylase activity under room temperature
The dissociant of bacillus expands culture, to obtain normal temperature type alpha-amylase；Normal temperature type alpha-amylase is in 22-35 DEG C of temperature
Under expeditiously hydrolyze starch, it is not necessary to as the thermal-stable α-amylase mostly used greatly at present needs high temperature（80-90℃）Condition, because
And reduce energy consumption and also reduce requirement to equipment, while greatly reducing the generation of side reaction.
It herein can be mildly by protein, Starch Hydrolysis at the peptides of small molecule, amino acid, maltose, Portugal with enzyme process
Grape sugar etc. enters in filtrate, to success deproteination matter and starch；To ensure the purity of cellulose.
A6）Mixture in enzymatic vessel is placed in bleaching tank, the mass fraction that hydrogen peroxide is added to hydrogen peroxide is 0.4%,
50 minutes are kept the temperature at 60 DEG C.The step is not intended to bleach, but is dissolved under alkaline condition with hydrogen peroxide and remain in fibre
The hemicellulose and lignin for tieing up pulp surface, are further purified fiber pulp.
A7）Hydrogen peroxide is continuously added, until the mass fraction of hydrogen peroxide is 4%, carries out bleaching.
A8）It is separated by solid-liquid separation, obtains filter residue three and filtrate three；Filter residue three is washed 3 times by 95% ethyl alcohol, is finally washed, is obtained filter residue
Four.The recyclable recycling of ethyl alcohol in this step.
Filter residue three is with cellulose fiber pulp crude product as main component.Ethyl alcohol removing remains in fiber pulp surface
Lignin and dissolution lipoid material.
A9）Filter residue four is spray-dried（Temperature is less than 120 DEG C）, slight crush to get fiber pulp finished product.After testing,
Fiber pulp alpha-cellulose content prepared by reed is 97.8%, the cellulosic molecule degree of polymerization 875.
Filtrate one prepares the products such as lignin, hemicellulose in step A, and for waste water in addition to the reuse of part, remaining prepares liquid
Fertilizer.
The preparation of B viscose rayons
B1）It uses mass fraction to impregnate the fiber pulp finished product for 11% potassium hydroxide solution, cellulose is made to be converted into
Alkali cellulose.
The mass fraction that the step generally uses in replacing usual viscose rayon to prepare with the potassium hydroxide of mass fraction 11%
18% sodium hydroxide, the fiber pulp degree of purity that on the one hand prepared by the present invention are very high, it is not necessary to use higher concentration lye de- again
Except impurity such as hemicelluloses remaining in fiber pulp, the presence of another aspect sodium ion can significantly affect carbon fiber in subsequent technique
The tensile strength of dimension and the difficulty for increasing wastewater treatment；The waste water containing potassium ion does not need water process but through adjusting in the present invention
The preparation of liquid fertilizer is used directly for after matching.
B2）It is separated by solid-liquid separation, obtains blocky alkali cellulose, crush the alkali cellulose that the bulk alkali cellulose obtains loose state；
B3）The alkali cellulose of loose state comes into full contact with oxygen, carries out burin-in process；
B4）The carbon disulfide of alpha-cellulose butt quality 32% in fiber pulp is added, the alkali cellulose after aging is carried out
Yellow is handled, and obtains cellulose xanthate；
B5）The potassium hydroxide of mass fraction 8%, cellulose xanthate hydrolysis, esterification are added into the alkali cellulose after yellow
Degree reduces；Filtering, to remove bubble and impurity, obtains viscose glue；
B6）The viscose glue forms thread by spinneret orifice and enters the coagulating bath containing acid, and alkali is neutralized, and thread is frozen into silk
Item, cellulose xanthate disintegrating and regeneration are cellulose hydrate, are configured to cellulose strand；In coagulating bath wherein containing acid, acid is
The sulfuric acid of mass fraction 3%.
B7）The cellulose strand use after washing mass fraction for 3% potassium hydroxide solution desulfurization, after dry, i.e.,
Obtain viscose final product.After testing, the viscose rayon line density that prepared by reed is 3.82dtex, dry break strength is
4.27cN/dtex, water free breaking elongation rate are 15.9%.
Viscose rayon is prepared by reed fiber pulp using wet spinning technology.Viscose rayon is prepared by fiber pulp
Production, whole process without use sodium salt, to next step prepare high intensity carbon fiber and Waste water reuse meaning weight
Greatly.
The preparation of C viscose-based carbon fibers
The viscose final product pre-oxidizes 2 hours in 230 DEG C of pre-oxidation furnaces, then low in 650 DEG C of retorts respectively
Temperature charing 3 minutes handles 15 seconds to get viscous in 1800 DEG C of retort high temperature carbonizations 8 minutes, in 3100 DEG C of graphitizing furnace high temperatures
Matrix carbon fiber.
Charing and graphitizing process carry out in an inert atmosphere, and feed inlet, discharge port are sealed using nitrogen.
After testing, the performance indicator of viscose-based carbon fiber obtained by the present embodiment is as follows：
Fibre diameter（μm） 6.6
Tensile strength（GPa） 3.5
Elasticity modulus（GPa） 87.6
Fiber total recovery（%） 40.9
Fibre density（g/ m3） 1.8
Phosphorus content（%） 95.3.
Embodiment 3
A method of carbon fiber, including step are prepared using crop material：
A prepares fiber pulp
A1）It is placed in steam explosion separator after bagasse impurity elimination, cleaning, the water of 12 times of bagasse quality is added, hydrogen-oxygen is added
It is 12% to change potassium to lye mass concentration, is passed through into steam explosion separator after water vapour to temperature rises to 80 DEG C, stops water flowing and steam
Vapour；It is passed through inert gas into steam explosion separator, air in steam explosion separator is emptied, is sealed；Then intermittent to steam explosion point
To maintain in steam explosion separator temperature it is 100 DEG C, pressure 1.3MPa from being passed through water vapour and inert gas in device, heat preservation
Pressurize is spurted after 90 minutes.
In the step steam explosion separation process, the components such as lignin, hemicellulose, ash content, resinae dissolve in lye；It adopts
With relatively low boiling temperature（It is passed through hot steam realization）Avoid decomposition reaction, dehydration of the cellulosic molecule in digestion process（It is burnt
Change）Reaction, peeling reaction etc., the higher pressure inside the tank of use（It is realized by being passed through inert gas）It ensure that lye to raw cell
Effective infiltration between wall, in addition, using inert environments（It is passed through inert gas realization）Avoid the oxidation of cellulosic molecule group
Reaction, acetyl esterification reaction etc., to ensure the integrality of cellulose.
A2）It slurry will be spurted will move in colloid mill and grind 15 minutes, and after grinding, cross 40 mesh sieve, screen out in slurries
Small short fibers.The step Mechanical Method continues to crack the part chemical bond between macromolecular, contributes to the enzymolysis of next step.
A3）It is separated by solid-liquid separation, obtains filter residue one and filtrate one；Filter residue one is the slurry containing cellulose, and filtrate one is half fiber
Tie up the inorganic salts such as element, lignin, ash content be siliceous.
A4）Filter residue one uses mass fraction to be washed 3 times for 8% dilute hot alkaline solution, is separated by solid-liquid separation, obtains filter residue two and filtrate
Two.The hemicellulose, lignin, ash that the step dissolves cellulose surface remaining using thermokalite grade.
A5）Filter residue two is placed in enzymatic vessel, the water of 27 times of quality of filter residue is added, and compound protease is added（600U/
Kilogram butt filter residue two）, digest 20 minutes；Normal temperature type alpha-amylase is then added（500U/ kilograms of butt filter residue two）, enzymolysis 20
Minute；It then passes to steam and is warming up to 70 DEG C, keep the temperature 6 minutes, the activity of inactivator.
Wherein, compound protease is by having the alkali protease of endopeptidase activity and having the active Proteinase K of peptide ending enzyme
It forms, the alkali protease for having endopeptidase activity in compound protease is with the ratio for having the active Proteinase K of peptide ending enzyme
1: 3；The compound protease can effectively hydrolyzing protein at normal temperatures.
Normal temperature type alpha-amylase is by microwave induced gained variation bacillus licheniformis secretion gained alpha-amylase；It is microwave induced
Gained variation bacillus licheniformis obtaining step be specially：The culture solution of bacillus licheniformis is placed in microwave generator, if
It is 900W, pulse frequency 2300MHz, microwave treatment 20s to set microwave power, cooling 20s, reciprocal 30 times according to this；At microwave
Culture solution after reason is coated on solid medium, is cultivated 1-2 days under the conditions of 30 DEG C, by screening four plants in the bacterium colony that survives
The dissociant of the high bacillus licheniformis of alpha-amylase activity under room temperature.Select the highest lichens of alpha-amylase activity under room temperature
The dissociant of bacillus expands culture, to obtain normal temperature type alpha-amylase；Normal temperature type alpha-amylase is in 22-35 DEG C of temperature
Under expeditiously hydrolyze starch, it is not necessary to as the thermal-stable α-amylase mostly used greatly at present needs high temperature（80-90℃）Condition, because
And reduce energy consumption and also reduce requirement to equipment, while greatly reducing the generation of side reaction.
It herein can be mildly by protein, Starch Hydrolysis at the peptides of small molecule, amino acid, maltose, Portugal with enzyme process
Grape sugar etc. enters in filtrate, to success deproteination matter and starch；To ensure the purity of cellulose.
A6）Mixture in enzymatic vessel is placed in bleaching tank, the mass fraction that hydrogen peroxide to hydrogen peroxide is added is
0.25%, keep the temperature 80 minutes at 60 DEG C.The step is not intended to bleach, but is dissolved under alkaline condition with hydrogen peroxide residual
There are the hemicellulose on fiber pulp surface and lignin, and fiber pulp is further purified.
A7）Hydrogen peroxide is continuously added, until the mass fraction of hydrogen peroxide is 3.5%, carries out bleaching.
A8）It is separated by solid-liquid separation, obtains filter residue three and filtrate three；Filter residue three is washed 3 times by 95% ethyl alcohol, is finally washed, is obtained filter residue
Four.The recyclable recycling of ethyl alcohol in this step.
Filter residue three is with cellulose fiber pulp crude product as main component.Ethyl alcohol removing remains in fiber pulp surface
Lignin and dissolution lipoid material.
A9）Filter residue four is spray-dried（Temperature is less than 120 DEG C）, slight crush to get fiber pulp finished product.After testing,
Fiber pulp alpha-cellulose content prepared by bagasse is 97.9%, the cellulosic molecule degree of polymerization 1084.
Filtrate one prepares the products such as lignin, hemicellulose in step A, and for waste water in addition to the reuse of part, remaining prepares liquid
Fertilizer.
The preparation of B viscose rayons
B1）It uses mass fraction to impregnate the fiber pulp finished product for 11.5% potassium hydroxide solution, cellulose is made to convert
For alkali cellulose.
The quality point that the step generally uses in replacing usual viscose rayon to prepare with the potassium hydroxide of mass fraction 11.5%
The sodium hydroxide of number 18%, the fiber pulp degree of purity that on the one hand prepared by the present invention are very high, it is not necessary to use higher concentration lye again
Impurity, the presence of another aspect sodium ion such as remaining hemicellulose can significantly affect carbon in subsequent technique in removing fiber pulp
The tensile strength of fiber and the difficulty for increasing wastewater treatment；The waste water containing potassium ion does not need water process but passes through in the present invention
The preparation of liquid fertilizer is used directly for after allotment.
B2）It is separated by solid-liquid separation, obtains blocky alkali cellulose, crush the alkali cellulose that the bulk alkali cellulose obtains loose state；
B3）The alkali cellulose of loose state comes into full contact with oxygen, carries out burin-in process；
B4）33% carbon disulfide of alpha-cellulose butt quality in fiber pulp is added, the alkali cellulose after aging is carried out yellow
Change is handled, and obtains cellulose xanthate；
B5）The potassium hydroxide of mass fraction 4%, cellulose xanthate hydrolysis, esterification are added into the alkali cellulose after yellow
Degree reduces；Filtering, to remove bubble and impurity, obtains viscose glue；
B6）The viscose glue forms thread by spinneret orifice and enters the coagulating bath containing acid, and alkali is neutralized, and thread is frozen into silk
Item, cellulose xanthate disintegrating and regeneration are cellulose hydrate, are configured to cellulose strand；In coagulating bath wherein containing acid, acid is
The sulfuric acid of mass fraction 7%.
B7）The cellulose strand use after washing mass fraction for 7% potassium hydroxide solution desulfurization, after dry, i.e.,
Obtain viscose final product.After testing, viscose rayon line density is 4.96dtex made from bagasse, dry break strength is
5.11cN/dtex, water free breaking elongation rate are 15.7%.
Viscose rayon is prepared by bagasse fibre pulp using wet spinning technology.Viscose glue fibre is prepared by fiber pulp
The production of dimension, whole process prepare next step on the carbon fiber and Waste water reuse meaning of high intensity without using sodium salt
It is great.
The preparation of C viscose-based carbon fibers
The viscose final product pre-oxidizes 1.5 hours in 260 DEG C of pre-oxidation furnaces, then respectively in 600 DEG C of retorts
Low-temperature carbonization 4 minutes, 2400 DEG C of retort high temperature carbonizations 3 minutes, 3200 DEG C of graphitizing furnace high temperatures handle 10 seconds to get
Viscose-based carbon fiber.
Charing and graphitizing process carry out in an inert atmosphere, and feed inlet, discharge port are sealed using nitrogen.
After testing, the performance indicator of viscose-based carbon fiber obtained by the present embodiment is as follows：
Fibre diameter（μm） 7.5
Tensile strength（GPa） 3.7
Elasticity modulus（GPa） 82.2
Fiber total recovery（%） 43.2
Fibre density（g/ m3） 1.9
Phosphorus content（%） 96.
Claims (9)
1. a kind of method preparing carbon fiber using crop material, which is characterized in that including step：
A prepares fiber pulp
A1）Stalk through impurity elimination, dedusting, rub silk, segment, cleaning after in merging steam explosion separator, 1-20 times of stalk quality is added
Water, it is 5-25% that alkali to lye mass concentration, which is added, is passed through after water vapour rises to 60-95 DEG C to temperature, stops into steam explosion separator
Only water flowing steam；It is passed through inert gas into steam explosion separator, air in steam explosion separator is emptied, is sealed；Then intermittent
Water vapour and inert gas are passed through into steam explosion separator, temperature is 80-110 DEG C, pressure is to maintain in steam explosion separator
0.5-2MPa, heat-insulation pressure keeping spurt after 20-180 minutes；
A2）To spurt slurry move to grinding mill in grind, after grinding, cross 30-50 mesh sieve, screen out the short and small fibre in slurries
Dimension；
A3）It is separated by solid-liquid separation, obtains filter residue one and filtrate one；
A4）Filter residue one is washed several times using dilute hot alkaline solution, is separated by solid-liquid separation, is obtained filter residue two and filtrate two；Step A4）In, institute
It is potassium hydroxide solution, sodium hydroxide solution or the calcium hydroxide solution that mass fraction is 1%-10% to state hot alkaline solution；
A5）Filter residue two is placed in enzymatic vessel, the water of the 1-10 times of quality of filter residue two is added, and compound protease is added, digests 10-
80 minutes；Normal temperature type alpha-amylase is then added, digests 10-80 minutes；It then passes to steam and is warming up to 60-70 DEG C, keep the temperature 2-
20 minutes, the activity of inactivator；The compound protease is by having the alkali protease of endopeptidase activity and having peptide ending enzyme work
Property Proteinase K composition；The normal temperature type alpha-amylase is by microwave induced gained variation bacillus licheniformis secretion gained α-shallow lake
The preference temperature of powder enzyme, the normal temperature type alpha-amylase is 22-35 DEG C；
A6）Mixture in enzymatic vessel is placed in bleaching tank, the mass fraction that hydrogen peroxide is added to hydrogen peroxide is 0.1%-
0.5%, keep the temperature 10-120 minutes at 50-80 DEG C；
A7）Hydrogen peroxide is continuously added, until the mass fraction of hydrogen peroxide is 2%-5%, carries out bleaching；
A8）It is separated by solid-liquid separation, obtains filter residue three and filtrate three；Filter residue three obtains filter residue four after alcohol is washed and is washed；
A9）Filter residue four is through drying, crushing to get fiber pulp finished product；
The preparation of B viscose rayons
B1）It uses mass fraction to impregnate the fiber pulp finished product for the potassium hydroxide solution of 10%-15%, cellulose is made to be converted into
Alkali cellulose；
B2）It is separated by solid-liquid separation, obtains blocky alkali cellulose, crush the alkali cellulose that the bulk alkali cellulose obtains loose state；
B3）The alkali cellulose of loose state comes into full contact with oxygen, carries out burin-in process；
B4）Carbon disulfide is added, the alkali cellulose after aging carries out yellow processing, obtains cellulose xanthate；
B5）The potassium hydroxide of mass fraction 3%-20%, cellulose xanthate hydrolysis, esterification are added into the alkali cellulose after yellow
Degree reduces；Filtering, to remove bubble and impurity, obtains viscose glue；
B6）The viscose glue forms thread by spinneret orifice and enters the coagulating bath containing acid, and alkali is neutralized, and thread is frozen into strand, fine
The plain xanthate acid disintegrating and regeneration of dimension is cellulose hydrate, is configured to cellulose strand；
B7）The cellulose strand is through washing, caustic wash desulfuration, to get viscose final product after drying；
The preparation of C viscose-based carbon fibers
The viscose final product pre-oxidizes 0.5-3 hours in 200-300 DEG C of pre-oxidation furnace, then respectively at 200-800 DEG C
Retort low-temperature carbonization 1-10 minutes, in 1000-3000 DEG C of retort high temperature carbonization 0.2-10 minutes, in 2000-4000 DEG C of stone
Inkization stove high temperature handles 5-50 seconds to get viscose-based carbon fiber.
2. the method for preparing carbon fiber using crop material as described in claim 1, it is characterised in that：Step A3）Gained filtrate
One is used to prepare lignin and hemicellulose.
3. the method for preparing carbon fiber using crop material as described in claim 1, it is characterised in that：Step A5）In, it is described micro-
Wave induction gained variation bacillus licheniformis obtaining step be specially：The culture solution of bacillus licheniformis is placed in microwave
Device, setting microwave power are 850-950W, pulse frequency 2300MHz, microwave treatment 20s, cool down 20s, according to this reciprocal 25-35
It is secondary；Culture solution after microwave treatment is coated on solid medium, is cultivated 1-2 days under the conditions of 30 DEG C, by the bacterium survived
Fall the dissociant of the high bacillus licheniformis of alpha-amylase activity under four plants of room temperature of screening.
4. the method for preparing carbon fiber using crop material as claimed in claim 3, it is characterised in that：Select alphalise starch under room temperature
The dissociant of the highest bacillus licheniformis of enzymatic activity expands culture, to obtain the normal temperature type alpha-amylase.
5. the method for preparing carbon fiber using crop material as described in claim 1 or 3, it is characterised in that：Step A5）In, institute
It is 1 to state the alkali protease for having endopeptidase activity in compound protease and the ratio for having the active Proteinase K of peptide ending enzyme:1-
3；The addition of the compound protease meets every kilogram of two 400-800U of butt filter residue, the addition of the normal temperature type alpha-amylase
Amount meets every kilogram of two 300-700U of butt filter residue.
6. the method for preparing carbon fiber using crop material as described in claim 1, it is characterised in that：Step A8）In, using body
The ethyl alcohol alcohol that fraction is 95% is washed several times, is finally washed.
7. the method for preparing carbon fiber using crop material as described in claim 1, it is characterised in that：Step B4）Middle curing
The addition of carbon is the 25%-50% of alpha-cellulose butt quality in fiber pulp.
8. the method for using crop material to prepare carbon fiber as described in claim 1 or 7, it is characterised in that：Step B6）In, contain
In the coagulating bath of acid, acid is the sulfuric acid that mass fraction is 1%-10%.
9. the method for using crop material to prepare carbon fiber as described in claim 1 or 7, it is characterised in that：Step B7）In, institute
State the potassium hydroxide solution desulfurization that caustic wash desulfuration uses mass fraction as 1%-10%.
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| CN107299419A (en) * | 2017-08-28 | 2017-10-27 | 德阳力久云智知识产权运营有限公司 | A kind of preparation method of high strength starch base carbon fibre |
| RU2671709C1 (en) * | 2017-11-24 | 2018-11-06 | Акционерное общество "Научно-исследовательский институт конструкционных материалов на основе графита "НИИграфит" | Method of obtaining carbon fibrous materials from hydrate cellulose fibers |
| FR3083547B1 (en) * | 2018-07-09 | 2021-07-30 | Inst De Rech Tech Jules Verne | CARBON FIBER AND PROCESS FOR MANUFACTURING SUCH A CARBON FIBER FROM CELLULOSE |
| CN109608177A (en) * | 2018-11-20 | 2019-04-12 | 武汉纺织大学 | It is integrally formed the preparation method of reed straw base carbon fibre intelligent electric-heating ceramic wafer |
| CN109957860B (en) * | 2019-04-01 | 2021-10-22 | 梁继选 | Preparation method of viscose high-temperature graphite carbon fiber |
| KR102191650B1 (en) * | 2019-06-14 | 2020-12-28 | 전주대학교 산학협력단 | A method of manufacturing active carbon paper for super-capacitor electrode, the active carbon paper and the super-capacitor electrode thereof |
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