CN108251919B - Intermittent and continuous asphalt-based graphite fiber filament preparation method - Google Patents
Intermittent and continuous asphalt-based graphite fiber filament preparation method Download PDFInfo
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- CN108251919B CN108251919B CN201810135906.2A CN201810135906A CN108251919B CN 108251919 B CN108251919 B CN 108251919B CN 201810135906 A CN201810135906 A CN 201810135906A CN 108251919 B CN108251919 B CN 108251919B
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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
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
Abstract
A method for preparing pitch-based graphite fiber filament with intermittent and continuous addition comprises the steps of flatly paving pitch precursor into a porous tray; pre-oxidizing the porous tray paved with the asphalt protofilaments in a hot air circulating furnace, wherein the specific conditions of the pre-oxidation are as follows: heating to 280-320 ℃ from 160 ℃ at a heating rate of 0.5-10 ℃/min, and pre-oxidizing for 10-20 min at 280-320 ℃; carrying out low-temperature carbonization on the obtained pitch pre-oxidized fiber in an inert atmosphere furnace; and carrying out continuous high-temperature carbonization, continuous graphitization and rolling to obtain the pitch-based graphite fiber filament. The invention combines the advantages of intermittent type and continuous type, improves the production efficiency, has the modulus of more than 800GPa, and is suitable for engineering large-scale production.
Description
Technical Field
The invention belongs to the technical field of high polymer fiber materials, and particularly relates to a preparation method of an intermittent and continuous asphalt-based graphite fiber filament.
Background
The carbon fiber is a fibrous carbon material, has lower density than metal aluminum, but higher strength than steel, and has the characteristics of corrosion resistance and high modulus. The graphite fiber generally refers to carbon fiber with carbon content of more than 99%, and compared with the carbon fiber, the graphite fiber has high carbon content, high tensile modulus, small thermal expansion coefficient, good thermal stability, stable dimension and other excellent performances, so that the graphite fiber is used for manufacturing rigid, thin and stable-dimension composite material members and is widely applied to the fields of space vehicles and aerospace. The pitch-based graphite fiber is characterized by extremely high modulus and thermal conductivity, which is widely concerned in recent years, and the invention patent with the application number of 201510582099.5 discloses a continuous pitch-based precursor preoxidation, carbonization and graphitization method, but because the filament-moving speed is very low, a very long preoxidation furnace is needed to ensure the full progress of the preoxidation, the pitch precursor itself is very fragile, and a large amount of filaments are generated by the friction when the filament bundle passes through a drawing roller for many times, so that the improvement of the production efficiency and the product performance is limited, but the continuous method has the advantages that the drawing force and the subsequent other treatments are applied at different reaction stages, and some process means are added; the batch type has an advantage in mass production, and the batch type high-temperature carbonization furnace and the graphitization furnace inevitably increase use and maintenance costs due to the limitation of material and equipment manufacturing costs.
Disclosure of Invention
The invention aims to provide a preparation method of a high-performance asphalt-based graphite fiber filament, which solves the problems of low production efficiency and high cost in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing pitch-based graphite fiber filaments in an intermittent and continuous mode comprises the following steps:
the method comprises the following steps: raw silk dropping barrel
Laying the asphalt protofilaments into a porous tray;
step two: batch pre-oxidation
Pre-oxidizing the porous tray paved with the asphalt protofilaments in a hot air circulating furnace;
step three: intermittent low-temp. charring
Carrying out low-temperature carbonization on the pitch pre-oxidized fiber obtained in the step two in an inert atmosphere furnace;
step four: and carrying out continuous high-temperature carbonization, continuous graphitization and rolling to obtain the pitch-based graphite fiber filament.
The further improvement of the invention is that the asphalt protofilament is laid in the porous tray by a translation or rotation mechanism at an unwinding speed of 5-40 m/min.
The further improvement of the invention is that in the second step, the specific preoxidation conditions are as follows: pre-oxidizing at the final temperature of 280-320 ℃ for 10-20 min; wherein the temperature is increased from 160 ℃ to 280-320 ℃ at a heating rate of 0.5-10 ℃/min.
The further improvement of the invention is that in the third step, the specific conditions of low-temperature carbonization are as follows: carbonizing at 900 ℃ for 10-20 min; wherein the temperature is increased from 300 ℃ to 900 ℃ at a temperature increase rate of 2-10 ℃/min.
The invention is further improved in that the temperature deviation in the effective temperature zone of the hot air circulating furnace is not more than +/-2.5 ℃, and the air speed is less than 2.5 m/s.
The further improvement of the invention is that the low-temperature carbonization is carried out in an inert atmosphere furnace, argon or nitrogen is introduced into the inert atmosphere furnace, and the flow rate of the argon or the nitrogen is 40-80L/min, so that the micro-positive pressure of 500-2000 Pa is achieved in the inert atmosphere furnace; the continuous high-temperature carbonization is carried out in a high-temperature carbonization furnace, the continuous graphitization is carried out in a graphitization furnace, the inlet and the outlet of the high-temperature carbonization furnace and the graphitization furnace are in open structures, the hearth is separated from the atmosphere by 3-4 vertically symmetrical nitrogen or argon gas curtains at the furnace mouth, the inlet pressure of the nitrogen or the argon gas is 0.1-0.15 MPa, and the micro positive pressure of more than 20Pa in the hearth is formed.
The further improvement of the invention is that the pitch carbon fiber carbonized in the third step enters the high-temperature carbonization furnace and the graphitization furnace in sequence at the wire moving speed of 0.15-1.0 m/min.
A further improvement of the invention is that a draft of 1% to 9% is applied during the running.
The further improvement of the invention is that the temperature of high-temperature carbonization is 950-1800 ℃.
The invention is further improved in that the graphitization temperature is 2000 ℃ or higher.
Compared with the prior art, the invention has the following beneficial effects: the mesophase pitch-based precursor has certain strength only after being subjected to pre-oxidation and low-temperature carbonization treatment, so that the production method adopts intermittent pre-oxidation, intermittent low-temperature carbonization, continuous high-temperature carbonization, continuous graphitization and rolling, improves the production efficiency, reduces the damage of tows during pre-oxidation and low-temperature carbonization, and is suitable for engineering large-scale production. The invention combines the advantages of batch type and continuous type, the strength of the prepared 2K asphalt-based graphite fiber can reach more than 2500MPa, the modulus can reach more than 800GPa, the thermal conductivity can reach more than 600W/(m.K), and the asphalt-based carbon fiber or graphite fiber can be provided according to specific requirements.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
Referring to fig. 1, the intermittent-feeding continuous pitch-based graphite fiber filament preparation method of the present invention comprises the following steps:
the method comprises the following steps: raw silk dropping barrel
Continuously and uniformly spreading the asphalt protofilaments in a loose manner into a porous tray at an unwinding speed of 5-40 m/min by a translation or rotation mechanism;
the porous tray is made of stainless steel or high-temperature-resistant materials, the wall thickness is 1-2 mm, deformation is avoided at high temperature, the specification of the asphalt protofilament is 2k, the continuous filament withdrawing length is not less than 500m, and the filament drawing position is marked;
step two: batch pre-oxidation
Putting the porous tray with the paved asphalt protofilaments into a hot air circulating furnace, taking air as a medium, raising the temperature from room temperature to 160 ℃ at a heating rate of 5-10 ℃, preserving the heat for 10min at 160 ℃, so as to ensure that the temperature of the hot air circulating furnace is uniform, then raising the temperature to 280-320 ℃ at a heating rate of 0.5-10 ℃/min, and carrying out pre-oxidation for 10-20 min, wherein the temperature deviation in an effective temperature zone in the furnace is not more than +/-2.5 ℃, and the wind speed is less than 2.5 m/s;
step three: intermittent low-temp. charring
Putting the asphalt pre-oxidized fiber obtained in the step two and the porous tray into an inert atmosphere furnace, heating to 300 ℃ from room temperature at a heating rate of 5-10 ℃/min, and preserving heat for 10min, so as to ensure uniform temperature in the inert atmosphere furnace, heating to 900 ℃ at a heating rate of 2-10 ℃/min, and carrying out low-temperature carbonization for 10-20 min, wherein a hearth is made of integral stainless steel, 40-80L/min of high-purity argon or nitrogen is continuously introduced in the operation process, and the micro-positive pressure of 500-2000 Pa in the hearth is kept;
step four: continuous high-temperature carbonization, continuous graphitization and rolling
Drawing the pitch carbon fibers obtained in the third step, sequentially feeding the pitch carbon fibers into a high-temperature carbonization furnace and a graphitization furnace at the high temperature of 950-1800 ℃ and graphitizing at the temperature of more than 2000 ℃ at the filament feeding speed of 0.15-1.0 m/min to obtain pitch-based graphite fibers, and applying 1-9% of drafting amount in the filament feeding process;
the inlet and outlet of the high-temperature carbonization furnace and the graphitization furnace are in open structures, the hearth is separated from the atmosphere by 3-4 vertically symmetrical nitrogen or argon gas curtains at the furnace mouth, the inlet pressure of the nitrogen or argon gas is 0.1-0.15 MPa, a micro positive pressure of more than 20Pa in the hearth is formed, oxygen in the environment is prevented from entering the high-temperature hearth, and the filament bundle is ensured to be always in an inert atmosphere at high temperature during continuous filament traveling, so that the high-temperature carbonization furnace and graphitization furnace are suitable for continuous fiber production;
the pitch-based graphite fibers may be surface treated and sized as desired prior to being wound.
Example 1
The method comprises the following steps: raw silk dropping barrel
Uniformly spreading the coiled 1200 m 2k asphalt protofilaments into a stainless steel porous tray with the diameter of 800mm multiplied by 600mm multiplied by 250mm at the speed of 15m/min by a translation mechanism, wherein the filament withdrawal length is 500 m;
step two: batch pre-oxidation
Placing the stainless steel porous tray paved with the asphalt protofilaments into a hot air circulating furnace, heating to 160 ℃ from room temperature at a heating rate of 6 ℃ and preserving heat for 10min, then heating to 300 ℃ from 160 ℃ at a heating rate of 2 ℃/min and preserving heat for 20min, then powering off and naturally cooling, taking out, and continuously supplementing fresh air into the hot air circulating furnace at a flow rate of 30L/min during the heating, preserving heat and cooling period;
and the asphalt pre-oxidized fiber obtained in the step two is smooth and soft in appearance and free of broken fibers.
Step three: intermittent low-temp. charring
Putting the whole stainless steel porous tray filled with the pitch pre-oxidized fibers obtained in the second step into an inert atmosphere furnace, heating to 300 ℃ from room temperature at a heating rate of 8 ℃ and preserving heat for 10min, then heating to 900 ℃ at a heating rate of 8 ℃/min and preserving heat for 10min, then powering off and naturally cooling, taking out, and continuously introducing high-purity argon to keep the micro-positive pressure in a hearth in the heating, preserving heat and cooling process;
step four: continuous high-temperature carbonization, graphitization and rolling
And (3) drawing out the pitch carbon fibers obtained in the step three, sequentially feeding the pitch carbon fibers into a 950-1600 ℃ high-temperature carbonization furnace and a 2450 ℃ graphitization furnace at a wire feeding speed of 0.15m/min, applying 1% of positive traction during high-temperature carbonization, applying 2% of positive traction during graphitization, passing through a sizing tank and a drying furnace, and then rolling in a wire collecting machine to obtain the pitch-based graphite fiber filament.
The pitch-based graphite fiber obtained in this example had a density of 2.13g/cm3The strength is 1682MPa, the modulus is 659GPa, and the thermal conductivity is 314W/(K.m).
Example 2
The method comprises the following steps: raw silk dropping barrel
Uniformly spreading the coiled 1200 m 2k asphalt protofilaments into a stainless steel porous tray with the diameter of 800mm multiplied by 600mm multiplied by 250mm at the speed of 25m/min by a translation mechanism, wherein the filament withdrawal length is 500 m;
step two: batch pre-oxidation
Placing the stainless steel porous tray paved with the asphalt protofilaments into a hot air circulating furnace, heating to 160 ℃ from room temperature at a heating rate of 6 ℃ and preserving heat for 10min, then heating to 280 ℃ from 160 ℃ at a heating rate of 1.5 ℃/min and preserving heat for 20min, then powering off, naturally cooling and taking out, and continuously supplementing fresh air into the hot air circulating furnace at a flow rate of 30L/min during heating, preserving heat and reducing temperature;
and the asphalt pre-oxidized fiber obtained in the step two is smooth and soft in appearance and free of broken fibers.
Step three: intermittent low-temp. charring
Putting the whole stainless steel porous tray filled with the asphalt pre-oxidized fibers into an inert atmosphere furnace, heating to 300 ℃ from room temperature at a heating rate of 8 ℃ and preserving heat for 10min, then heating to 900 ℃ at a heating rate of 5 ℃/min and preserving heat for 10min, then powering off and naturally cooling, taking out, and continuously introducing high-purity argon to keep micro-positive pressure in a hearth in the heating, preserving heat and cooling process;
step four: continuous high-temperature carbonization, graphitization and rolling
And (3) drawing out the pitch carbon fibers obtained in the step three, sequentially feeding the pitch carbon fibers into a 950-1600 ℃ high-temperature carbonization furnace and a 2550 ℃ graphitization furnace at a wire feeding speed of 0.3m/min, applying 1% of positive traction during high-temperature carbonization, applying 3% of positive traction during graphitization, passing through a sizing tank and a drying furnace, and then rolling in a wire collecting machine to obtain the pitch-based graphite fiber filament.
The pitch-based graphite fiber obtained in this example had a density of 2.14g/cm3The strength was 2206MPa, the modulus was 762GPa, and the thermal conductivity was 462W/(m.K).
Example 3
The method comprises the following steps: raw silk dropping barrel
Uniformly spreading the coiled 1200 m 2k asphalt protofilament into a stainless steel porous tray with the diameter of 800mm multiplied by 600mm multiplied by 250mm at the speed of 35m/min by a translation mechanism, wherein the filament withdrawal length is 500 m;
step two: batch pre-oxidation
Placing the stainless steel porous tray paved with the asphalt protofilaments into a hot air circulating furnace, heating to 160 ℃ from room temperature at a heating rate of 6 ℃ and preserving heat for 10min, then heating to 280 ℃ from 160 ℃ at a heating rate of 1 ℃/min and preserving heat for 20min, then powering off and naturally cooling, taking out, and continuously supplementing fresh air into the hot air circulating furnace at a flow rate of 30L/min during the heating, preserving heat and cooling period;
the pitch pre-oxidized fibers obtained in the step two are smooth and soft in appearance and free of broken fibers;
step three: intermittent low-temp. charring
Putting the whole stainless steel porous tray filled with the asphalt pre-oxidized fibers into an inert atmosphere furnace, heating to 300 ℃ from room temperature at a heating rate of 8 ℃ and preserving heat for 10min, then heating to 900 ℃ at a heating rate of 5 ℃/min and preserving heat for 10min, then powering off and naturally cooling, taking out, and continuously introducing high-purity argon to keep micro-positive pressure in a hearth in the heating, preserving heat and cooling process;
step four: continuous high-temperature carbonization, graphitization and rolling
And (3) drawing out the pitch carbon fibers obtained in the step three, sequentially feeding the pitch carbon fibers into a 950-1600 ℃ high-temperature carbonization furnace and a 2650 ℃ graphitization furnace at a wire feeding speed of 0.6m/min, applying 1% of positive traction during high-temperature carbonization, applying 4% of positive traction during graphitization, passing through a sizing tank and a drying furnace, and then rolling in a wire collecting machine to obtain the pitch-based graphite fiber filament.
The pitch-based graphite fiber obtained in this example had a density of 2.15g/cm3The strength was 2537MPa, the modulus was 807GPa, and the thermal conductivity was 613W/(m.K).
Example 4
The method comprises the following steps: raw silk dropping barrel
Uniformly spreading the coiled 1200 m 2k asphalt protofilaments into a stainless steel porous tray with the diameter of 800mm multiplied by 600mm multiplied by 250mm at the speed of 25m/min by a translation mechanism, wherein the filament withdrawal length is 500 m;
step two: batch pre-oxidation
Placing the stainless steel porous tray paved with the asphalt protofilaments into a hot air circulating furnace, heating to 160 ℃ from room temperature at a heating rate of 5 ℃ and preserving heat for 10min, then heating to 320 ℃ from 160 ℃ at a heating rate of 0.5 ℃/min and preserving heat for 15min, then powering off, naturally cooling and taking out, and continuously supplementing fresh air into the hot air circulating furnace at a flow rate of 30L/min during heating, preserving heat and reducing temperature;
and the asphalt pre-oxidized fiber obtained in the step two is smooth and soft in appearance and free of broken fibers.
Step three: intermittent low-temp. charring
Putting the whole stainless steel porous tray filled with the pitch pre-oxidized fibers obtained in the second step into an inert atmosphere furnace, heating to 300 ℃ from room temperature at a heating rate of 5 ℃ and preserving heat for 10min, then heating to 900 ℃ at a heating rate of 2 ℃/min and preserving heat for 10min, then taking out after powering off and naturally cooling, and continuously introducing high-purity argon to keep micro-positive pressure in a hearth in the heating, preserving heat and cooling process;
step four: continuous high-temperature carbonization, graphitization and rolling
And (3) drawing out the pitch carbon fibers obtained in the step three, sequentially feeding the pitch carbon fibers into a high-temperature carbonization furnace at 950-1700 ℃ and a graphitization furnace at 2100 ℃ at a wire moving speed of 0.6m/min, applying 1% of positive draft during high-temperature carbonization, applying 6% of positive draft during graphitization, passing through a sizing tank and a drying furnace, and then rolling in a wire collecting machine to obtain the pitch-based graphite fiber filament.
The pitch-based graphite fiber obtained in this example had a density of 2.08g/cm3The strength was 1361MPa, the modulus was 426GPa, and the thermal conductivity was 206W/(m.K).
Example 5
The method comprises the following steps: raw silk dropping barrel
Uniformly spreading the coiled 1200 m 2k asphalt protofilaments into a stainless steel porous tray with the diameter of 800mm multiplied by 600mm multiplied by 250mm at the speed of 25m/min by a translation mechanism, wherein the filament withdrawal length is 500 m;
step two: batch pre-oxidation
Placing the stainless steel porous tray paved with the asphalt protofilaments into a hot air circulating furnace, heating to 160 ℃ from room temperature at a heating rate of 10 ℃ and preserving heat for 10min, then heating to 310 ℃ from 160 ℃ at a heating rate of 10 ℃/min and preserving heat for 20min, then powering off and naturally cooling, taking out, and continuously supplementing fresh air into the hot air circulating furnace at a flow rate of 30L/min during the heating, preserving heat and cooling period;
and the asphalt pre-oxidized fiber obtained in the step two is smooth and soft in appearance and free of broken fibers.
Step three: intermittent low-temp. charring
Putting the whole stainless steel porous tray filled with the pitch pre-oxidized fibers obtained in the second step into an inert atmosphere furnace, heating to 300 ℃ from room temperature at a heating rate of 10 ℃ and preserving heat for 10min, then heating to 900 ℃ at a heating rate of 10 ℃/min and preserving heat for 15min, then powering off and naturally cooling, taking out, and continuously introducing high-purity argon gas to keep the micro-positive pressure in a hearth in the heating, preserving heat and cooling process;
step four: continuous high-temperature carbonization, graphitization and rolling
And (3) drawing out the pitch carbon fibers obtained in the step three, sequentially feeding the pitch carbon fibers into a 950-1750 ℃ high-temperature carbonization furnace and a 2200 ℃ graphitization furnace at a wire feeding speed of 0.8m/min, applying 1% of positive traction during high-temperature carbonization, applying 8% of positive traction during graphitization, passing through a sizing tank and a drying furnace, and then rolling in a wire collecting machine to obtain the pitch-based graphite fiber filament.
The pitch-based graphite fiber obtained in this example had a density of 2.03g/cm3The strength was 1257MPa, the modulus was 437GPa, and the thermal conductivity was 193W/(m.K).
Example 6
The method comprises the following steps: raw silk dropping barrel
Uniformly spreading the coiled 1200 m 2k asphalt protofilaments into a stainless steel porous tray with the diameter of 800mm multiplied by 600mm multiplied by 250mm at the speed of 25m/min by a translation mechanism, wherein the filament withdrawal length is 500 m;
step two: batch pre-oxidation
Placing the stainless steel porous tray paved with the asphalt protofilaments into a hot air circulating furnace, heating to 160 ℃ from room temperature at a heating rate of 8 ℃ and preserving heat for 10min, then heating to 290 ℃ from 160 ℃ at a heating rate of 6 ℃/min and preserving heat for 15min, then powering off, naturally cooling and taking out, and continuously supplementing fresh air into the hot air circulating furnace at a flow rate of 30L/min during the heating, preserving heat and cooling period;
and the asphalt pre-oxidized fiber obtained in the step two is smooth and soft in appearance and free of broken fibers.
Step three: intermittent low-temp. charring
Putting the whole stainless steel porous tray filled with the pitch pre-oxidized fibers obtained in the second step into an inert atmosphere furnace, heating to 300 ℃ from room temperature at a heating rate of 7 ℃ and preserving heat for 10min, then heating to 900 ℃ at a heating rate of 6 ℃/min and preserving heat for 20min, then powering off and naturally cooling, taking out, and continuously introducing high-purity argon to keep the micro-positive pressure in a hearth in the heating, preserving heat and cooling process;
step four: continuous high-temperature carbonization, graphitization and rolling
And (3) drawing out the pitch carbon fibers obtained in the step three, sequentially feeding the pitch carbon fibers into a high-temperature carbonization furnace at 950-1800 ℃ and a graphitization furnace at 2300 ℃ at a wire moving speed of 1.0m/min, applying 1% of positive draft during high-temperature carbonization, applying 6% of positive draft during graphitization, passing through a sizing tank and a drying furnace, and then winding in a wire collecting machine to obtain the pitch-based graphite fiber filament.
The pitch-based graphite fiber obtained in this example had a density of 2.05g/cm3The strength is 1584MPa, the modulus is 552GPa, and the thermal conductivity is 269W/(m.K).
TABLE 1 Properties of Pitch-based graphite fiber filaments prepared in examples 1-6
After the mesophase pitch-based carbon fibers are melt-spun to form precursor fibers, the precursor fibers need to be subjected to the procedures of pre-oxidation, carbonization, graphitization and the like, and the precursor fibers can form a uniform and compact graphitized crystal structure to obtain excellent fiber performance. The method comprises the steps of uniformly paving asphalt protofilaments into a porous tray according to a certain rule, then placing the tray with the asphalt protofilaments in a hot air circulating furnace to be pre-oxidized at the final temperature of 280-320 ℃ by taking air as a medium, placing the tray in an inert atmosphere furnace to be carbonized at the low temperature of 900 ℃ after the pre-oxidation is finished, pumping asphalt tows out after the low-temperature carbonization is finished, and treating and rolling the asphalt tows in a continuous high-temperature carbonization furnace and a graphitization furnace to obtain an asphalt-based graphite fiber finished product, wherein the modulus of the asphalt-based graphite fiber can reach more than 800 GPa. The invention combines the advantages of the batch type and the continuous type, improves the production efficiency and is suitable for the engineering large-scale production.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (4)
1. A method for preparing pitch-based graphite fiber filaments in an intermittent and continuous mode is characterized by comprising the following steps:
the method comprises the following steps: raw silk dropping barrel
Laying the asphalt protofilaments into a porous tray;
step two: batch pre-oxidation
Pre-oxidizing the porous tray paved with the asphalt protofilaments in a hot air circulating furnace; wherein, the specific conditions of the pre-oxidation are as follows: pre-oxidizing at the final temperature of 280-320 ℃ for 10-20 min; step three: intermittent low-temp. charring
Carrying out low-temperature carbonization on the pitch pre-oxidized fiber obtained in the step two in an inert atmosphere furnace; wherein, the specific conditions of the low-temperature carbonization are as follows: carbonizing at 900 ℃ for 10-20 min; wherein the temperature is increased from 300 ℃ to 900 ℃ at the temperature increase rate of 2-10 ℃/min; the low-temperature carbonization is carried out in an inert atmosphere furnace, argon or nitrogen is introduced into the inert atmosphere furnace, and the flow rate of the argon or the nitrogen is 40-80L/min, so that the micro-positive pressure of 500-2000 Pa is achieved in the inert atmosphere furnace;
step four: obtaining the pitch-based graphite fiber filament through continuous high-temperature carbonization, continuous graphitization and rolling;
continuous high-temperature carbonization is carried out in a high-temperature carbonization furnace, continuous graphitization is carried out in a graphitization furnace, the inlet and outlet of the high-temperature carbonization furnace and the graphitization furnace are in open structures, the hearth is separated from the atmosphere by 3-4 vertically symmetrical nitrogen or argon gas curtains at the furnace mouth, the inlet pressure of the nitrogen or argon gas is 0.1-0.15 MPa, and the micro positive pressure of more than 20Pa in the hearth is formed;
the pitch carbon fiber carbonized in the third step sequentially enters a high-temperature carbonization furnace and a graphitization furnace at a filament traveling speed of 0.15-1.0 m/min;
applying 1% -9% drafting amount in the process of running.
2. A method for preparing pitch-based graphite fiber filament according to claim 1, wherein pitch precursor is laid on a porous tray by a translation or rotation mechanism at an unwinding speed of 5-40 m/min.
3. The method of claim 1, wherein in the second step, the temperature is increased from 160 ℃ to 280-320 ℃ at a temperature increase rate of 0.5-10 ℃/min.
4. The method according to claim 1, wherein the temperature deviation in the effective temperature range of the hot air circulating furnace is not more than ± 2.5 ℃, and the air speed is less than 2.5 m/s.
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| CN114164524A (en) * | 2020-09-11 | 2022-03-11 | 宝武炭材料科技有限公司 | Efficient pre-oxidation method of general-purpose asphalt-based non-woven felt |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088420A (en) * | 2015-09-14 | 2015-11-25 | 陕西天策新材料科技有限公司 | Preparation method for high-heat-conduction asphalt graphite fibers |
| CN105734723A (en) * | 2016-03-25 | 2016-07-06 | 山东瑞城宇航碳材料有限公司 | Method for manufacturing ultrahigh-modulus graphite fiber continuous filament from coal tar |
| CN105887245A (en) * | 2016-06-22 | 2016-08-24 | 湖南大学 | Preparation method of continuous high-performance intermediate-phase asphalt-based carbon fiber |
-
2018
- 2018-02-09 CN CN201810135906.2A patent/CN108251919B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088420A (en) * | 2015-09-14 | 2015-11-25 | 陕西天策新材料科技有限公司 | Preparation method for high-heat-conduction asphalt graphite fibers |
| CN105734723A (en) * | 2016-03-25 | 2016-07-06 | 山东瑞城宇航碳材料有限公司 | Method for manufacturing ultrahigh-modulus graphite fiber continuous filament from coal tar |
| CN105887245A (en) * | 2016-06-22 | 2016-08-24 | 湖南大学 | Preparation method of continuous high-performance intermediate-phase asphalt-based carbon fiber |
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