CA1320484C - Method for manufacturing lignin for carbon fiber spinning - Google Patents
Method for manufacturing lignin for carbon fiber spinningInfo
- Publication number
- CA1320484C CA1320484C CA000601952A CA601952A CA1320484C CA 1320484 C CA1320484 C CA 1320484C CA 000601952 A CA000601952 A CA 000601952A CA 601952 A CA601952 A CA 601952A CA 1320484 C CA1320484 C CA 1320484C
- Authority
- CA
- Canada
- Prior art keywords
- lignin
- carbon fiber
- spinning
- phenolated
- heat treatment
- 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.)
- Expired - Fee Related
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 55
- 238000009987 spinning Methods 0.000 title claims abstract description 29
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 24
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000029087 digestion Effects 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007499 fusion processing Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- WHRZCXAVMTUTDD-UHFFFAOYSA-N 1h-furo[2,3-d]pyrimidin-2-one Chemical compound N1C(=O)N=C2OC=CC2=C1 WHRZCXAVMTUTDD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000006173 Larrea tridentata Nutrition 0.000 description 3
- 244000073231 Larrea tridentata Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960002126 creosote Drugs 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000202567 Fatsia japonica Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- -1 amide salts Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000004459 forage Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
Abstract of the Disclosure:
A method for manufacturing lignin for carbon fiber spinning, comprising subjecting to heat treatment in a non-oxidizing atmosphere a phenolated lignin obtained by phenolation of lignin dissolved out in delignification of a woody material, or a phenolated lignin derived from digestion of a woody material with a phenol.
A method for manufacturing lignin for carbon fiber spinning, comprising subjecting to heat treatment in a non-oxidizing atmosphere a phenolated lignin obtained by phenolation of lignin dissolved out in delignification of a woody material, or a phenolated lignin derived from digestion of a woody material with a phenol.
Description
1320~
Background of the Invention:
Field of the Invention:
The present invention relates to a method for manufacturing a lignin for continuous carbon fiber spinning by heat-fusion process, employing lignin as a starting material, which is contained in woody material in an amount of about 20 to 30 %.
Nowadays comprehensive studies are being made on separation or modification of cellulose, hemicellulose and lignin from woody resources for the purpose of utilizing such materials as food, forage, and chemical industrial starting materials. In certain fields, development for industrialization is going on. In the field of pulping technology, new organic solvent digestion processes are extensively studied, where an alcohol, a phenol, acetic acid, or the like are used as the digesting agent. However, success of these new technologies depends upon the accomplishment of effective utilization of lignin.
Description of the Related Arts:
One technology of converting lignin to industrial materials of high added value relates to manufacture of carbon fiber therefrom.
One prior art regarding lignin carbon fiber relates to lignin-poval type carbon fiber proposed by Professor Ohtani of Gumma University on 1963: See Japanese Patent Publications No. 15727/1966, and No. 26356/1967.
1 3 2 $~
This process is characterized by drawing out thread from a spinning solution prepared by heating and dissolving lignin (of industrial grade) and polyvinyl alcohol in a highly concentrated aqueous NaOH solution. This process was ousted by PAN type and pitch type carbon fiber because of the cost and the properties. After 20 years therefrom, the present inventors proposed a process for manufacturing lignin for continuous spinning by hydrogenolysis, and heating lignin obtained by digestion and explosion-disintegration of wood, as well as a process of carbon fiber therefrom: See Japanese Laid-Open Patent Application No. 110922/1987. The carbon fiber of the former of the above processes has disadvantages such that the manufacturing cost is high because of the wet spinning process and of high temperature treatment at 1400C or higher for vaporizing-off of sodium, and that the product is significantly low in strength characteristics. The latter of the above processes is now under study for industrialization.
20- This process involves the problems of high capital cost resulting from high energy consumption and use of pressure vessels in hydrogenolysis in the spinning-lignin preparation process, and further of low yield of the carbon fiber.
Summary of the Invention:
The present invention has been accomplished from the aforementioned view point, and provides a method ~ 32~
for manufacturing lignin for carbon fiber spinning which process makes it feasible to manufacture carbon fiber of high added value in high yield and economically from lignin separated from woody resources as mentioned above.
In accordance with the present invention, there is provided a method of manufacturing a lignin for carbon fiber spinning, which comprises subjecting a phenolated lignin deriving from woody material to heat treatment in a non-oxidizing atmosphere.
Preferably, the phenolated lignin is prepared by phenolation of lignin dissolved out from the woody material by delignification. The phenolated lignin can also be prepared by digestion of the woody material with a phenolic substance.
Detailed Description of the Invention:
In this invention, the lignin derived from woody materials includes lignins exhausted from or produced as a by-product in paper plants or pulp plants using woody materials as a raw material; and lignins produced as a by-product in a new separation process such as a boiling process, explosive disintegration, and organic solvent digestion, or in a new pulping technology.
In this invention, the lignin is phenolated, and subjected to heat treatment in non-oxidizing atmosphere to prepare lignin material for spinning, and subsequently it is spun, made infusible, and carbonized to produce carbon fiber.
The gist of the present invention is to heat the lignin and phenolic solvent to reflux at its boiling point to produce phenolated lignin having thermal f~
~J
132~
fluidity, and to continue further heating in a reaction vessel in a non-oxidizlng atmosphere to complete heat tretment, thus producing lignin for spinning.
The phenolation may be conducted by heating the mixture of the above-mentioned lignin with a phenol in presence of or absence of catalyst such as an acidic organic catalyst as an accelerator. The phenols useful for the phenolation includes pure substance such as phenol, cresole as well as mixtures of phenolic substances like quaiacol such as creosote, and methyl creosole and xylenol. The catalyst useful for accelerating phenolation includes organic acidic catalysts such as p-toluene sulfonic acid, sulfonyl chloride, amide salts and hydroxyamine salts thereof.
The heat treatment for densification may be conducted by heating a phenolated lignin in a non-oxidizing atmosphere. The non-oxidizing atmosphere may be prepared with nitrogen stream under reduced pressure. The pressure reduction is preferable in many cases and the heat treatment mainly for increased viscosity or densification in the present invention is conducted under a reduced pressure of several tens of mmHg, or preferably of 10 mmHg or less, and the solvent is easily recovered. The heating is conducted at a temperature and for a lapse of time sufficient to polycondensation of phenolated lignin for viscosity increase of the solution. Generally, heating is preferably conducted to such a degree that the spinning ~32~
temperature of l50C or more is attained. For example, heat treatment in a temperature range of from 180 to 300C for 30 minutes to 6 hours is preferable.
The lignin for spinning prepared as mentioned above may be continuously spun by conventional heat-fusion process.
This fiber is made infusible by heating in the air at a constant rate of temperature elevation.
This process for infusibleness may be carried out according to a conventional method, for example, by starting at 80C and completing at 200C. The fiber thus made infusible is generally carbonized by elevation of the temperature at a rate of 200C per hour up to 800C in nitrogen stream.
The present invention provides lignin for spinning with a high yield of 80 % or more which is twice or more times that of the conventional method conducted by the pres$nt inventors. The yield of the carbon fiber as the final product is about 30 ~, which is higher than not only the conventional method but also pitch type carbon fiber.
Description of the Preferred Embodiments:
The present invention is explained below by referring to examples. This invention, however, is not limited by these examples.
Raw material The lignin material was obtained from white 1 3 ~
birch wood by boiling with saturated steam of 15 kg/cm (guage pressure) for 10 minutes, disintegration by means of a refiner, removal of hemicellulose by extraction with water, and extraction with methanol.
Example l:
10 grams of the above-described lignin material was made to react with an equal amount of phenol in an glass flask equipped with a stirrer and a cooler for 3 to 5 hours at the boiling temperature (180C) of phenol.
p-Toluence sulfonic acid was added at the reaction in an amount of 2 % relative to the lignin.
After the reaction, the reaction vessel was evacuated (to approximately 10 mmHg), and the heat treatment was conducted (for further 3 to 5 hours) at the same temperature for recovery of the unreacted phenol and for densification. Lumpy solid matter was thus obtained by the treatment.
Table 1 shows the yield of the lignin for spinning thus prepared, spinning characteristics thereof in continuous spinning according to conventional heat-fusion process, and heat stability of the spun fiber.
The spinning characteristics was evaluated by spinning speed within which continuous spinning is feasible.
The heat stability was evaluated by occurrence of fusion-bonding between fibers.
'7 ~ - 6 -i ' Table 1 ___ _ Heat Treatment Exper- Condition Yield Spinning Heat No. (~) istics Stability Temper- Time (C) (Hours) 1 180 3 100.3 +++ _ 2 180 4 96.8 +++
3 180 5 93.8 + ++
In the Table:
Yields are shown in percentage by weight of lignin, The symbol "+" means feasibility of spinning at the rate of 100 m per minute for one +, and the number of the symbol is the multiple thereof, Thermal stability is represented by the symbols as below:
- : Fusion-bonding occurs between fibers, + : Slight fusion-bonding is observed between fibers, ++ : No fusion-bonding was observed.
As shown in Table 1, the yields of lignin for spinning were not less than 90 % in all Examples, which are twice or more that of the conventional process (Japanese Laid-Open Patent Application No. 110922/1987).
All samples could be spun at a spinning rate of 100 m per minute or more in the thermal fusion process. The f.~ t thermal s~ability of fiber was inclined to depend on the length of the neat treatment time: the fiber spun after 3 hours of heat treatment became fused during the thermal stabilization treatment, while the fibers from the lignin for spinning obtained by 4 hours or 5 hours of the treatment could be made infusible by heating up to 200C with temperature elevation rate of 6C per hour.
By changing the heat treatment conditions, it is possible to substantially change the time required by the thermal stabilization treatment. For example, the fibers prepared by spinning the phenolated lignin - heated at 300C for 30 minutes under reduced pressure can be made infusible by heating up to 250C with a heating rate of 10C/minute.
The lignin for spinning which had been made infusible in Experiment 2 was carbonized by elevating the temperature at a rate of 100C per hour up to 1000C
in nitrogen;stream in a firing furnace. Table 2 shows the properties of the resulting carbon fiber.
l~2a~
Table 2: Properties of Li~nin Carbon ~iber Fiber Breadth 21.4 + 5.44 ~m Tensile Strength 52.8 + 11.6 kg/mm Elongation 1.06 + 0.18 %
Elasticity Modulus 4.99 + 0.63 t/mm The yield of this carbon fiber was about 30 %.
Table 3 shows the yield in each steps from lignin to carbon fiber in comparison with that of conventional method.
Table 3: Yields in Manufacturing Steps and of Carbon Fiber Hydrogenolysis Method of , Method Present Invention - .
Sample Preparation Step 0.4 0.9 20 Spinning Step 0.8 0.8 Heat Stabilization Step 1.0 1.0 Carbonization Step 0.5 0.4 Yield of Carbon Fiber (%) 16 28.8 From Table 3, it is understood that the present invention provides carbon fiber in a high yield.
1 ~2 ,~ `i `, 1 Example 2:
The above-mentioned raw material and the equal amount of creosote were made to react in an autoclave under agitation at 300C for one hour. Then the reaction liquor was transferred into a glass vessel and heated under a reduced pressure to remove and recover the unreacted creosote and to prepare phenolated lignin.
No catalyst was added in this Example.
The resulting phenolated lignin was densified by heating at 250C for 15 minutes under a reduced pressure (the pressure being the same as in Example 1) to prepare lignin for spinning.
The yield was 85.5 %.
The spinning characteristics in the heat fusion method, and the stability of the fiber were tested in the same manner as in Example 1 to find that it was as excellent as the product of Example 1 for use as the starting material for carbon fiber.
In the above examples, the lignin extracted from the woody material is used as the starting material.
However, the woody material can directly be treated with a phenolic substance to obtain the phenolated lignin for further heat treatment. In this case also similar results can be obtained.
,
Background of the Invention:
Field of the Invention:
The present invention relates to a method for manufacturing a lignin for continuous carbon fiber spinning by heat-fusion process, employing lignin as a starting material, which is contained in woody material in an amount of about 20 to 30 %.
Nowadays comprehensive studies are being made on separation or modification of cellulose, hemicellulose and lignin from woody resources for the purpose of utilizing such materials as food, forage, and chemical industrial starting materials. In certain fields, development for industrialization is going on. In the field of pulping technology, new organic solvent digestion processes are extensively studied, where an alcohol, a phenol, acetic acid, or the like are used as the digesting agent. However, success of these new technologies depends upon the accomplishment of effective utilization of lignin.
Description of the Related Arts:
One technology of converting lignin to industrial materials of high added value relates to manufacture of carbon fiber therefrom.
One prior art regarding lignin carbon fiber relates to lignin-poval type carbon fiber proposed by Professor Ohtani of Gumma University on 1963: See Japanese Patent Publications No. 15727/1966, and No. 26356/1967.
1 3 2 $~
This process is characterized by drawing out thread from a spinning solution prepared by heating and dissolving lignin (of industrial grade) and polyvinyl alcohol in a highly concentrated aqueous NaOH solution. This process was ousted by PAN type and pitch type carbon fiber because of the cost and the properties. After 20 years therefrom, the present inventors proposed a process for manufacturing lignin for continuous spinning by hydrogenolysis, and heating lignin obtained by digestion and explosion-disintegration of wood, as well as a process of carbon fiber therefrom: See Japanese Laid-Open Patent Application No. 110922/1987. The carbon fiber of the former of the above processes has disadvantages such that the manufacturing cost is high because of the wet spinning process and of high temperature treatment at 1400C or higher for vaporizing-off of sodium, and that the product is significantly low in strength characteristics. The latter of the above processes is now under study for industrialization.
20- This process involves the problems of high capital cost resulting from high energy consumption and use of pressure vessels in hydrogenolysis in the spinning-lignin preparation process, and further of low yield of the carbon fiber.
Summary of the Invention:
The present invention has been accomplished from the aforementioned view point, and provides a method ~ 32~
for manufacturing lignin for carbon fiber spinning which process makes it feasible to manufacture carbon fiber of high added value in high yield and economically from lignin separated from woody resources as mentioned above.
In accordance with the present invention, there is provided a method of manufacturing a lignin for carbon fiber spinning, which comprises subjecting a phenolated lignin deriving from woody material to heat treatment in a non-oxidizing atmosphere.
Preferably, the phenolated lignin is prepared by phenolation of lignin dissolved out from the woody material by delignification. The phenolated lignin can also be prepared by digestion of the woody material with a phenolic substance.
Detailed Description of the Invention:
In this invention, the lignin derived from woody materials includes lignins exhausted from or produced as a by-product in paper plants or pulp plants using woody materials as a raw material; and lignins produced as a by-product in a new separation process such as a boiling process, explosive disintegration, and organic solvent digestion, or in a new pulping technology.
In this invention, the lignin is phenolated, and subjected to heat treatment in non-oxidizing atmosphere to prepare lignin material for spinning, and subsequently it is spun, made infusible, and carbonized to produce carbon fiber.
The gist of the present invention is to heat the lignin and phenolic solvent to reflux at its boiling point to produce phenolated lignin having thermal f~
~J
132~
fluidity, and to continue further heating in a reaction vessel in a non-oxidizlng atmosphere to complete heat tretment, thus producing lignin for spinning.
The phenolation may be conducted by heating the mixture of the above-mentioned lignin with a phenol in presence of or absence of catalyst such as an acidic organic catalyst as an accelerator. The phenols useful for the phenolation includes pure substance such as phenol, cresole as well as mixtures of phenolic substances like quaiacol such as creosote, and methyl creosole and xylenol. The catalyst useful for accelerating phenolation includes organic acidic catalysts such as p-toluene sulfonic acid, sulfonyl chloride, amide salts and hydroxyamine salts thereof.
The heat treatment for densification may be conducted by heating a phenolated lignin in a non-oxidizing atmosphere. The non-oxidizing atmosphere may be prepared with nitrogen stream under reduced pressure. The pressure reduction is preferable in many cases and the heat treatment mainly for increased viscosity or densification in the present invention is conducted under a reduced pressure of several tens of mmHg, or preferably of 10 mmHg or less, and the solvent is easily recovered. The heating is conducted at a temperature and for a lapse of time sufficient to polycondensation of phenolated lignin for viscosity increase of the solution. Generally, heating is preferably conducted to such a degree that the spinning ~32~
temperature of l50C or more is attained. For example, heat treatment in a temperature range of from 180 to 300C for 30 minutes to 6 hours is preferable.
The lignin for spinning prepared as mentioned above may be continuously spun by conventional heat-fusion process.
This fiber is made infusible by heating in the air at a constant rate of temperature elevation.
This process for infusibleness may be carried out according to a conventional method, for example, by starting at 80C and completing at 200C. The fiber thus made infusible is generally carbonized by elevation of the temperature at a rate of 200C per hour up to 800C in nitrogen stream.
The present invention provides lignin for spinning with a high yield of 80 % or more which is twice or more times that of the conventional method conducted by the pres$nt inventors. The yield of the carbon fiber as the final product is about 30 ~, which is higher than not only the conventional method but also pitch type carbon fiber.
Description of the Preferred Embodiments:
The present invention is explained below by referring to examples. This invention, however, is not limited by these examples.
Raw material The lignin material was obtained from white 1 3 ~
birch wood by boiling with saturated steam of 15 kg/cm (guage pressure) for 10 minutes, disintegration by means of a refiner, removal of hemicellulose by extraction with water, and extraction with methanol.
Example l:
10 grams of the above-described lignin material was made to react with an equal amount of phenol in an glass flask equipped with a stirrer and a cooler for 3 to 5 hours at the boiling temperature (180C) of phenol.
p-Toluence sulfonic acid was added at the reaction in an amount of 2 % relative to the lignin.
After the reaction, the reaction vessel was evacuated (to approximately 10 mmHg), and the heat treatment was conducted (for further 3 to 5 hours) at the same temperature for recovery of the unreacted phenol and for densification. Lumpy solid matter was thus obtained by the treatment.
Table 1 shows the yield of the lignin for spinning thus prepared, spinning characteristics thereof in continuous spinning according to conventional heat-fusion process, and heat stability of the spun fiber.
The spinning characteristics was evaluated by spinning speed within which continuous spinning is feasible.
The heat stability was evaluated by occurrence of fusion-bonding between fibers.
'7 ~ - 6 -i ' Table 1 ___ _ Heat Treatment Exper- Condition Yield Spinning Heat No. (~) istics Stability Temper- Time (C) (Hours) 1 180 3 100.3 +++ _ 2 180 4 96.8 +++
3 180 5 93.8 + ++
In the Table:
Yields are shown in percentage by weight of lignin, The symbol "+" means feasibility of spinning at the rate of 100 m per minute for one +, and the number of the symbol is the multiple thereof, Thermal stability is represented by the symbols as below:
- : Fusion-bonding occurs between fibers, + : Slight fusion-bonding is observed between fibers, ++ : No fusion-bonding was observed.
As shown in Table 1, the yields of lignin for spinning were not less than 90 % in all Examples, which are twice or more that of the conventional process (Japanese Laid-Open Patent Application No. 110922/1987).
All samples could be spun at a spinning rate of 100 m per minute or more in the thermal fusion process. The f.~ t thermal s~ability of fiber was inclined to depend on the length of the neat treatment time: the fiber spun after 3 hours of heat treatment became fused during the thermal stabilization treatment, while the fibers from the lignin for spinning obtained by 4 hours or 5 hours of the treatment could be made infusible by heating up to 200C with temperature elevation rate of 6C per hour.
By changing the heat treatment conditions, it is possible to substantially change the time required by the thermal stabilization treatment. For example, the fibers prepared by spinning the phenolated lignin - heated at 300C for 30 minutes under reduced pressure can be made infusible by heating up to 250C with a heating rate of 10C/minute.
The lignin for spinning which had been made infusible in Experiment 2 was carbonized by elevating the temperature at a rate of 100C per hour up to 1000C
in nitrogen;stream in a firing furnace. Table 2 shows the properties of the resulting carbon fiber.
l~2a~
Table 2: Properties of Li~nin Carbon ~iber Fiber Breadth 21.4 + 5.44 ~m Tensile Strength 52.8 + 11.6 kg/mm Elongation 1.06 + 0.18 %
Elasticity Modulus 4.99 + 0.63 t/mm The yield of this carbon fiber was about 30 %.
Table 3 shows the yield in each steps from lignin to carbon fiber in comparison with that of conventional method.
Table 3: Yields in Manufacturing Steps and of Carbon Fiber Hydrogenolysis Method of , Method Present Invention - .
Sample Preparation Step 0.4 0.9 20 Spinning Step 0.8 0.8 Heat Stabilization Step 1.0 1.0 Carbonization Step 0.5 0.4 Yield of Carbon Fiber (%) 16 28.8 From Table 3, it is understood that the present invention provides carbon fiber in a high yield.
1 ~2 ,~ `i `, 1 Example 2:
The above-mentioned raw material and the equal amount of creosote were made to react in an autoclave under agitation at 300C for one hour. Then the reaction liquor was transferred into a glass vessel and heated under a reduced pressure to remove and recover the unreacted creosote and to prepare phenolated lignin.
No catalyst was added in this Example.
The resulting phenolated lignin was densified by heating at 250C for 15 minutes under a reduced pressure (the pressure being the same as in Example 1) to prepare lignin for spinning.
The yield was 85.5 %.
The spinning characteristics in the heat fusion method, and the stability of the fiber were tested in the same manner as in Example 1 to find that it was as excellent as the product of Example 1 for use as the starting material for carbon fiber.
In the above examples, the lignin extracted from the woody material is used as the starting material.
However, the woody material can directly be treated with a phenolic substance to obtain the phenolated lignin for further heat treatment. In this case also similar results can be obtained.
,
Claims (4)
1. A method for manufacturing a lignin for carbon fiber spinning, which comprises subjecting a phenolated lignin deriving from woody material to heat treatment in a non-oxidizing atmosphere.
2. A method according to claim 1, wherein the phenolated lignin is prepared by phenolation of lignin dissolved out from the woody material by delignification.
3. A method according to claim 1, wherein the phenolated lignin is prepared by digestion of the woody material with a phenolic substance.
4. A method according to claim 1, where the heat treatment is done at a temperature ranging from 180 to 300°C for 30 minutes to 6 hours under a reduced pressure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPSHO63-138747 | 1988-06-06 | ||
| JP63138747A JPH01306618A (en) | 1988-06-06 | 1988-06-06 | Preparation of lignin for spinning of carbon fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1320484C true CA1320484C (en) | 1993-07-20 |
Family
ID=15229232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000601952A Expired - Fee Related CA1320484C (en) | 1988-06-06 | 1989-06-06 | Method for manufacturing lignin for carbon fiber spinning |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH01306618A (en) |
| CA (1) | CA1320484C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11993624B2 (en) | 2013-05-03 | 2024-05-28 | Virdia, Llc | Methods for preparing thermally stable lignin fractions |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5818066B2 (en) * | 2011-06-07 | 2015-11-18 | 国立研究開発法人産業技術総合研究所 | Carbon fiber manufacturing method |
| SG11201407183SA (en) | 2012-05-03 | 2014-12-30 | Virdia Ltd | Methods for treating lignocellulosic materials |
| CN103014920B (en) * | 2012-12-17 | 2014-03-19 | 北京林业大学 | Wood carbon fiber precursor and preparation method thereof |
| US10767308B2 (en) | 2014-07-09 | 2020-09-08 | Virdia, Inc. | Methods for separating and refining lignin from black liquor and compositions thereof |
| JP2019050152A (en) * | 2017-09-11 | 2019-03-28 | 株式会社藤井基礎設計事務所 | Separator for nonaqueous electrolyte secondary battery, nonaqueous electrolyte secondary battery, and manufacturing method of separator for nonaqueous electrolyte secondary battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6034623U (en) * | 1983-08-12 | 1985-03-09 | 三菱自動車工業株式会社 | Flexible chain lever |
-
1988
- 1988-06-06 JP JP63138747A patent/JPH01306618A/en active Granted
-
1989
- 1989-06-06 CA CA000601952A patent/CA1320484C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11993624B2 (en) | 2013-05-03 | 2024-05-28 | Virdia, Llc | Methods for preparing thermally stable lignin fractions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0329887B2 (en) | 1991-04-25 |
| JPH01306618A (en) | 1989-12-11 |
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