CN108611703A - A method of preparing carbon fiber using the lignin of extraction with aqueous solution - Google Patents
A method of preparing carbon fiber using the lignin of extraction with aqueous solution Download PDFInfo
- Publication number
- CN108611703A CN108611703A CN201810431925.XA CN201810431925A CN108611703A CN 108611703 A CN108611703 A CN 108611703A CN 201810431925 A CN201810431925 A CN 201810431925A CN 108611703 A CN108611703 A CN 108611703A
- Authority
- CN
- China
- Prior art keywords
- lignin
- carbon fiber
- aqueous solution
- extraction
- control
- 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
- 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
- D01F9/17—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 from lignin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses a kind of methods that the lignin using extraction with aqueous solution prepares carbon fiber, this method is dissolved in the weakly acidic aqueous solution of the characteristic in acidic aqueous solution according to most inorganic salts first and extracts lignin, the lignin extracted by weakly acidic aqueous solution is modified using medicament again, then melt drawing is carried out again, and the precursor after wire drawing is subjected to pre-oxidation treatment, its processing mode can be that directly preheating either directly progress ultraviolet light is preheated again after adding coupling agent, then the intermediate product of pre-oxidation treatment is carbonized, get product carbon fiber wire.The present invention can greatly shorten the time needed for stabilizing, and to increase substantially production efficiency, and then reduce production cost.
Description
Technical field
It is specially a kind of to utilize the wooden of extraction with aqueous solution the present invention relates to the carbon fibre material field in new material technology
The method that element prepares carbon fiber.
Background technology
Lignin is a kind of reproducible biological raw material, is widely present in the plant of nature, it is total to account for plant
The 25~35% of weight.In modern industry, for lignin primarily as the byproduct of paper industry, raw material are extensive, produce
Amount is big, and annual yield is more than 50,000,000 tons, but its practical efficiency is extremely low, other than a minimum part is utilized,
The overwhelming majority is all taken as fuel and is burned, and this lignose fuel efficiency of combustion is low, and combustion process can release
Great amount of carbon dioxide, carbon monoxide and some other burning pollutant can cause environment larger pressure.
And still further aspect, lignin is due to its price and its cheaply, and its phosphorus content is high, is also considered as carbon fiber
The desirable material of preparation, the main preparation process that common lignin prepares carbon fiber include:(1) Lignin pufification;(2) wooden
Quality raw material proportioning can such as add plasticizer, organic solvent and other chemical reagent etc.;(3) formation of precursor;(4) precursor
Stabilisation;(5) high temperature cabonization.And in the prior art, Ye You research teams carry according to different raw material (lignin source)
The different methods of purification gone out, but result of study is extremely disperseed, and without important breakthrough, master in terms of crucial cost control
Concentrate on two aspects:
Although being on the one hand that lignin yield is cheap greatly, needed first to it if preparing carbon fiber using it
Purification operations are carried out, and lignin structure is complicated, and the performance difference of different lignin is big, the purification for lignin is existing
Most of research organic solvent extraction lignin (because inorganic salts do not dissolve in organic solvent), refining effect is good, but at
This possibility is relatively high, including solvent cost (solvent most can recycle), removes solvent cost (heating evaporation), and may
Environmental costs.In addition, since organic solvent cannot dissolve the lignin macromolecule component of macromolecule, the yield of purification is general
Less than 80%, the further up of the cost of raw material is caused.
And on the other hand be exactly lignin carbon fibers the thermostabilization i.e. required time of heated oxide it is very long, generally up to
Ten a few to tens of hours, and solution of the existing technology to such problem, are all by different lignin source (such as corks
The stabilisation time of lignin carbon fibers is relatively short), different lignin component (different organic solvent extractions) is extracted, and
Raw material lignin formula (such as mixing different lignin) finds the carbon fiber stabilization procedures of relative short time, still
These methods are unable to tackle the problem at its root (total stabilisation time is still very long), and its is of high cost, complicated for operation,
Possibility without actual production operation.
For these reasons, the prior art is not all fully solved adding for lignin carbon fibers caused by above-mentioned two problems
The excessively high problem of work inefficiency, production cost, thus the influence to its industrialization production is smaller.
Invention content
Technical problem solved by the invention is to provide a kind of preparing carbon fiber using the lignin of extraction with aqueous solution
Method, to solve the defects of above-mentioned technical background.
Technical problem solved by the invention is realized using following technical scheme:
A method of carbon fiber being prepared using the lignin of extraction with aqueous solution, specifically includes following operating procedure:
1) weak acid purifying lignin:Lignin is added in the slightly acidic water solution that pH is 2~6 first, controls faintly acid
Aqueous solution and lignin weight ratio in aqueous solution are 4:1~20:Between 1, then solution temperature is controlled in room temperature~60 DEG C
Between, stir evenly, after the completion of stirring with clear water clean, and with this complete one purification cycle, to same lignin material into
2~5 purification cycles of row, then first dry the lignin after purification, then be dried in vacuo water content < 2%.
In aforesaid operations step, when being dried to the lignin after purification and be dried in vacuo operation, environment temperature is controlled
Degree is less than 80 DEG C.
2) low cost stabilizes operation:Lignin and plasticizer, coupling agent by purification in step 1) and after drying mix,
The mass ratio of lignin and plasticizer is controlled 95:5 to 50:Between 50, control coupling agent be added quality be lignin and
0.1% to the 10% of plasticiser mixture gross mass, and to said mixture is carried out melting operation, pulled down in melting condition
Then silk carries out heating pre-oxidation to the precursor after wire-drawing shape and stablizes processing, the temperature control for controlling pre-oxidation is arrived 250
Between 350 DEG C, 1.2~6h is handled, then the carbon fiber after pre-oxidation is carbonized, control carburizing temperature is 800 to 1400
DEG C until material carbonization to get to finished product carbon fiber.
In aforesaid operations step, the plasticizer is organic solvent, polymer or their mixing of 100 DEG C of boiling point >
Object, it is preferred to use PEG.
In aforesaid operations step, the coupling agent is the low-molecular weight amines compound of carbon atom quantity < 6, sub-
Mixture under the conditions of amine compounds or their arbitrary proportion, polymer, copolymer.
In aforesaid operations step, the wire-drawing temperature control of melt drawing operation is at 80~200 DEG C, wire drawing mode
One kind in silk is blown for melt drawing, melting centrifugal drying silk and melting.
In the above-mentioned methods, pass through the side of addition plasticizer and coupling agent in the mixture of lignin and plasticizer
Formula coordinates specific technique to carry out stabilisation operation, and it is to reduce the melting temperature of mixture, make coupling that plasticizer, which is added,
Agent is stablized relatively under carbon fiber wire-drawing temperature, but during heating pre-oxidation (stabilizing), coupling agent can promote
The formation of high molecular weight polymers is accelerated in polymerization between lignin molecule chain, improves the glass transition temperature of carbon fibre precursor, from
And reduce and stabilize the required time, it is cost-effective.
In addition, in the present invention, as parallel technical solution, can also pass through ultraviolet lighting in the case where being not added with coupling agent
It injects row low cost and stabilizes operation, concrete operation step is as follows:
Lignin and plasticizer first by purification in step 1) and after drying mix, and control the matter of lignin and plasticizer
Amount ratio is 95:5 to 50:Between 50, and by said mixture wire drawing under melting condition, then to the precursor after wire-drawing shape
Be collected, and in air use ultra violet lamp, control ultraviolet lamp power be 1~20KW, 5~120min of light application time, most
Heating pre-oxidation is carried out to the precursor after wire-drawing shape afterwards and stablizes processing, controls the temperature of pre-oxidation between 250 to 350 DEG C,
1.2~6h is handled, then the carbon fiber after pre-oxidation is carbonized, control carburizing temperature is 800 to 1400 DEG C until material is complete
Full carbonization is to get to finished product carbon fiber.
In aforesaid operations step, the plasticizer is organic solvent, polymer or their mixing of 100 DEG C of boiling point >
Object.
In aforesaid operations step, the wire-drawing temperature control of melt drawing operation is at 80~200 DEG C, wire drawing mode
One kind in silk is blown for melt drawing, melting centrifugal drying silk and melting.
In aforesaid operations step, ultra violet lamp processing can be in batches can also be continuous processing mistake
Journey.
Lignin carbon fibers precursor can be carried out ultraviolet lighting by the parallel technical solution in the case where being not added with coupling agent
It penetrates.Using the ozone of strong ultraviolet photogenerated as strong oxidizer, promote carbon fibre precursor surface in the case where being not required to heating
Oxidation, to reach the stabilization effect similar with above-mentioned heat pre-treatment, then carries out heat again by pretreated precursor again
It stabilizes, and at this point, since filament face is oxidized, so the time of thermostabilization processing can be greatly lowered, also can
Effectively reduce production cost.
In the present invention, it is cork, hardwood and herbaceous plant as the lignin source of raw material, preferably straw, straw,
Reed, maize straw, bamboo.
In the present invention, it is single kind lignin as the lignin of raw material.
In the present invention, the mixing as the arbitrary proportion that the lignin of raw material is two or more lignin
Object.
Advantageous effect:The method that lignin provided by the invention using extraction with aqueous solution prepares carbon fiber, using cork,
The lignin extracted in hardwood and herbaceous plant is purified and is stabilized operation as raw material, to it, and purification mode can have
The lignin component of the middle high molecular weight of 99.5% or more DNA purity from primary lignin is imitated, and can effectively reduce and be processed into
This, improves yield;And stabilize operation can be operated by two kinds of distinct methods, can greatly shorten stabilize needed for when
Between, to increase substantially production efficiency, and then reduce production cost.
Description of the drawings
Fig. 1 is the technique frame diagram of presently preferred embodiments of the present invention one.
Fig. 2 is the technique frame diagram of presently preferred embodiments of the present invention two.
Specific implementation mode
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, tie below
Specific embodiment and its diagram are closed, the present invention is further explained.
Embodiment one:
Referring to a kind of method preparing carbon fiber by the lignin of extraction with aqueous solution of Fig. 1 technique frame diagram in the way of
Carbon fiber processing is carried out, in the present embodiment, using single reed as raw material, and using lignin extraction technique to reed
Lignin in reed extracts, and the lignin of extraction is added in the slightly acidic water solution that pH value is 6, and control faintly acid is water-soluble
Aqueous solution and lignin weight ratio in liquid are 16:1, mixture solution is subjected to acidolysis reaction at room temperature, in acidolysis reaction
It stirs evenly, then will stir evenly in the process, cleaned with clear water after reactant stirs evenly, and a purification is completed with this
Cycle carries out 3 purification cycles to same lignin material, then first dries the lignin after purification, then be dried in vacuo
Water content < 2%, it is spare.
The lignin purified in above-mentioned steps and after drying is mixed with plasticizer, coupling agent, controls lignin and plasticising
The mass ratio of agent is 80:20, the quality that control coupling agent is added is the 4% of lignin and plasticiser mixture gross mass,
In, plasticizer uses PEG, and coupling agent uses dimethylamine.Said mixture is melted, wire drawing is controlled under melting condition
120 DEG C of temperature carries out melting centrifugal drying silk, is then heated to 300 DEG C to the precursor after wire-drawing shape and carries out pre-oxidizing stable place
Then carbon fiber after pre-oxidation treatment is carbonized by reason, processing time 4h, control carburizing temperature is 1200 DEG C until material
Expect carbonization to get to finished product carbon fiber.
In the above-mentioned methods, pass through the side of addition plasticizer and coupling agent in the mixture of lignin and plasticizer
Formula coordinates specific technique to carry out stabilisation operation, and it is to reduce the melting temperature of mixture, make coupling that plasticizer, which is added,
Agent is stablized relatively under carbon fiber wire-drawing temperature, but during heating pre-oxidation (stabilizing), coupling agent can promote
The formation of high molecular weight polymers is accelerated in polymerization between lignin molecule chain, improves the glass transition temperature of carbon fibre precursor, from
And reduce and stabilize the required time, the method that the lignin using extraction with aqueous solution of the present embodiment prepares carbon fiber utilizes
It is more environmentally-friendly that regenerated resources as raw material, relative to traditional technology using graphite ore prepare carbon fiber as raw material, while cost
Being equivalent to traditional carbon fiber (PAN carbon fibers and asphalt-based carbon fiber) manufacturing cost reduces 20~50%.Thus more
It is economic and environment-friendly.
Embodiment two:
Referring to a kind of method preparing carbon fiber by the lignin of extraction with aqueous solution of Fig. 2 technique frame diagram in the way of
Carry out carbon fiber processing, in the present embodiment, using straw, reed, maize straw 1:1:1 mixture as raw material,
And the lignin in reed is extracted using lignin extraction technique, it is by the lignin of extraction addition pH value first when extraction
In 4 slightly acidic water solution, the aqueous solution and lignin weight ratio that control in slightly acidic water solution are 10:1, by mixture solution
Acidolysis reaction is carried out at room temperature, is stirred evenly during acidolysis reaction, then will be stirred evenly, and waits for that reactant stirs evenly
It is cleaned afterwards with clear water, and a purification cycle is completed with this, 5 purification cycles are carried out to same lignin material, then will be carried
Lignin after pure is first dried, then is dried in vacuo water content < 2%, spare.
The lignin purified in above-mentioned steps and after drying is mixed with plasticizer, controls the quality of lignin and plasticizer
Ratio is 70:30, and plasticizer selects PEG, and said mixture is melted, and wire-drawing temperature 100 is controlled under melting condition
DEG C carry out melt drawing, then the precursor after wire-drawing shape is collected, the precursor after collection is shakeout in air, with purple
Outer lamp carries out Continuous irradiation processing, and control ultraviolet lamp power is 16KW, light application time 90min, then by the original after wire-drawing shape
Silk carries out heating pre-oxidation and stablizes processing, controls the temperature of pre-oxidation between 320 DEG C, handles 2h, then by the carbon after pre-oxidation
Fiber is carbonized, and control carburizing temperature is 1100 DEG C until material carbonization is to get to finished product carbon fiber.
Lignin carbon fibers precursor is carried out ultraviolet light by the processing method of embodiment two in the case where being not added with coupling agent
Irradiation.Using the ozone of strong ultraviolet photogenerated as strong oxidizer, promote carbon fibre precursor surface in the case where being not required to heating
Oxidation pretreated precursor is subjected to thermostabilization again to reach the stabilization effect similar with above-mentioned heat pre-treatment
Change, and at this point, since filament face is oxidized, so the time of thermostabilization processing can be greatly lowered, it also can be effective
Production cost is reduced, the time needed for stabilisation in the basic production with traditional carbon fibres is similar, and due to being carried using aqueous solution
The lignin taken prepares the method for carbon fiber using regenerated resources as raw material, relative to traditional technology using graphite ore as former
Material prepares that carbon fiber is more environmentally-friendly, and manufacturing cost also reduces 20~50%.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. a kind of method that lignin using extraction with aqueous solution prepares carbon fiber, which is characterized in that specifically include following operation
Step:
1) weak acid purifying lignin:Lignin is added in the slightly acidic water solution that pH is 2~6 first, control faintly acid is water-soluble
Aqueous solution and lignin weight ratio in liquid are 4:1~20:Between 1, then by solution temperature control between room temperature~60 DEG C,
It stirs evenly, is cleaned with clear water after the completion of stirring, and a purification cycle is completed with this, 2~5 are carried out to same lignin material
Secondary purification cycle, then first dries the lignin after purification, then be dried in vacuo water content < 2%;
2) low cost stabilizes operation:Lignin and plasticizer, coupling agent by purification in step 1) and after drying mix, control
The mass ratio of lignin and plasticizer is 95:5 to 50:Between 50, the quality that control coupling agent is added is lignin and plasticising
0.1% to the 10% of agent composition gross mass, and to said mixture is carried out melting operation, the wire drawing under melting condition, so
Afterwards to the precursor after wire-drawing shape carry out heating pre-oxidation stablize processing, control pre-oxidation temperature control 250 to 350 DEG C it
Between, 1.2~6h is handled, then the carbon fiber after pre-oxidation is carbonized, control carburizing temperature is 800 to 1400 DEG C until material
Expect carbonization to get to finished product carbon fiber.
2. a kind of method that lignin using extraction with aqueous solution prepares carbon fiber, which is characterized in that specifically include following operation
Step:
1) weak acid purifying lignin:Lignin is added in the slightly acidic water solution that pH is 2~6 first, control faintly acid is water-soluble
Aqueous solution and lignin weight ratio in liquid are 4:1~20:Between 1, then by solution temperature control between room temperature~60 DEG C,
It stirs evenly, is cleaned with clear water after the completion of stirring, and a purification cycle is completed with this, 2~5 are carried out to same lignin material
Secondary purification cycle, then first dries the lignin after purification, then be dried in vacuo water content < 2%;
2) low cost stabilizes operation:Lignin and plasticizer by purification in step 1) and after drying mix, and control lignin
Mass ratio with plasticizer is 95:5 to 50:Between 50, and by said mixture wire drawing under melting condition, then to wire drawing
Precursor after molding is collected, and uses ultra violet lamp in air, and control ultraviolet lamp power is 1~20KW, light application time 5
~120min finally carries out heating pre-oxidation to the precursor after wire-drawing shape and stablizes processing, and the temperature for controlling pre-oxidation is arrived 250
Between 350 DEG C, 1.2~6h is handled, then the carbon fiber after pre-oxidation is carbonized, control carburizing temperature is 800 to 1400 DEG C
Until material carbonization is to get to finished product carbon fiber.
3. special according to the method that any lignin using extraction with aqueous solution prepares carbon fiber in claims 1 or 2
Sign is, when being dried to the lignin after purification in the step 1) and be dried in vacuo operation, control environment temperature is less than
80℃。
4. special according to the method that any lignin using extraction with aqueous solution prepares carbon fiber in claims 1 or 2
Sign is that the plasticizer is organic solvent, polymer or their mixture of 100 DEG C of boiling point >.
5. the method that the lignin according to claim 1 using extraction with aqueous solution prepares carbon fiber, which is characterized in that institute
State the low-molecular weight amines compound that coupling agent is carbon atom quantity < 6, group with imine moiety or their arbitrary proportion
Under the conditions of mixture, polymer, copolymer.
6. special according to the method that any lignin using extraction with aqueous solution prepares carbon fiber in claims 1 or 2
Sign is, the wire-drawing temperature control of the melt drawing operation at 80~200 DEG C, wire drawing mode is melt drawing, melt from
The heart gets rid of silk and melts the one kind blown in silk.
7. the method that the lignin according to claim 2 using extraction with aqueous solution prepares carbon fiber, which is characterized in that institute
Ultra violet lamp processing is stated as processing operation in batches.
8. the method that the lignin according to claim 2 using extraction with aqueous solution prepares carbon fiber, which is characterized in that institute
It is that continuous processing operates to state ultra violet lamp processing.
9. special according to the method that any lignin using extraction with aqueous solution prepares carbon fiber in claims 1 or 2
Sign is, the lignin as raw material is cork, single kind lignin in hardwood and herbaceous plant or two kinds or two kinds with
On lignin arbitrary proportion mixture.
10. according to the method that any lignin using extraction with aqueous solution prepares carbon fiber in claims 1 or 2,
It is characterized in that, the lignin source as raw material is straw, straw, reed, maize straw, the single kind lignin in bamboo
Or the mixture of the arbitrary proportion of two or more lignin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810431925.XA CN108611703A (en) | 2018-05-08 | 2018-05-08 | A method of preparing carbon fiber using the lignin of extraction with aqueous solution |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810431925.XA CN108611703A (en) | 2018-05-08 | 2018-05-08 | A method of preparing carbon fiber using the lignin of extraction with aqueous solution |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108611703A true CN108611703A (en) | 2018-10-02 |
Family
ID=63662342
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810431925.XA Pending CN108611703A (en) | 2018-05-08 | 2018-05-08 | A method of preparing carbon fiber using the lignin of extraction with aqueous solution |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108611703A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160230009A1 (en) * | 2012-10-09 | 2016-08-11 | Iowa State University Research Foundation, Inc. | Compositions including esterified lignin and poly (lactic acid) and carbon fibers produced therefrom |
CN106400206A (en) * | 2016-05-25 | 2017-02-15 | 南通慧源塑胶有限公司 | Preparation method for lignin-based carbon fiber |
CN106978653A (en) * | 2017-01-11 | 2017-07-25 | 嘉兴学院 | A kind of cellulose whiskers strengthen the preparation method of lignin-base carbon fiber |
-
2018
- 2018-05-08 CN CN201810431925.XA patent/CN108611703A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160230009A1 (en) * | 2012-10-09 | 2016-08-11 | Iowa State University Research Foundation, Inc. | Compositions including esterified lignin and poly (lactic acid) and carbon fibers produced therefrom |
CN106400206A (en) * | 2016-05-25 | 2017-02-15 | 南通慧源塑胶有限公司 | Preparation method for lignin-based carbon fiber |
CN106978653A (en) * | 2017-01-11 | 2017-07-25 | 嘉兴学院 | A kind of cellulose whiskers strengthen the preparation method of lignin-base carbon fiber |
Non-Patent Citations (2)
Title |
---|
刘兰燕等: "熔喷法制备木质素基碳纤维毡研究", 《人造纤维》 * |
朱美芳等: "《中国战略性新兴产业.新材料.高性能纤维》", 30 November 2017, 中国铁道出版社 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106977695B (en) | A kind of epoxyn and preparation method thereof of original position alkali lignin self-catalysis synthesis | |
CN104030269B (en) | The preparation method of red carbon quantum dot and application | |
CN106745246B (en) | A kind of method for preparing vanadic sulfate | |
CN106167702A (en) | A kind of preparation method of the azepine graphene quantum dot launching white fluorescent | |
CN109193063A (en) | A kind of waste lithium ion cell anode active material dissolving method | |
CN108929049A (en) | A method of Basalt fiber high-temperature resisting performance is promoted by surface modification | |
CN109679113A (en) | A kind of preparation method of low contamination lignosulfonates | |
CN105542761A (en) | Method for preparing fluorescence carbon dots taking rice bran as carbon source | |
CN102127369A (en) | Method for preparing disproportionated rosin | |
CN103993382A (en) | Method for improving pre-oxidation speed of polyacrylonitrile fiber through physical blending | |
CN103554247A (en) | Method for preparing collagen microfiber by use of ionic liquid mixing solvent | |
CN108611703A (en) | A method of preparing carbon fiber using the lignin of extraction with aqueous solution | |
CN103993366B (en) | Zirconium oxycarbonate-methanol system prepares the method for zirconia crystal fiber | |
CN105401261A (en) | Electrolytic oxidization method for preparing coal asphalt based carbon fiber | |
CN109056120A (en) | A method of inexpensive carbon fiber is prepared using lignin | |
CN111484012A (en) | Method for producing decolored active carbon by using phosphoric acid method | |
CN108285174B (en) | WO (WO)3-ZrO2Preparation method of photocatalytic sewage treatment membrane | |
CN103183837A (en) | Preparation method of heat resistant soy protein/graphene oxide composite membrane | |
CN106810412A (en) | A kind of production method of the method and Dispersant MF for improving sulfonating reaction efficiency | |
CN104177580B (en) | A kind of Graphene modified furan resin and preparation method thereof | |
CN107419359A (en) | Heat-resisting chemical fibre silk and preparation method thereof | |
JPH01306618A (en) | Preparation of lignin for spinning of carbon fiber | |
CN102627531A (en) | Method for producing acicular 2, 5-dimethylphenol by water melt crystallization | |
CN104592377B (en) | The extracting method of silk gum in a kind of silk cocoon | |
CN106317418A (en) | Method for preparing sodium ligninsulfonate from corncob acidolysis residue soda-boiling black liquid |
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: 20181002 |
|
WD01 | Invention patent application deemed withdrawn after publication |