CN103014919B - Preparation method of general purpose pitch-based carbon fiber - Google Patents
Preparation method of general purpose pitch-based carbon fiber Download PDFInfo
- Publication number
- CN103014919B CN103014919B CN201210590858.9A CN201210590858A CN103014919B CN 103014919 B CN103014919 B CN 103014919B CN 201210590858 A CN201210590858 A CN 201210590858A CN 103014919 B CN103014919 B CN 103014919B
- Authority
- CN
- China
- Prior art keywords
- pitch
- carbon fiber
- preparation
- autoclave
- asphalt
- 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
Landscapes
- Inorganic Fibers (AREA)
Abstract
The invention relates to a preparation method of a general purpose pitch-based carbon fiber. The preparation method has the beneficial effects that isotropic pitch with high softening point and excellent spinnability is obtained through the comprehensive treatment technologies such as heat treatment, heat filtration, reduced pressure distillation, oxidation treatment and modification with an additive and then the general purpose pitch-based carbon fiber is prepared through melt spinning, non-melting treatment and carbonization treatment; the pitch blended by the method is low in heteroatom content, narrow in molecular weight distribution and high in carbon content, contains defined amount of short alkyl side chains and can solve the technical problems that the melt spinning materials are brittle and are not easy to operate and non-melting treatment costs long time; the carbon fiber prepared by the method has good quality, high strength and good continuity; and the preparation method is simple in process, mild in reaction conditions and low in environmental pollution and is applicable to industrial production.
Description
Technical field
The present invention relates to the preparing technical field of carbon fiber, particularly relate to a kind of preparation method of universal pitch-based carbon fiber.
Background technology
Asphalt base carbon fiber refers to that the material that is rich in condensed-nuclei aromatics taking pitch etc. is as raw material, by polymerization, spinning, do not melt, a based carbon fiber prepared by carbonization treatment, be divided into again general purpose grade asphalt-based carbon fiber and high-performance asphalt-based carbon fiber by the difference of its performance, the former is prepared by isotropic pitch, claim again isotropic pitch grade carbon fiber, the latter is by the mesophase pitch preparation of setting out, therefore be called again mesophase pitch grade carbon fiber.The process spinning such as polyvinyl chloride pyrolyzed bitumen, lignin pitch, coal tar asphalt and petroleum residual oil pitch, do not melt, carbonization treatment all can be made into carbon fiber.Wherein forerunner's raw material of asphalt base carbon fiber is cheap, and source is abundant, and carbonization rate is also high than polyacrylonitrile fibre, for the exploitation of asphalt base carbon fiber provide effective guarantee.The strength and modulus of general purpose grade asphalt-based carbon fiber is all far short of what is expected compared with PAN base carbon fibre, can not be used as the reinforcing material of aircraft, physical culture and entertainment article, but for concrete, can improve 5～10 times of concrete intensity, counter-bending toughness improves several times to 50 times, can save steel, attenuate structure, parts quality is alleviated, be beneficial to construction.
The key technology of preparation general purpose grade asphalt-based carbon fiber is modulation melt spinning presoma pitch.Prepare that precursor pitch requirement raw material has hetero atom and ash impurities content is low, carbon content is high, need to there is certain rheological property to meet the demand of spinning, also require to there is higher chemical reactivity to meet the not needs fiber of melt processed simultaneously, require the softening point of material asphalt high, good spinnability, contain alkyl side chain simultaneously.
In prior art, normally adopt the processing of polycondensation reaction method, can effectively improve pitch condensed-nuclei aromatics condensation level, but when phase crystallite and mother liquor isotropic pitch coexist in the middle of the anisotropy that the excessive polycondensation of liquid phase carbonisation forms is also, reduce the spinnability of melt; Another kind is to process by oxidation cross-linked method, and by carrying out oxidation reaction after pitch heat treatment, to improve the condensation degree of dissolved of pitch, but the spinnability of this kind of method is also very low, and difficulty in spinning is difficult to meet the demand of suitability for industrialized production.
Summary of the invention
In order to overcome existing deficiency in universal pitch-based carbon fiber preparation process of the prior art, the invention provides that a kind of pitch spinnability is good, softening point is high, the preparation method of the universal pitch-based carbon fiber that spinning quality is good.
The present invention solves the problems of the technologies described above adopted technical scheme and is made up of following steps:
(1) heat treatment
Coal tar soft asphalt is placed in to autoclave and under nitrogen protection, is heated to 360～440 DEG C, nitrogen flow is 70～100mL/min, and mixing speed 300～400r/min stirs, reaction 30～90min;
(2) heat filtering
The product of step (1) is left standstill to 15～40min to be separated with coking component to top pitch, pour top pitch in heat filtering still 300～600 mesh filter screens, controlling temperature is 330～400 DEG C, and pressure is 0.01～1.0MPa, removes the coking component in pitch;
(3) decompression distillation
The pitch that step (2) is removed to coking component be placed in vacuum Wei ?0.5～?the autoclave of 0.096MPa, be heated to 300～400 DEG C, constant temperature leaves standstill to lights removal;
(4) oxidation processes
After lights removal, in autoclave, pass into air, air mass flow is 0.1～1.0mL/min.g, mixing speed 300～400r/min, and oxidation reaction 30～200min, obtains oxidized asphalt;
(5) additive agent modified oxidized asphalt
In autoclave, pass into nitrogen purge, stir and be cooled to 280～380 DEG C, under nitrogen protection, add property-modifying additive, the mass ratio of oxidized asphalt and property-modifying additive is 1:0.001～0.05, mixes, and obtains modified pitch;
Any one or its any combination in the polyvinyl chloride that the polyvinyl butyral resin that above-mentioned property-modifying additive is number-average molecular weight is 12000 acrylonitrile-butadiene-styrene copolymer, number-average molecular weight is 13000 ethylene-vinyl acetate copolymer, number-average molecular weight is 10300, the polyvinyl alcohol that number-average molecular weight is 77000 and number-average molecular weight are 50500;
(6) melt spinning
Modified pitch is packed in melt spinning still, the spinnerets of melt spinning still is that aperture is the single hole spinnerets of 0.3～0.8mm, be heated to 300～350 DEG C, constant temperature leaves standstill to modified pitch and is molten, spray from spinneret orifice according to conventional melt spinning method, drawing-off top roll, drafting rate is 300～800m/min, is prepared into as-spun fibre;
(7) carbon fiber preparation
As-spun fibre is fixed on poroid graphite cake; keep straight configuration to put into tube furnace; pass into air; be heated to 300～350 DEG C with the heating rate of 0.5 DEG C/min, isothermal reaction 1～2h, obtains fusion-free fibre; by nitrogen purge; under nitrogen protection, be heated to 1000～1200 DEG C with the heating rate of 5 DEG C/min, constant temperature leaves standstill 30～60min, obtains asphalt base carbon fiber.
When above-mentioned steps (1) heat treatment, coal tar soft asphalt is placed in to autoclave, is heated to 380～400 DEG C under nitrogen protection, nitrogen flow is 80～90mL/min, and mixing speed 300～400r/min stirs, reaction 50～80min.
When above-mentioned steps (2) heat filtering, the product of step (1) is left standstill to 15～40min, top pitch separates with coking component, top pitch is poured in heat filtering still, the screen pack of heat filtering still is 400～600 orders, temperature is 350～390 DEG C, and pressure is 0.1～0.8MPa, removes the coking component in the pitch of top.
When above-mentioned steps (3) decompression distillation, the pitch that step (2) is removed to coking component be placed in vacuum Wei ?0.5～?the autoclave of 0.096MPa, be heated to 320～360 DEG C, constant temperature leaves standstill to lights removal.
When the additive agent modified oxidized asphalt of above-mentioned steps (5); in autoclave, pass into nitrogen purge; stirring is cooled to 280～380 DEG C; under nitrogen protection, add property-modifying additive; the mass ratio of oxidized asphalt and property-modifying additive is 1:0.002～0.04; mix, obtain modified pitch.
When the additive agent modified oxidized asphalt of above-mentioned steps (5), in autoclave, pass into nitrogen purge, stir and be cooled to 280～380 DEG C; under nitrogen protection, add property-modifying additive; the mass ratio of oxidized asphalt and property-modifying additive is 1:0.025, mixes, and obtains modified pitch.
The preparation method of universal pitch-based carbon fiber of the present invention is by heat treatment, heat filtering, decompression distillation, oxidation processes and the comprehensive treatment technique such as additive agent modified, obtain the good high softening-point isotropic pitch of spinnability, again through melt spinning, not melt processed and carbonization treatment, be prepared into universal pitch-based carbon fiber, the pitch content of heteroatoms that method of the present invention is modulated is low, narrow molecular weight distribution, phosphorus content is high and contain appropriate short alkyl side chain, can solve melt-spun material crisp not easy to operate, the not melt processed long technical barrier that waits consuming time, and the prepared carbon fiber quality of method of the present invention is good, intensity is high, can continuity good, and preparation process is simple, reaction condition gentleness, low in the pollution of the environment, be suitable for suitability for industrialized production application.
Brief description of the drawings
Fig. 1 is the made carbon fiber photo of embodiment 1.
Fig. 2 is the made carbon fiber photo of comparative example 1.
Fig. 3 be universal pitch-based carbon fiber La prepared by embodiment 1 stretch Qiang Du ?the relation curve of diameter.
Detailed description of the invention
Now technical scheme of the present invention is further described, but the present invention is not limited only to following embodiment in conjunction with the embodiments.
Embodiment 1
Get 150g as example taking raw material coal tar soft asphalt, the method for preparing universal pitch-based carbon fiber is made up of following steps:
(1) heat treatment
Get softening point and be the coal tar soft asphalt 150g of 59 DEG C, be placed in autoclave, be heated to 390 DEG C under nitrogen protection, nitrogen flow is 85mL/min, and mixing speed 350r/min stirs, reaction 60min.
(2) heat filtering
The product of step (1) is left standstill to 30min, and top pitch separates with coking component, and top pitch is poured in heat filtering still, the screen pack of heat filtering still is 600 orders, temperature is 360 DEG C, and pressure is 0.5MPa, removes the coking component in the pitch of top.
(3) decompression distillation
The pitch that step (2) is removed to coking component be placed in vacuum Wei ?the autoclave of 0.1MPa, be heated to 340 DEG C, constant temperature is to lights removal.
(4) oxidation processes
The backward autoclave of lights removal passes into air, and air mass flow is 0.5mL/min.g, mixing speed 350r/min, and reaction 90min, carries out oxidation processes, obtains oxidized asphalt.
(5) additive agent modified oxidized asphalt
In autoclave, pass into nitrogen purge, stir and be cooled to 300 DEG C, under nitrogen protection, adding 3.75g number-average molecular weight is 50500 polyvinyl chloride, and the mass ratio of oxidized asphalt and polyvinyl chloride is 1:0.025, mixes, and obtains modified pitch.
(6) melt spinning
Modified pitch is packed in melt spinning still, the spinnerets of melt spinning still is that aperture is the single hole spinnerets of 0.4mm, be heated to 320 DEG C, constant temperature to modified pitch is molten, spray from spinneret orifice according to conventional melt spinning method, drawing-off top roll, drafting rate is 600m/min, is prepared into as-spun fibre.
(7) carbon fiber preparation
As-spun fibre is fixed on porous graphite plate; keep straight configuration to put into tube furnace; pass into air; be heated to 320 DEG C with the heating rate of 0.5 DEG C/min, constant temperature 1.5h, obtains fusion-free fibre; by nitrogen purge; under nitrogen protection, be heated to 1100 DEG C with the heating rate of 5 DEG C/min, constant temperature 35min, obtains asphalt base carbon fiber.Can reach 12.5786 μ m with its diameter of microscopic.
Embodiment 2
Get 150g as example taking raw material coal tar soft asphalt, the method for preparing universal pitch-based carbon fiber is made up of following steps:
(1) heat treatment
Get softening point and be the coal tar soft asphalt 150g of 59 DEG C, be placed in autoclave, be heated to 380 DEG C under nitrogen protection, nitrogen flow is 80mL/min, and mixing speed 300r/min stirs, reaction 80min.
(2) heat filtering
The product of step (1) is left standstill to 15min, and top pitch separates with coking component, and top pitch is poured in heat filtering still, the screen pack of heat filtering still is 400 orders, temperature is 350 DEG C, and pressure is 0.8MPa, removes the coking component in the pitch of top.
(3) decompression distillation
The pitch that step (2) is removed to coking component be placed in vacuum Wei ?the autoclave of 0.096MPa, be heated to 320 DEG C, constant temperature is to lights removal.
(4) oxidation processes
The backward autoclave of lights removal passes into air, and air mass flow is 0.1mL/min.g, mixing speed 300r/min, and reaction 180min, carries out oxidation processes, obtains oxidized asphalt.
(5) additive agent modified oxidized asphalt
In autoclave, pass into nitrogen purge, stir and be cooled to 280 DEG C, under nitrogen protection, adding 3.75g number-average molecular weight is 50500 polyvinyl chloride, and the mass ratio of oxidized asphalt and polyvinyl chloride is 1:0.025, mixes, and obtains modified pitch.
(6) melt spinning
Modified pitch is packed in melt spinning still, the spinnerets of melt spinning still is that aperture is the single hole spinnerets of 0.4mm, be heated to 320 DEG C, constant temperature to modified pitch is molten, spray from spinneret orifice according to conventional melt spinning method, drawing-off top roll, drafting rate is 400m/min, is prepared into as-spun fibre.
(7) carbon fiber preparation
As-spun fibre is fixed on porous graphite plate; keep straight configuration to put into tube furnace; pass into air; be heated to 320 DEG C with the heating rate of 0.5 DEG C/min, constant temperature 2h, obtains fusion-free fibre; by nitrogen purge; under nitrogen protection, be heated to 1100 DEG C with the heating rate of 5 DEG C/min, constant temperature 35min, obtains asphalt base carbon fiber.
Embodiment 3
Get 150g as example taking raw material coal tar soft asphalt, the method for preparing universal pitch-based carbon fiber is made up of following steps:
(1) heat treatment
Get softening point and be the coal tar soft asphalt 150g of 59 DEG C, be placed in autoclave, be heated to 400 DEG C under nitrogen protection, nitrogen flow is 90mL/min, and mixing speed 400r/min stirs, reaction 50min.
(2) heat filtering
The product of step (1) is left standstill to 40min, and top pitch separates with coking component, and top pitch is poured in heat filtering still, the screen pack of heat filtering still is 400 orders, temperature is 390 DEG C, and pressure is 0.1MPa, removes the coking component in the pitch of top.
(3) decompression distillation
The pitch that step (2) is removed to coking component be placed in vacuum Wei ?the autoclave of 0.5MPa, be heated to 360 DEG C, constant temperature is to lights removal.
(4) oxidation processes
The backward autoclave of lights removal passes into air, and air mass flow is 1.0mL/min.g, mixing speed 400r/min, and reaction 60min, carries out oxidation processes, obtains oxidized asphalt.
(5) additive agent modified oxidized asphalt
In autoclave, pass into nitrogen purge, stir and be cooled to 380 DEG C, under nitrogen protection, adding 3.75g number-average molecular weight is 50500 polyvinyl chloride, and the mass ratio of oxidized asphalt and polyvinyl chloride is 1:0.025, mixes, and obtains modified pitch.
(6) melt spinning
Modified pitch is packed in melt spinning still, the spinnerets of melt spinning still is that aperture is the single hole spinnerets of 0.8mm, be heated to 340 DEG C, constant temperature to modified pitch is molten, spray from spinneret orifice according to conventional melt spinning method, drawing-off top roll, drafting rate is 600m/min, is prepared into as-spun fibre.
(7) carbon fiber preparation
As-spun fibre is fixed on porous graphite plate; keep straight configuration to put into tube furnace; pass into air; be heated to 340 DEG C with the heating rate of 0.5 DEG C/min, constant temperature 1.5h, obtains fusion-free fibre; by nitrogen purge; under nitrogen protection, be heated to 1000 DEG C with the heating rate of 5 DEG C/min, constant temperature 50min, obtains asphalt base carbon fiber.
Embodiment 4
Get 150g as example taking raw material coal tar soft asphalt, the method for preparing universal pitch-based carbon fiber is made up of following steps:
(1) heat treatment
Get softening point and be the coal tar soft asphalt 150g of 59 DEG C, be placed in autoclave, be heated to 360 DEG C under nitrogen protection, nitrogen flow is 70mL/min, and mixing speed 300r/min stirs, reaction 90min.
(2) heat filtering
The product of step (1) is left standstill to 15min, and top pitch separates with coking component, and top pitch is poured in heat filtering still, the screen pack of heat filtering still is 300 orders, temperature is 330 DEG C, and pressure is 1.0MPa, removes the coking component in the pitch of top.
(3) decompression distillation
The pitch that step (2) is removed to coking component be placed in vacuum Wei ?the autoclave of 0.5MPa, be heated to 300 DEG C, constant temperature is to lights removal.
(4) oxidation processes
The backward autoclave of lights removal passes into air, and air mass flow is 0.1mL/min.g, mixing speed 300r/min, and reaction 200min, carries out oxidation processes, obtains oxidized asphalt.
(5) additive agent modified oxidized asphalt
In autoclave, pass into nitrogen purge, stir and be cooled to 280 DEG C, under nitrogen protection, adding number-average molecular weight is 50500 polyvinyl chloride, and the mass ratio of oxidized asphalt and polyvinyl chloride is 1:0.025, mixes, and obtains modified pitch.
(6) melt spinning
Modified pitch is packed in melt spinning still, the spinnerets of melt spinning still is that aperture is the single hole spinnerets of 0.3mm, be heated to 300 DEG C, constant temperature to modified pitch is molten, spray from spinneret orifice according to conventional melt spinning method, drawing-off top roll, drafting rate is 300m/min, is prepared into as-spun fibre.
(7) carbon fiber preparation
As-spun fibre is fixed on porous graphite plate; keep straight configuration to put into tube furnace; pass into air; be heated to 300 DEG C with the heating rate of 0.5 DEG C/min, constant temperature 2h, obtains fusion-free fibre; by nitrogen purge; under nitrogen protection, be heated to 1000 DEG C with the heating rate of 5 DEG C/min, constant temperature 60min, obtains asphalt base carbon fiber.
Embodiment 5
Get 150g as example taking raw material coal tar soft asphalt, the method for preparing universal pitch-based carbon fiber is made up of following steps:
(1) heat treatment
Get softening point and be the coal tar soft asphalt 150g of 59 DEG C, be placed in autoclave, be heated to 440 DEG C under nitrogen protection, nitrogen flow is 100mL/min, and mixing speed 400r/min stirs, reaction 30min.
(2) heat filtering
The product of step (1) is left standstill to 40min, and top pitch separates with coking component, and top pitch is poured in heat filtering still, the screen pack of heat filtering still is 600 orders, temperature is 400 DEG C, and pressure is 0.01MPa, removes the coking component in the pitch of top.
(3) decompression distillation
The pitch that step (2) is removed to coking component be placed in vacuum Wei ?the autoclave of 0.096MPa, be heated to 400 DEG C, constant temperature is to lights removal.
(4) oxidation processes
The backward autoclave of lights removal passes into air, and air mass flow is 1.0mL/min.g, mixing speed 400r/min, and reaction 30min, carries out oxidation processes, obtains oxidized asphalt.
(5) additive agent modified oxidized asphalt
In autoclave, pass into nitrogen purge, stir and be cooled to 380 DEG C, under nitrogen protection, adding number-average molecular weight is 50500 polyvinyl chloride, and the mass ratio of oxidized asphalt and polyvinyl chloride is 1:0.025, mixes, and obtains modified pitch.
(6) melt spinning
Modified pitch is packed in melt spinning still, the spinnerets of melt spinning still is that aperture is the single hole spinnerets of 0.8mm, be heated to 350 DEG C, constant temperature to modified pitch is molten, spray from spinneret orifice according to conventional melt spinning method, drawing-off top roll, drafting rate is 800m/min, is prepared into as-spun fibre.
(7) carbon fiber preparation
As-spun fibre is fixed on porous graphite plate; keep straight configuration to put into tube furnace; pass into air; be heated to 350 DEG C with the heating rate of 0.5 DEG C/min, constant temperature 1h, obtains fusion-free fibre; by nitrogen purge; under nitrogen protection, be heated to 1200 DEG C with the heating rate of 5 DEG C/min, constant temperature 30min, obtains asphalt base carbon fiber.
Embodiment 6
In the preparation method of the universal pitch-based carbon fiber of above-described embodiment 1～5; in step (5); under nitrogen protection, adding number-average molecular weight is 50500 polyvinyl chloride; the mass ratio of oxidized asphalt and polyvinyl chloride is 1:0.002; in this step, other operation is identical with corresponding embodiment; other step is identical with corresponding embodiment, makes asphalt base carbon fiber.
Embodiment 7
In the preparation method of the universal pitch-based carbon fiber of above-described embodiment 1～5; in step (5); under nitrogen protection, adding number-average molecular weight is 50500 polyvinyl chloride; the mass ratio of oxidized asphalt and polyvinyl chloride is 1:0.04; in this step, other operation is identical with corresponding embodiment; other step is identical with corresponding embodiment, makes asphalt base carbon fiber.
Embodiment 8
In the preparation method of the universal pitch-based carbon fiber of above-described embodiment 1～5; in step (5); under nitrogen protection, adding number-average molecular weight is 50500 polyvinyl chloride; the mass ratio of oxidized asphalt and polyvinyl chloride is 1:0.05; in this step, other operation is identical with corresponding embodiment; other step is identical with corresponding embodiment, makes asphalt base carbon fiber.
Embodiment 9
In the preparation method of the universal pitch-based carbon fiber of above-described embodiment 1～5; in step (5); under nitrogen protection, adding number-average molecular weight is 50500 polyvinyl chloride; the mass ratio of oxidized asphalt and polyvinyl chloride is 1:0.001; in this step, other operation is identical with corresponding embodiment; other step is identical with corresponding embodiment, makes asphalt base carbon fiber.
Embodiment 10
In the preparation method of the universal pitch-based carbon fiber of above-described embodiment 1～9, the number-average molecular weight in step (5) be 50500 polyvinyl chloride can with on market, sell etc. any one is replaced in the mass number average molecular weight acrylonitrile-butadiene-styrene copolymer that is 12000, ethylene-vinyl acetate copolymer that number-average molecular weight is 13000, polyvinyl butyral resin that number-average molecular weight is 10300, polyvinyl alcohol that number-average molecular weight is 77000.Other raw material and proportioning are identical with corresponding embodiment, and other step is identical with corresponding embodiment.
Embodiment 11
In the preparation method of the universal pitch-based carbon fiber of above-described embodiment 1～9, property-modifying additive number-average molecular weight in step (5) is that 50500 polyvinyl chloride can be that the property-modifying additive that ethylene-vinyl acetate copolymer that 12000 acrylonitrile-butadiene-styrene copolymer and number-average molecular weight are 13000 is the quality such as 1:1 is mixed into according to mass ratio is replaced with selling number-average molecular weight on market, or also can number-average molecular weight any combination of the polyvinyl butyral resin that is 10300, polyvinyl alcohol that number-average molecular weight is 77000 replace.Other raw material and proportioning are identical with corresponding embodiment, and other step is identical with corresponding embodiment.
Other step is identical with corresponding embodiment, makes asphalt base carbon fiber.
In order to verify beneficial effect of the present invention, inventor compares the preparation method of the asphalt base carbon fiber preparation method of embodiment 1 and following comparative example 1, specific as follows:
Comparative example 1: get 150g as example taking raw material coal tar soft asphalt, adopt the step (1) in embodiment 1, step (4), step (6), step (7) is prepared into carbon fiber.
1, carbon fiber prepared embodiment 1 and the prepared carbon fiber of comparative example 1 are taken to its surface topography photo with camera respectively, referring to Fig. 1 and Fig. 2.
Can be found out by Fig. 1 and Fig. 2 contrast, the prepared asphalt base carbon fiber of embodiment 1 is thin and evenly and have continuity, and fiber thickness prepared by comparative example 1 is inhomogeneous and without continuity.
2, the prepared carbon fiber of embodiment 1 having been measured to carbon fiber by Dynamic Viscoelastic spectrometer (DMA) draws and stretches strong degree ?diametral curve relational result referring to Fig. 3.
As shown in Figure 3, in the time that diameter is 12.5 μ m, the TENSILE STRENGTH of carbon fiber wire can reach 1100MPa, in the time that diameter is 15.5 μ m, TENSILE STRENGTH reaches 850MPa, and along with the increase of diameter, TENSILE STRENGTH reduces gradually, therefore, the diameter of carbon fiber is thinner, and TENSILE STRENGTH is larger.
Claims (6)
1. a preparation method for universal pitch-based carbon fiber, is characterized in that being made up of following steps:
(1) heat treatment
Coal tar soft asphalt is placed in to autoclave and under nitrogen protection, is heated to 360～440 DEG C, nitrogen flow is 70～100mL/min, and mixing speed 300～400r/min stirs, reaction 30～90min;
(2) heat filtering
The product of step (1) is left standstill to 15～40min to be separated with coking component to top pitch, pour top pitch in heat filtering still 300～600 mesh filter screens, controlling temperature is 330～400 DEG C, and pressure is 0.01～1.0MPa, removes the coking component in pitch;
(3) decompression distillation
The pitch that step (2) is removed to coking component is placed in the autoclave that vacuum is-0.5～-0.096MPa, is heated to 300～400 DEG C, and constant temperature leaves standstill to lights removal;
(4) oxidation processes
After lights removal, in autoclave, pass into air, air mass flow is 0.1～1.0mL/min.g, mixing speed 300～400r/min, and oxidation reaction 30～200min, obtains oxidized asphalt;
(5) additive agent modified oxidized asphalt
In autoclave, pass into nitrogen purge, stir and be cooled to 280～380 DEG C, under nitrogen protection, add property-modifying additive, the mass ratio of oxidized asphalt and property-modifying additive is 1:0.001～0.05, mixes, and obtains modified pitch;
Any one or its any combination in the polyvinyl butyral resin that above-mentioned property-modifying additive is number-average molecular weight is 12000 acrylonitrile-butadiene-styrene copolymer, number-average molecular weight is 13000 ethylene-vinyl acetate copolymer, number-average molecular weight is 10300, the polyvinyl alcohol that number-average molecular weight is 77000, polyvinyl chloride that number-average molecular weight is 50500;
(6) melt spinning
Modified pitch is packed in melt spinning still, the spinnerets of melt spinning still is that aperture is the single hole spinnerets of 0.3～0.8mm, be heated to 300～350 DEG C, constant temperature leaves standstill to modified pitch and is molten, spray from spinneret orifice according to conventional melt spinning method, drawing-off top roll, drafting rate is 300～800m/min, is prepared into as-spun fibre;
(7) carbon fiber preparation
As-spun fibre is fixed on poroid graphite cake; keep straight configuration to put into tube furnace; pass into air; be heated to 300～350 DEG C with the heating rate of 0.5 DEG C/min, isothermal reaction 1～2h, obtains fusion-free fibre; by nitrogen purge; under nitrogen protection, be heated to 1000～1200 DEG C with the heating rate of 5 DEG C/min, constant temperature leaves standstill 30～60min, obtains asphalt base carbon fiber.
2. the preparation method of universal pitch-based carbon fiber according to claim 1; it is characterized in that: when described step (1) heat treatment; coal tar soft asphalt is placed in to autoclave; under nitrogen protection, be heated to 380～400 DEG C; nitrogen flow is 80～90mL/min; mixing speed 300～400r/min, stirs, reaction 50～80min.
3. the preparation method of universal pitch-based carbon fiber according to claim 1, it is characterized in that: when described step (2) heat filtering, the product of step (1) is left standstill to 15～40min, top pitch separates with coking component, top pitch is poured in heat filtering still, and the screen pack of heat filtering still is 400～600 orders, and temperature is 350～390 DEG C, pressure is 0.1～0.8MPa, removes the coking component in the pitch of top.
4. the preparation method of universal pitch-based carbon fiber according to claim 1, it is characterized in that: when described step (3) decompression distillation, the pitch that step (2) is removed to coking component is placed in the autoclave that vacuum is-0.5～-0.096MPa, be heated to 320～360 DEG C, constant temperature leaves standstill to lights removal.
5. the preparation method of universal pitch-based carbon fiber according to claim 1; it is characterized in that: when the additive agent modified oxidized asphalt of described step (5); in autoclave, pass into nitrogen purge; stirring is cooled to 280～380 DEG C; under nitrogen protection, add property-modifying additive; the mass ratio of oxidized asphalt and property-modifying additive is 1:0.002～0.04, mixes, and obtains modified pitch.
6. the preparation method of universal pitch-based carbon fiber according to claim 5; it is characterized in that: when the additive agent modified oxidized asphalt of described step (5); in autoclave, pass into nitrogen purge; stirring is cooled to 280～380 DEG C; under nitrogen protection, add property-modifying additive; the mass ratio of oxidized asphalt and property-modifying additive is 1:0.025, mixes, and obtains modified pitch.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210590858.9A CN103014919B (en) | 2012-12-28 | 2012-12-28 | Preparation method of general purpose pitch-based carbon fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210590858.9A CN103014919B (en) | 2012-12-28 | 2012-12-28 | Preparation method of general purpose pitch-based carbon fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103014919A CN103014919A (en) | 2013-04-03 |
| CN103014919B true CN103014919B (en) | 2014-09-10 |
Family
ID=47964017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210590858.9A Expired - Fee Related CN103014919B (en) | 2012-12-28 | 2012-12-28 | Preparation method of general purpose pitch-based carbon fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103014919B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305942A (en) * | 2013-06-06 | 2013-09-18 | 天津大学 | Spinneret plate and method for preparing mesophase pitch-based strip carbon fibers |
| CN106087118A (en) * | 2016-08-21 | 2016-11-09 | 山西三元炭素有限责任公司 | A kind of preparation method of general purpose grade pitch based carbon fiber |
| CN108611701A (en) * | 2018-04-26 | 2018-10-02 | 五邑大学 | Graphene oxide modified pitch base carbon fibre production method |
| CN111501134B (en) * | 2020-05-28 | 2022-05-06 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
| CN111925818B (en) * | 2020-08-14 | 2021-03-12 | 辽宁信德新材料科技股份有限公司 | Carbon fiber spinnable asphalt and preparation method and application thereof |
| CN111996619B (en) * | 2020-09-29 | 2021-09-17 | 中国矿业大学(北京) | Preparation method of general-purpose asphalt-based carbon fiber |
| CN113088263B (en) * | 2021-03-25 | 2022-07-05 | 渤瑞环保股份有限公司 | Method for preparing heat-conducting preform by blending industrial byproduct oil and waste plastic and application |
| CN114410049A (en) * | 2022-01-26 | 2022-04-29 | 北京宇阳泽丽防水材料有限责任公司 | High-weather-resistance synthetic polymer waterproof coiled material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6256198B2 (en) * | 1983-09-20 | 1987-11-24 | Kogyo Gijutsu Incho | |
| CN1040608A (en) * | 1988-08-25 | 1990-03-21 | 丸善石油化学株式会社 | Preparation is used to the bituminous method making the pitch of high-performance carbon fibers and be used to make common carbon fiber |
| CN101570904A (en) * | 2009-03-07 | 2009-11-04 | 垦利三合新材料科技有限责任公司 | Method for preparing asphalt-based carbon fiber |
| CN102399563A (en) * | 2010-09-10 | 2012-04-04 | 辽宁科技大学 | Method for preparing general type coal series asphalt with spinnability by solvent extraction and oxidative thermopolymerization |
-
2012
- 2012-12-28 CN CN201210590858.9A patent/CN103014919B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6256198B2 (en) * | 1983-09-20 | 1987-11-24 | Kogyo Gijutsu Incho | |
| CN1040608A (en) * | 1988-08-25 | 1990-03-21 | 丸善石油化学株式会社 | Preparation is used to the bituminous method making the pitch of high-performance carbon fibers and be used to make common carbon fiber |
| CN101570904A (en) * | 2009-03-07 | 2009-11-04 | 垦利三合新材料科技有限责任公司 | Method for preparing asphalt-based carbon fiber |
| CN102399563A (en) * | 2010-09-10 | 2012-04-04 | 辽宁科技大学 | Method for preparing general type coal series asphalt with spinnability by solvent extraction and oxidative thermopolymerization |
Non-Patent Citations (2)
| Title |
|---|
| 沥青基碳纤维的制备及应用研究进展;韩笑等;《安徽化工》;20110831;第37卷(第4期);7-9 * |
| 韩笑等.沥青基碳纤维的制备及应用研究进展.《安徽化工》.2011,第37卷(第4期),7-9. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103014919A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103014919B (en) | Preparation method of general purpose pitch-based carbon fiber | |
| CN105256409B (en) | A kind of mesophase pitch-based carbon fibers and preparation method thereof | |
| RU2652244C2 (en) | Thermoreactive thermoplastic intermediate product and the method of its manufacturing | |
| CN106087118A (en) | A kind of preparation method of general purpose grade pitch based carbon fiber | |
| CN103320901A (en) | Mesophase pitch-based carbon fiber doped with graphene | |
| CN103290527A (en) | Method for lowering ash content of polyacrylonitrile-based carbon fiber | |
| CN111501134B (en) | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues | |
| CN111718740B (en) | Spinnable mesophase pitch prepared by solvent synergistic hydrogenation, preparation method and application | |
| CN103361096B (en) | Preparation method of high-softening-point asphalt for producing general-grade carbon fibers | |
| CN103305942A (en) | Spinneret plate and method for preparing mesophase pitch-based strip carbon fibers | |
| CN109181733A (en) | A kind of method that coal tar pitch preparation can spin pitch | |
| CN108611701A (en) | Graphene oxide modified pitch base carbon fibre production method | |
| CN102776014B (en) | Preparation method of petroleum-based high softening point spinning pitch | |
| CN111004641A (en) | Spinnable asphalt and preparation method thereof | |
| CN109161973A (en) | The production technology of acid fiber by polylactic | |
| CN115369520B (en) | Mesophase pitch-based carbon fiber with mixed structure and preparation method thereof | |
| CN103122151A (en) | Preparation method of pitch applied to high-strength and high-modulus pitch-based fiber | |
| CN103952168B (en) | A kind of coal tar pitch produces the preparation method of general purpose grade asphalt-based carbon fiber high softening point bitumen | |
| WO2023000079A1 (en) | Transforming asphaltenes to carbon fibres | |
| Mochida et al. | Comparative evaluation of mesophase pitches derived from coal tar and FCC-DO | |
| CN104177591B (en) | Mesophase pitch raw material and preparation method and application for low-temp spinning | |
| TWI643988B (en) | Method of fabricating carbon fiber composite with biomass feedstock transformed | |
| CN110578188B (en) | Method for preparing spinnable asphalt by co-thermal polycondensation of acid anhydride modified coal asphalt and kerosene co-refining residue | |
| CN109402784A (en) | A kind of method of low temperature coal tar pitch during hydrogenated styrene-butadiene block copolymer is modified | |
| CN110540853B (en) | Method for preparing spinnable asphalt from pyromellitic dianhydride and polystyrene modified coal pitch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140910 Termination date: 20161228 |