CN105017791A - Lignin-based carbon fiber precursor, and preparation method and application thereof - Google Patents
Lignin-based carbon fiber precursor, and preparation method and application thereof Download PDFInfo
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- CN105017791A CN105017791A CN201510364997.3A CN201510364997A CN105017791A CN 105017791 A CN105017791 A CN 105017791A CN 201510364997 A CN201510364997 A CN 201510364997A CN 105017791 A CN105017791 A CN 105017791A
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Abstract
The invention relates to a lignin-based carbon fiber precursor and a preparation method thereof. The preparation method of the lignin-based carbon fiber precursor comprises the following steps: mixing wood powder with phenol, liquefying in the presence of an acidic catalyst, adding a surfactant and a stabilizer to the obtained liquefied wood, stirring to obtain a product, carrying out pumping filtration, and drying to obtain the lignin-based carbon fiber precursor. In the invention, liquefaction utilization of all components of wood effectively solves the negative influences of complex wood components on the performances of wood carbon fibers, and the carbon fiber precursor with high content of lignin is prepared; and influences of pores formed by ammonia gas generated in the spinning process due to addition of hexamethylene tetramine as a curing agent in the melt spinning process on the construction and the performances of the carbon fibers are avoided, and damages of harmful gases to human body and pollution of the harmful gases to environment in the production process due to use of a large amount of hydrochloric acid and formaldehyde in the curing process are reduced.
Description
Technical field
The present invention relates to Wood liquefied technology, specifically, relate to a kind of lignin-base carbon fiber precursor, its preparation method and application.
Background technology
Wood liquefied technology starts from nineteen twenty-five, under the existence of some organism as phenol or polyhydroxy-alcohol, it is the thermochemical process of the thick fluid of similar liquids by wood conversion, its product can be used for manufacturing the new polymer substance such as tackiness agent, urethane foam, fiber and carbon fiber, especially there is the polymer substance of biodegradability, greatly extend utilization and the recovery field of timber resources, there is more and more wide application prospect.
Containing a large amount of phenolate things and a small amount of unreacted phenol in Liquefaction Products in Phenol timber, as long as add formaldehyde or hexamethylenetetramine etc. just can generate lacquer resins (Novolak).Because phenolic aldehyde has certain stringiness in molten state, can be used for spinning phenolic fibre, the lacquer resins that therefore Wood Liquefaction Products in Phenol product generates may be used for preparing spinning solution completely.
Although obtain by Wood liquefied technology this technology of spinning solution prepared needed for carbon fiber to reach the utilization of expansion timber resources and the object in the field of recovery, but due in liquefaction technology, the existence of the large element (Mierocrystalline cellulose, hemicellulose, xylogen) of timber three causes spinning solution complicated component, unstable properties.In addition, in melt-spinning process, need in spinning solution to add hexamethylenetetramine as solidifying agent, otherwise Wood liquefied spinning liquid can not become silk, and the membership that adds of hexamethylenetetramine produces ammonia by product in melt-spinning process, thus cause the hole of initial fiber to increase, reduce the mechanical property of fiber.In addition, in curing process, the initial fiber of melt-spinning needs hot setting in the hydrochloric acid and formaldehyde of higher concentration, and this process can produce toxic gas, larger to equipment corrosion degree.
Summary of the invention
The object of this invention is to provide a kind of lignin-base carbon fiber precursor and preparation method thereof.
Another object of the present invention is to provide the application of described lignin-base carbon fiber precursor.
In order to realize the object of the invention, the method preparing lignin-base carbon fiber precursor provided by the invention, comprises the following steps:
1) obtain wood powder after being pulverized by timber, mix with phenol after wood powder is dried, liquefy in the presence of acidic, obtain timber liquefied matter;
2) timber liquefied matter is after suction filtration, mix with the weight ratio of water by 1:1-100, adjust mixed solution pH value 2-10, then tensio-active agent is added by mixed solution weight 1-20%, stablizer is added again by mixed solution weight 1-30%, at 25-90 DEG C, stir 1-10h, products therefrom, through suction filtration, oven dry, obtains lignin-base carbon fiber precursor.
Wherein, step 2) in the tensio-active agent that uses be polyoxyethylene glycol PEG400, PEG600, PEG800 or PEG1000, stablizer is dodecane sulfonate.Preferably, tensio-active agent is PEG400, and stablizer is sodium laurylsulfonate.
Aforesaid method, step 1) be specially: obtain wood powder after being pulverized by timber, mix according to weight ratio 1:4 with phenol after wood powder is dried, then add an acidic catalyst by phenol weight 8-12%, at 160 DEG C, stir liquefaction 2.5h, obtain timber liquefied matter.
Aforesaid method, step 1) in timber comprise the timber of the various plant origin such as softwood, pourous wood.
Aforesaid method, step 1) in timber pulverize after the wood powder that obtains be 20-100 order, the temperature of oven dry is 103 ± 2 DEG C.
Aforesaid method, step 1) in an acidic catalyst that the uses phosphoric acid that is concentration 85%.
Aforesaid method, step 1) in the speed that stirs be 200-600rpm.
Aforesaid method, step 2) in use Büchner funnel to carry out suction filtration.
Aforesaid method, step 2) in the speed that stirs be 100-1000rpm, the temperature of oven dry is 45-80 DEG C.
The present invention also provides the lignin-base prepared according to preceding method carbon fiber precursor.
The present invention further provides the application of described lignin-base carbon fiber precursor in melt-spinning technology is produced.
Described application is specially: by lignin-base carbon fiber precursor grind into powder, be placed in spin duct, setting spinning temperature 190-210 DEG C, and after the complete melting of lignin-base carbon fiber precursor, setting spinning roller rotating speed 100-300rpm, carries out spinning.
The present invention has the following advantages:
(1) the lignin-base carbon fiber precursor adopting the inventive method to prepare, wherein content of lignin is more than 70%, and productive rate can reach 28.5%, and ash oontent is minimum is 0.36%.
(2) at 190-210 DEG C, lignin-base carbon fiber precursor viscosity number is suitable for melt-spinning, and viscosity number is stablized.
(3) in melt-spinning process, without the need to adding solidifying agent, as hexamethylenetetramine etc., decrease the discharge of waste gas, and reduce the negative impact that ammonia constructs for initial fiber.
(4) reduce hydrochloric acid and the formaldehyde of a large amount of use in solidification process, avoid the infringement of obnoxious flavour for human body and the pollution to environment in production process.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the lignin-base carbon fiber precursor utilizing embodiment 1-3 to prepare in the embodiment of the present invention 4 carries out melt-spinning.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art, is raw materials usedly commercial goods.
The preparation of embodiment 1 lignin-base carbon fiber precursor
The method preparing lignin-base carbon fiber precursor is as follows:
1, wooden shavings plant pulverizing is machined to 80 object wood powders, uses the loft drier being prepended to 103 DEG C to dry stand-by.
2, by wood powder and phenol (weight ratio of wood powder and phenol is 1:4) mixing, join in there-necked flask, then add phosphoric acid (concentration 85% of phosphoric acid) by phenol weight 10% and be placed in the oil bath pan that design temperature is 160 DEG C, install condenser, start whipping appts (stirring velocity is 500rpm) and carry out liquefaction reaction, after reaction 2.5h, remove oil bath, timber liquefied matter is poured into Büchner funnel suction filtration, stand-by.
3, in reactor, add timber liquefied matter and water (liquefied substance and water weight ratio are 1:80), adjustment solution ph is 7, then the Surfactant PEG 600 of solution weight 10% is added, add the stablizer sodium laurylsulfonate of solution weight 20% again, start whipping appts (stirring velocity is 800rpm), temperature is set as 80 DEG C, churning time 8 hours, by product Büchner funnel suction filtration, 80 DEG C of oven dry, obtain lignin-base carbon fiber precursor, wherein content of lignin is more than 80%, and productive rate is 25.9%, and ash oontent is 0.43%.
The lignin-base carbon fiber precursor prepared in the present embodiment is at 190-210 DEG C, and viscosity number is suitable for melt-spinning, and viscosity number is stablized.
The preparation of embodiment 2 lignin-base carbon fiber precursor
The method preparing lignin-base carbon fiber precursor is as follows:
1, wooden shavings plant pulverizing is machined to 20 object wood powders, uses the loft drier being prepended to 101 DEG C to dry stand-by.
2, by wood powder and phenol (weight ratio of wood powder and phenol is 1:4) mixing, join in there-necked flask, then add phosphoric acid (concentration 85% of phosphoric acid) by phenol weight 8% and be placed in the oil bath pan that design temperature is 160 DEG C, install condenser, start whipping appts (stirring velocity is 200rpm) and carry out liquefaction reaction, after reaction 2.5h, remove oil bath, timber liquefied matter is poured into Büchner funnel suction filtration, stand-by.
3, in reactor, add timber liquefied matter and water (liquefied substance and water weight ratio are 1:1), adjustment solution ph is 2, then the Surfactant PEG 400 of solution weight 1% is added, add the stablizer sodium laurylsulfonate of solution weight 1% again, start whipping appts (stirring velocity is 100rpm), temperature is set as 25 DEG C, churning time 8 hours, by product Büchner funnel suction filtration, 45 DEG C of oven dry, obtain lignin-base carbon fiber precursor, wherein content of lignin is more than 70%, and productive rate is 28.5%, and ash oontent is 0.36%.
The lignin-base carbon fiber precursor prepared in the present embodiment is at 190-210 DEG C, and viscosity number is suitable for melt-spinning, and viscosity number is stablized.
The preparation of embodiment 3 lignin-base carbon fiber precursor
The method preparing lignin-base carbon fiber precursor is as follows:
1, wooden shavings plant pulverizing is machined to 100 object wood powders, uses the loft drier being prepended to 105 DEG C to dry stand-by.
2, by wood powder and phenol (weight ratio of wood powder and phenol is 1:4) mixing, join in there-necked flask, then add phosphoric acid (concentration 85% of phosphoric acid) by phenol weight 12% and be placed in the oil bath pan that design temperature is 160 DEG C, install condenser, start whipping appts (stirring velocity is 600rpm) and carry out liquefaction reaction, after reaction 2.5h, remove oil bath, timber liquefied matter is poured into Büchner funnel suction filtration, stand-by.
3, in reactor, add timber liquefied matter and water (liquefied substance and water weight ratio are 1:100), adjustment solution ph is 10, then the Surfactant PEG 1000 of solution weight 20% is added, add the stablizer sodium laurylsulfonate of solution weight 30% again, start whipping appts (stirring velocity is 1000rpm), temperature is set as 90 DEG C, churning time 10 hours, by product Büchner funnel suction filtration, 65 DEG C of oven dry, obtain lignin-base carbon fiber precursor, wherein content of lignin is more than 80%, and productive rate is 26.8%, and ash oontent is 0.47%.
The lignin-base carbon fiber precursor prepared in the present embodiment is at 190-210 DEG C, and viscosity number is suitable for melt-spinning, and viscosity number is stablized.
The application of embodiment 4 lignin-base carbon fiber precursor
Utilize the lignin-base carbon fiber precursor of preparation in embodiment 1 to carry out melt-spinning, technique is as follows:
By the lignin-base carbon fiber precursor grind into powder of preparation in embodiment 1, be placed in spin duct, setting spinning temperature 190 DEG C, after the complete melting of presoma, setting spinning roller rotating speed 100rpm, carry out spinning, the initial fiber obtained is for the preparation of carbon fiber.
The application of embodiment 5 lignin-base carbon fiber precursor
Utilize the lignin-base carbon fiber precursor of preparation in embodiment 2 to carry out melt-spinning, technique is as follows:
By the lignin-base carbon fiber precursor grind into powder of preparation in embodiment 2, be placed in spin duct, setting spinning temperature 200 DEG C, after the complete melting of presoma, setting spinning roller rotating speed 200rpm, carry out spinning, the initial fiber obtained is for the preparation of carbon fiber.
The application of embodiment 6 lignin-base carbon fiber precursor
Utilize the lignin-base carbon fiber precursor of preparation in embodiment 3 to carry out melt-spinning, technique is as follows:
By the lignin-base carbon fiber precursor grind into powder of preparation in embodiment 3, be placed in spin duct, setting spinning temperature 210 DEG C, after the complete melting of presoma, setting spinning roller rotating speed 300rpm, carry out spinning, the initial fiber obtained is for the preparation of carbon fiber.
The lignin-base carbon fiber precursor utilizing embodiment 1-3 to prepare carries out the process flow sheet of melt-spinning as shown in Figure 1.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. prepare the method for lignin-base carbon fiber precursor, it is characterized in that, comprise the following steps:
1) obtain wood powder after being pulverized by timber, mix with phenol after wood powder is dried, liquefy in the presence of acidic, obtain timber liquefied matter;
2) timber liquefied matter is after suction filtration, mix with the weight ratio of water by 1:1-100, adjust mixed solution pH value 2-10, then tensio-active agent is added by mixed solution weight 1-20%, stablizer is added again by mixed solution weight 1-30%, at 25-90 DEG C, stir 1-10h, products therefrom, through suction filtration, oven dry, obtains lignin-base carbon fiber precursor;
Wherein, step 2) in the tensio-active agent that uses be PEG400, PEG600, PEG800 or PEG1000, stablizer is dodecane sulfonate.
2. method according to claim 1, it is characterized in that, step 1) be specially: obtain wood powder after being pulverized by timber, mix according to weight ratio 1:4 with phenol after wood powder is dried, then an acidic catalyst is added by phenol weight 8-12%, at 160 DEG C, stir liquefaction 2.5h, obtain timber liquefied matter.
3. method according to claim 1, is characterized in that, step 1) in timber comprise softwood, pourous wood, timber pulverize after the wood powder that obtains be 20-100 order, the temperature of oven dry is 103 ± 2 DEG C.
4. method according to claim 2, is characterized in that, step 1) in an acidic catalyst that the uses phosphoric acid that is concentration 85%.
5. method according to claim 2, is characterized in that, step 1) in stir speed be 200-600rpm.
6. method according to claim 2, is characterized in that, step 2) in use Büchner funnel carry out suction filtration.
7. method according to claim 2, step 2) in the speed that stirs be 100-1000rpm, the temperature of oven dry is 40-80 DEG C.
8. the lignin-base carbon fiber precursor that according to any one of claim 1-7 prepared by method.
9. the application of lignin-base carbon fiber precursor described in claim 8 in melt-spinning technology is produced.
10. application according to claim 9, is characterized in that, by lignin-base carbon fiber precursor grind into powder, be placed in spin duct, setting spinning temperature 190-210 DEG C, after the complete melting of lignin-base carbon fiber precursor, setting spinning roller rotating speed 100-300rpm, carries out spinning.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105384896A (en) * | 2015-12-22 | 2016-03-09 | 中国科学院山西煤炭化学研究所 | Method for preparing lignin-based carbon fiber spinning solution |
| CN106480606A (en) * | 2016-10-21 | 2017-03-08 | 天津工业大学 | A kind of carbon fiber preparation method of lignin-base fiber felt |
| CN108330569A (en) * | 2018-02-08 | 2018-07-27 | 北京林业大学 | A kind of lignin-base activated carbon fiber presoma and the preparation method and application thereof |
| CN105384896B (en) * | 2015-12-22 | 2018-08-31 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of lignin-base carbon fiber spinning solution |
| CN109537104A (en) * | 2018-11-29 | 2019-03-29 | 青岛大学 | A kind of preparation method of lignin-base carbon fiber precursor |
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| CN1528824A (en) * | 2003-09-26 | 2004-09-15 | 中国科学院广州化学研究所 | Vegetable fiber liquefied matter, and preparing method and use thereof |
| CN101135075A (en) * | 2007-10-11 | 2008-03-05 | 北京林业大学 | Wood liquefied carbide fiber, protofilament and preparation method thereof |
| CN103304765A (en) * | 2013-06-03 | 2013-09-18 | 北京林业大学 | Preparation method of wood liquefied product spinning solution |
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Patent Citations (3)
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| CN1528824A (en) * | 2003-09-26 | 2004-09-15 | 中国科学院广州化学研究所 | Vegetable fiber liquefied matter, and preparing method and use thereof |
| CN101135075A (en) * | 2007-10-11 | 2008-03-05 | 北京林业大学 | Wood liquefied carbide fiber, protofilament and preparation method thereof |
| CN103304765A (en) * | 2013-06-03 | 2013-09-18 | 北京林业大学 | Preparation method of wood liquefied product spinning solution |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384896A (en) * | 2015-12-22 | 2016-03-09 | 中国科学院山西煤炭化学研究所 | Method for preparing lignin-based carbon fiber spinning solution |
| CN105384896B (en) * | 2015-12-22 | 2018-08-31 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of lignin-base carbon fiber spinning solution |
| CN106480606A (en) * | 2016-10-21 | 2017-03-08 | 天津工业大学 | A kind of carbon fiber preparation method of lignin-base fiber felt |
| CN108330569A (en) * | 2018-02-08 | 2018-07-27 | 北京林业大学 | A kind of lignin-base activated carbon fiber presoma and the preparation method and application thereof |
| CN109537104A (en) * | 2018-11-29 | 2019-03-29 | 青岛大学 | A kind of preparation method of lignin-base carbon fiber precursor |
| CN109537104B (en) * | 2018-11-29 | 2021-05-14 | 青岛大学 | Preparation method of lignin-based carbon fiber precursor |
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