CN112813538B - Preparation method of biological intermediate phase and asphalt-based carbon fiber - Google Patents
Preparation method of biological intermediate phase and asphalt-based carbon fiber Download PDFInfo
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- CN112813538B CN112813538B CN202110043050.8A CN202110043050A CN112813538B CN 112813538 B CN112813538 B CN 112813538B CN 202110043050 A CN202110043050 A CN 202110043050A CN 112813538 B CN112813538 B CN 112813538B
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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
- D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
Abstract
The invention provides a preparation method of biological mesophase and pitch-based carbon fiber, which selects the aromatic carbon rate after being treated by an ultrasonic heat filtering coupling extraction systemC A The aromatic-rich oil with the concentration of more than 40 percent is doped with 5 to 30 weight percent of biomass and is uniformly mixed to be used as a raw material, and the raw material is placed in a reaction kettle and protected by inert gas to carry out the following operations: (1) carrying out normal pressure or reduced pressure polycondensation at the reaction temperature of 350-500 ℃, the reaction pressure of 0.001-0.1 MPa and the reaction time of 0.5-4 h; (2) then, carrying out pressure thermal polycondensation treatment under the reaction pressure of 0.1-10 MPa and the reaction time of 4-10 h; (3) and sequentially carrying out melt spinning, pre-oxidation, carbonization/graphitization on the obtained biological intermediate phase to prepare the pitch-based carbon fiber. The method has the advantages of simple process flow, wide biomass source, low price, obvious reduction of production cost, single anisotropic structure of the prepared biological mesophase, high content (50-100%), low softening point (250-280 ℃) and good spinnability.
Description
Technical Field
The invention relates to a preparation method of biological mesophase and pitch-based carbon fiber, belonging to the technical field of carbon materials.
Background
Mesophase pitch is an anisotropic nematic liquid crystal formed by a series of complex chemical reactions such as thermal cracking, thermal polycondensation and the like at a certain temperature and pressure from petroleum, coal, pure aromatic compounds and the like. The molecular weight of the asphalt is relatively larger and is about 2000 due to the polycyclic aromatic hydrocarbon, the hydrogen-carbon atomic ratio is 0.3-0.6, the density of anisotropic mesophase asphalt is about 3-4 times higher than that of isotropic mesophase asphalt, and the softening point of the asphalt is greatly influenced by a reaction process and raw materials. Due to the specific highly-oriented planar macromolecular structure of the mesophase pitch and the structure of stacking layers under the action of pi electron cloud, the mesophase pitch has many characteristics and can be used for manufacturing high-modulus and high-strength carbon materials, ultrahigh-power electrodes, electricity storage materials with excellent performance and the like. In view of the fact that thermal conversion is an important technical route for processing inferior heavy oil and biomass, the synergistic conversion of the inferior oil and the biomass is creatively explored, the deep processing of the inferior heavy oil and the biomass and the improvement of product quality are expected to be realized, meanwhile, the production cost of mesophase pitch and the cost of biomass energy scale production can be greatly reduced, the scale utilization of biomass energy is greatly promoted, and the quality improvement and the efficiency improvement of the refining industry in China are realized.
CN02151063.6 discloses a method for preparing a biomass-derived carbonaceous intermediate phase, which comprises the steps of crushing biomass resources, mixing the biomass resources with phenols and concentrated sulfuric acid, carrying out modification chemical reaction treatment, treating with water, and carrying out post-treatment to finally obtain the carbonaceous intermediate phase with optical anisotropy.
Disclosure of Invention
The invention provides a preparation method of biological mesophase and pitch-based carbon fiber. The method is characterized in that the aromatic-rich oil after specific pretreatment and the biomass are mixed according to a certain proportion to synthesize a high-quality biological intermediate phase at a higher temperature and form the pitch-based carbon fiber through subsequent treatment.
The invention adopts the following technical scheme:
selecting pretreated aromatic-rich oil with specific properties, doping 5-30 wt% of biomass, uniformly mixing the biomass to serve as a raw material, placing the raw material in a reaction kettle, carrying out normal-pressure or reduced-pressure thermal polycondensation under the protection of nitrogen or argon inert gas and stirring at the rotating speed of 500-800 r/min, controlling the reaction temperature to be 350-500 ℃, the reaction pressure to be 0.001-0.1 MPa and the reaction time to be 0.5-4 h, and enabling the raw material to rapidly generate mesophase globules through thermal cracking thermal polycondensation; then, carrying out pressurized polycondensation for 4-10 h under the pressure of 0.1-10 MPa to enable the aromatic sheet structure to be formed by polycondensation and stacked in the longitudinal direction, and obtaining a biological intermediate phase with good fluidity and 50-100% of optical anisotropic structure; and sequentially carrying out melt spinning, pre-oxidation, carbonization/graphitization on the mesophase pitch to prepare the pitch-based carbon fiber.
Further, the property of the aromatic-rich oil is that the average molecular weight is 200-500, the number of aromatic rings is 2-6, the aromatic carbon rate is more than 40%, and the aromatic-rich oil is obtained by pretreating one or more of catalytic slurry oil, vacuum distillate oil, ethylene tar and coal tar serving as raw materials.
The pretreatment process comprises the following steps: the raw materials are subjected to reduced pressure fractionation to obtain heavy fraction sections with the temperature of more than 300 ℃, and the heavy fraction sections are mixed with furfural according to the solvent-oil ratio of 1-5 and then are mixed at the speed of 0.5-1m 3 The flow rate of the flow is sent to an ultrasonic heat filtration coupling extraction system for treatment, the power of an ultrasonic generator is adjusted to be 600-900W, the temperature of the mixed material is 60-90 ℃, and a ceramic membrane with the aperture of 20-200 nm is used as a filter medium; and then standing the filtrate for settling, separating the mixed oil from the solvent, taking the extract oil, introducing the extract oil into a gel permeation chromatographic column for separation, and obtaining the aromatic-rich oil.
The ultrasonic heat filtering coupling extraction system comprises an ultrasonic cavitation unit, a heat filtering unit and a solvent extraction unit, wherein an ultrasonic generator is arranged on the inner side wall of the system and is connected with a power supply and a controller through an external lead; the filter membrane is horizontally arranged at the middle lower part of the inner cavity of the system, and two ends of the filter membrane are fixed on the inner side wall of the ultrasonic generator through clamping grooves, so that the filter membrane is convenient to clean and replace; the stirring paddle is positioned in the middle above the filter membrane, and the top of the stirring rod is provided with a driving motor and a control unit, so that the stirring speed can be flexibly adjusted; the material inlet is positioned at the top of the system, and the raw oil and the premixed component of the extracting agent are conveyed into the system through a pipeline pump; a feed liquid outlet at the bottom end of the system is connected with a material standing unit, and the separation of the agent oil is realized in a standing mode; the bottom of the equipment is provided with a buckle connecting device, so that the equipment is convenient to clean and maintain.
The gel permeation chromatography filler adopts polystyrene gel, and the pore diameter of the filler is
The diameter of the gel column bed is 50-100mm, the height of the gel column bed is 800-1000mm, the flushing agent is Tetrahydrofuran (THF), the elution temperature is 30-80 ℃, and the flow rate is 0.5-3 ml/min.
Further, the biomass is one or more of wood chips, lignin, chitosan and biomass pyrolysis oil.
The softening point of the obtained biological mesophase is 250-280 ℃, the H/C ratio is 0.4-0.6, the carbon residue value is 80-85%, and the content of the anisotropic mesophase pitch is 50-100%.
The density of the obtained pitch-based carbon fiber is 1.75-1.85 g/cm 3 The tensile strength is 1500-2000 MPa, and the tensile modulus is 200-350 GPa.
The invention also provides the biological mesophase and the pitch-based carbon fiber prepared by the preparation method.
According to the invention, the heavy oil is pretreated by adopting a filtration deashing coupling reinforced extraction process based on ultrasonic assistance, the extractant is used for extracting polycyclic aromatic hydrocarbon components, the viscosity of crude oil is reduced, and transmembrane pressure difference of a filtering membrane is reduced; meanwhile, under the assistance of ultrasound, the cavitation effect of the material can be utilized to break the supermolecular association structures such as asphaltene in the raw oil, and the like, so that the viscosity of the material is further reduced; the device can also play a role in dispersing solid impurities such as catalyst particles, quinoline insoluble substances and the like, delay the sedimentation and blockage of fine solid impurities on the filter membrane and prolong the filtering operation period; in addition, multiple effects such as cavitation and disturbance caused by ultrasound promote the solvent penetration of the extractant, and the extraction effect is greatly enhanced. Therefore, the filtration deashing coupling reinforced extraction process based on ultrasonic assistance can realize high-efficiency deashing and aromatic hydrocarbon enrichment, and the structural composition of the enriched aromatic hydrocarbon can be flexibly modulated by modulating process parameters. The process is further integrated with the separation of the gel permeation chromatographic column, and the efficient gel permeation chromatography can separate the hydrocarbons according to the carbon number order and the molecular weight distribution, so that the aromatic-rich oil with narrower molecular weight distribution and specific aromatic ring number is further obtained by separation, and the precise regulation and control of the properties of the raw materials are realized.
The aromatic hydrocarbon-rich oil obtained by the specific pretreatment means and the biomass are mixed as raw materials, the source is wide, the price is low, the aromatic hydrocarbon-rich oil plays the roles of a solvent and a hydrogen donor, aromatic hydrocarbon compounds generated by biomass pyrolysis and heavy oil aromatic-rich components form mesophase aromatic hydrocarbon macromolecules through copolycondensation reaction after hydrogen donor and deoxidation, the conversion of the biomass to the mesophase aromatic hydrocarbon is effectively promoted, and the prepared biological mesophase has a good optical structure, a low softening point and high anisotropy content.
The synthetic biological intermediate phase also adopts a graded thermal polycondensation reaction, the first stage reaction is carried out under normal pressure or reduced pressure, when the raw oil is subjected to rapid pyrolysis in the early stage of the reaction, the reduction of the reaction pressure enables light components to be rapidly discharged out of the system, the viscosity of the reaction system is larger than that of a pressurized reaction section at the moment, the depth of a carbonization reaction is deepened, the rapid generation of intermediate phase pellets is facilitated, meanwhile, the fracture effect of alkyl or cycloalkyl side chains is obvious under the normal pressure or vacuum pumping condition, the steric hindrance between aromatic molecules is reduced, and favorable conditions are created for the stacking of subsequent aromatic sheet layers; the second stage reaction is carried out under the condition of pressurization, the micromolecular substance mainly acts as a solvent and a hydrogen donor in the reaction system, and the reaction system is at a level with relatively moderate liquidity at the moment, so that the hydrogen transfer reaction is favorably carried out, the planar aromatic sheets are favorably inserted into each other, and the biological mesophase asphalt with the optical structure presenting a wide area type is formed.
Compared with the prior art, the invention has the following advantages:
1. the raw material pretreatment process integrates ultrasonic cavitation, solvent extraction and thermal filtration, multi-level treatment is synchronously carried out and mutually influenced, raw material oil de-solidification and group composition regulation are realized by one-step operation, the method is a brand new integrated treatment process, the intermediate phase preparation process flow is simple, no catalyst is added in the reaction process, the product is easy to separate and obtain, and the requirement on equipment is low.
2. The raw materials have wide sources and low price, the obtained product has high added value, the problem of large-scale production and utilization of inferior residual oil and biomass is solved, and natural resources are reasonably allocated.
3. The invention adopts the graded thermal polycondensation reaction, the first stage reaction is carried out through the normal pressure/reduced pressure thermal polycondensation reaction, the reaction time is shortened, the molecular structure of the mixed raw materials is adjusted, the planar condensed ring aromatic hydrocarbon molecules suitable for layer-by-layer self-assembly are generated, and the formation of the subsequent large-basin mesophase asphalt is facilitated; the second stage of reaction regulates the flowability of the reaction system through a pressurizing process, creates reaction conditions for orderly stacking of planar polycyclic aromatic hydrocarbon molecules, and forms the large-basin biological mesophase pitch with a proper softening point.
Drawings
FIG. 1 is a schematic diagram of an ultrasonic-thermal filtration-coupled extraction system,
wherein, 1 is supersonic generator, 2 is the filter membrane, 3 is the draw-in groove, 4 is the stirring thick liquids, 5 is the material import, 6 is the feed liquid export, 7 is buckle connecting device.
FIG. 2 is an optical structural view of a large-flow-domain structure in which the anisotropic phase of the biological mesophase is a continuous phase.
Detailed Description
In order to make the technical scheme of the preparation method of the biological intermediate phase and the pitch-based carbon fiber more clearly understood, the technical scheme of the invention is further described with reference to the specific embodiments.
The ultrasonic heat filtering coupling extraction system comprises an ultrasonic cavitation unit, a heat filtering unit and a solvent extraction unit, wherein an ultrasonic generator 1 is arranged on the inner side wall of the system and is connected with a power supply and a controller through an external lead; the filter membrane 2 is horizontally arranged at the middle lower part of the inner cavity of the system, and two ends of the filter membrane are fixed on the inner side wall of the ultrasonic generator through the clamping grooves 3, so that the filter membrane is convenient to clean and replace; the stirring paddle 4 is positioned in the middle above the filter membrane, and a driving motor and a control unit are arranged at the top of the stirring rod, so that the stirring speed can be flexibly adjusted; the material inlet 5 is positioned at the top of the system and conveys the premixed components of the raw oil and the extracting agent into the system through a pipeline pump; a feed liquid outlet 6 at the bottom end of the system is connected with a material standing unit, and the separation of the agent oil is realized in a standing mode; the bottom of the device is provided with a snap connection device 7.
Example 1: pretreating to obtain aromatic-rich oil
Under the condition of 5KPa absolute pressure, carrying out reduced pressure precise fractionation on 3000g of one or more of catalytic oil slurry, reduced distillate oil, ethylene tar and coal tar to obtain heavy fraction sections with the temperature of more than 300 ℃, and mixing the heavy fraction sections with an extractant furfural (the mixing volume ratio is 1-5) at 0.5-1m 3 The flow rate of/h is transmitted to an ultrasonic heat filtration coupling extraction system, the power of an ultrasonic generator is adjusted to 600-900W, and the mixture is mixedThe material temperature is 60-90 ℃, a ceramic membrane with the aperture of 20-200nm is used as a filtering medium, then the filtrate is subjected to standing sedimentation and separation of solvent and oil, and the extract oil is taken and introduced into a gel permeation chromatographic column;
adding a glass cotton pad at the bottom of a gel column, adding polystyrene gel, adding a glass cotton pad at the top, wetting the gel column by 50ml of tetrahydrofuran, taking 100ml of tetrahydrofuran, mixing 300g of the extract oil, preheating to 50 ℃, adding the extract oil into the column for multiple times, keeping the temperature of a thermostatic water bath at 50 ℃, pressurizing the top of a column layer to keep the flow rate at 0.5-3ml/min, and collecting to obtain the aromatic-rich oil, wherein the molecular weight of the aromatic-rich oil is 200-500, the number of aromatic rings is 2-6, and the aromatic carbon rate is more than 40%.
Example 2
Adding 180g of the aromatic-rich hydrocarbon oil obtained by the pretreatment in the example 1 and 20g of wood chips into a reaction kettle, replacing air in the reaction kettle with nitrogen for 3 times, finally enabling the pressure in the reaction kettle to be normal pressure, raising the temperature to 100 ℃ at the heating rate of 3 ℃/min, starting stirring, maintaining the stirring rate to be 500r/min, enabling the reaction temperature to be 430 ℃, enabling the reaction pressure to be normal pressure, and reacting for 4 hours; and then keeping the reaction temperature unchanged, increasing the reaction pressure to 3MPa, continuing the reaction for 10 hours, finally closing the heating power supply, the stirring power supply, the circulating water and the exhaust valve, putting the reaction kettle into cold water for cooling, and opening the reaction kettle to obtain the biological mesophase pitch when the temperature is cooled to room temperature. The obtained biological mesophase pitch is a large-watershed structure with an anisotropic phase as a continuous phase, the H/C ratio is 0.45, the carbon residue value is 82%, the content of the mesophase is 95%, and the softening point is 263 ℃; melt spinning the obtained mesophase pitch at the spinning temperature of 300 ℃, and then pre-oxidizing, carbonizing/graphitizing to obtain the mesophase pitch with the density of 1.78g/cm 3 And a high-performance pitch-based carbon fiber having a tensile strength of 1630MPa and a tensile modulus of 320 GPa.
Example 3
Adding 180g of the aromatic-rich oil obtained by pretreatment in example 1 and 20g of lignin into a reaction kettle, replacing air in the reaction kettle with nitrogen for 3 times, finally starting a vacuumizing device to reduce the reaction pressure to 0.05MPa, increasing the temperature to 100 ℃ at the heating rate of 3 ℃/min, starting stirring, maintaining the stirring rate at 700r/min and the reaction temperature at 480 ℃,maintaining the reaction pressure at 0.05MPa and the reaction time at 3 h; and then keeping the reaction temperature unchanged, increasing the reaction pressure to 8MPa, continuing to react for 5 hours, finally closing the heating power supply, the stirring power supply, the circulating water and the exhaust valve, putting the reaction kettle into cold water for cooling, and opening the reaction kettle to obtain the biological mesophase pitch when the temperature is cooled to room temperature. The obtained biological mesophase pitch is a large-watershed structure with an anisotropic phase as a continuous phase, the H/C ratio is 0.52, the carbon residue value is 89%, the mesophase content is 92%, and the softening point is 268 ℃; carrying out melt spinning on the obtained biological mesophase pitch at the spinning temperature of 300 ℃, and then carrying out preoxidation, carbonization/graphitization to obtain the biological mesophase pitch with the density of 1.81g/cm 3 The high-performance asphalt-based carbon fiber has the tensile strength of 1700MPa and the tensile modulus of 280 GPa.
Example 4
Adding 180g of aromatic-rich oil and 35g of chitosan obtained by pretreatment in the example 1 into a reaction kettle, replacing air in the reaction kettle with nitrogen for 3 times, finally starting a vacuumizing device to reduce the reaction pressure to 0.01MPa, increasing the temperature to 100 ℃ at the heating rate of 3 ℃/min, starting stirring, maintaining the stirring rate at 600r/min, the reaction temperature at 360 ℃, maintaining the reaction pressure at 0.01MPa, and reacting for 2 hours; and then keeping the reaction temperature unchanged, increasing the reaction pressure to 4MPa, continuing the reaction for 10 hours, finally closing the heating power supply, the stirring power supply, the circulating water and the exhaust valve, putting the reaction kettle into cold water for cooling, and opening the reaction kettle to obtain the biological mesophase pitch when the temperature is cooled to room temperature. The obtained biological mesophase pitch is a large-watershed structure with an anisotropic phase as a continuous phase, the H/C ratio is 0.55, the carbon residue value is 83%, the mesophase content is 86%, the softening point is 252 ℃, the obtained biological mesophase pitch is subjected to melt spinning at the spinning temperature of 300 ℃, and then preoxidation, carbonization/graphitization is carried out to obtain the biological mesophase pitch with the density of 1.80g/cm 3 The high-performance asphalt-based carbon fiber has the tensile strength of 1550MPa and the tensile modulus of 240 GPa.
Example 5
Adding 180g of the aromatic-rich oil obtained by pretreatment in example 1 and 30g of biomass pyrolysis oil into a reaction kettle, replacing air in the reaction kettle with nitrogen for 3 times, and finally starting a vacuumizing device to reduce the reaction pressure to 0.001M Pa, heating to 100 ℃ at the heating rate of 3 ℃/min, starting stirring, maintaining the stirring rate at 600r/min, the reaction temperature at 410 ℃, the reaction pressure at 0.001MPa and the reaction time at 0.5 h; and then keeping the temperature unchanged, increasing the reaction pressure to 6MPa, continuing to react for 7h, finally closing an exhaust valve, a vacuum pump, a heating power supply, a stirring power supply and circulating water in sequence, putting the reaction kettle into cold water for cooling, and opening the reaction kettle when the temperature is cooled to room temperature to obtain the biological mesophase pitch. The obtained biological mesophase pitch is a large-watershed structure with an anisotropic phase as a continuous phase, the H/C ratio is 0.54, the carbon residue value is 84%, the mesophase content is 97%, the softening point is 277 ℃, the obtained biological mesophase pitch is subjected to melt spinning at the spinning temperature of 300 ℃, and then preoxidation, carbonization/graphitization is carried out to obtain the biological mesophase pitch with the density of 1.82g/cm 3 The high-performance asphalt-based carbon fiber has tensile strength of 1900MPa and tensile modulus of 340 GPa.
Claims (5)
1. A method for preparing biological mesophase and pitch-based carbon fiber is characterized by comprising the following steps:
(1) selecting the average molecular weight of 200-500, the number of aromatic rings of 2-6 and the aromatic carbon rate C A More than 40% of aromatic-rich oil is doped with 5 wt% -30 wt% of biomass and uniformly mixed to serve as a raw material, the raw material is placed in a reaction kettle, and under the stirring conditions of inert atmosphere and 500-800 r/min of rotating speed, normal-pressure or reduced-pressure thermal polycondensation reaction is firstly carried out, the reaction temperature is controlled to be 350-500 ℃, the reaction pressure is 0.001-0.1 MPa, and the reaction time is 0.5-4 h, so that the raw material is subjected to thermal cracking thermal polycondensation reaction to quickly generate mesophase globules;
(2) Secondly, performing a pressurized thermal polycondensation reaction, adjusting the pressure of the reaction kettle to 0.1-10 MPa, and performing polycondensation for 4-10 hours under a pressurized condition so as to form an aromatic lamellar structure by polycondensation and stack the aromatic lamellar structure in the longitudinal direction to obtain a biological intermediate phase with good fluidity and an optical anisotropic structure;
(3) sequentially carrying out melt spinning, pre-oxidation, carbonization and graphitization on the biological intermediate phase to prepare the pitch-based carbon fiber;
the aromatic-rich oil is obtained by pretreating one or more of catalytic slurry oil, vacuum distillate oil, ethylene tar and coal tar serving as raw materials;
the pretreatment process comprises the following steps: the raw materials are subjected to reduced pressure fractionation to obtain heavy fraction sections with the temperature of more than 300 ℃, and the heavy fraction sections are mixed with furfural according to the solvent-oil ratio of 1-5 and then are mixed at the speed of 0.5-1m 3 The flow rate of the flow is sent to an ultrasonic heat filtration coupling extraction system for treatment, the power of an ultrasonic generator is adjusted to be 600-900W, the temperature of the mixed material is 60-90 ℃, and a ceramic membrane with the aperture of 20-200 nm is used as a filter medium; then standing the filtrate for settling, separating the mixed oil from the filtrate, and introducing the extract oil into a gel permeation chromatographic column for separation to obtain aromatic-rich oil;
the ultrasonic heat filtering coupling extraction system comprises an ultrasonic cavitation unit, a heat filtering unit and a solvent extraction unit, wherein an ultrasonic generator is arranged on the inner side wall of the system and is connected with a power supply and a controller through an external lead; the filter membrane is horizontally arranged at the middle lower part of the inner cavity of the system, and two ends of the filter membrane are fixed on the inner side wall of the ultrasonic generator through clamping grooves, so that the filter membrane is convenient to clean and replace; the stirring paddle is positioned in the middle above the filter membrane, and a driving motor and a control unit are arranged at the top of the stirring rod, so that the stirring speed can be flexibly adjusted; the material inlet is positioned at the top of the system, and the raw oil and the premixed component of the extracting agent are conveyed into the system through a pipeline pump; a feed liquid outlet at the bottom end of the system is connected with a material standing unit, and the separation of the agent oil is realized in a standing mode; the bottom of the equipment is provided with a buckle connecting device, so that the equipment is convenient to clean and maintain.
2. The method of claim 1 for preparing a biological mesophase and pitch-based carbon fiber, wherein: the gel permeation chromatographic column filler adopts polystyrene gel, and the pore diameter of the filler is
The diameter of the gel column bed is 50-100mm, the height of the gel column bed is 800-1000mm, the flushing agent is tetrahydrofuran, the elution temperature is 30-80 ℃, and the flow rate is 0.5-3 ml/min.
3. The method of claim 1 for preparing a biological mesophase and pitch-based carbon fiber, wherein: the biomass is one or more of wood chips, lignin, chitosan and biomass pyrolysis oil.
4. The method of claim 1 for preparing a biological mesophase and pitch-based carbon fiber, wherein: the softening point of the obtained biological mesophase is 250-280 ℃, the H/C ratio is 0.4-0.6, the carbon residue value is 80-85%, and the content of the anisotropic mesophase pitch is 50-100%.
5. The method of claim 1 for preparing a biological mesophase and pitch-based carbon fiber, wherein: the density of the obtained pitch-based carbon fiber is 1.75-1.85 g/cm 3 The tensile strength is 1500-2000 MPa, and the tensile modulus is 200-350 GPa.
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