CN112831336B - Continuous preparation process of oil-based raw material for producing mesophase pitch and pitch-based carbon fiber - Google Patents

Continuous preparation process of oil-based raw material for producing mesophase pitch and pitch-based carbon fiber Download PDF

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CN112831336B
CN112831336B CN202110043951.7A CN202110043951A CN112831336B CN 112831336 B CN112831336 B CN 112831336B CN 202110043951 A CN202110043951 A CN 202110043951A CN 112831336 B CN112831336 B CN 112831336B
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oil
unit
pitch
raw material
ion exchange
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CN112831336A (en
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刘�东
柴鲁宁
沈国波
杜辉
段雅静
付玉娥
张建国
袁辉志
吴青
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China University of Petroleum East China
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/06—Working-up pitch, asphalt, bitumen by distillation
    • 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

The invention provides a continuous preparation process of an oil-based raw material for producing mesophase pitch and pitch-based carbon fiber, which comprises the following specific steps: (1) decompressing to obtain heavy fraction with temperature higher than 300 ℃ and taking the heavy fraction as raw material, (2) filtering, deashing and coupling reinforced extraction treatment under the assistance of ultrasound; (3) settling and separating raffinate oil from extract oil in a standing mode; (4) separating agent oil by a heating distillation mode, and recovering an extracting agent; (5) introducing an ion exchange chromatography unit to remove polar components containing heteroatoms, and finally obtaining refined raw oil with single structural composition, narrow molecular weight distribution and low content of heteroatoms and solid impurities; the catalytic polycondensation reaction can prepare mesophase pitch with softening point of 270-300 ℃, mesophase content of more than 97 percent and good spinning performance. The invention realizes high value-added utilization of heavy distillate oil through a highly integrated process, has large operable space and high universality, and lays an important foundation for preparing high-performance petroleum-based carbon materials.

Description

Continuous preparation process of oil-based raw material for producing mesophase pitch and pitch-based carbon fiber
Technical Field
The invention relates to a continuous preparation process of an oil-based raw material for producing mesophase pitch and pitch-based carbon fibers, belonging to the fields of deep petroleum processing technology and research on carbonaceous mesophase materials.
Background
The mesophase pitch is thermotropic liquid crystal formed by orderly stacking a large number of flaky polycyclic aromatic hydrocarbon molecules, has optical anisotropy, and simultaneously, the special crystal-like structure endows various novel carbon materials derived from the mesophase pitch with various excellent characteristics, such as high modulus, high strength, corrosion resistance, high heat and electrical conductivity, low thermal expansion coefficient and the like, in particular high-performance pitch-based carbon fibers, electrode materials, mesophase carbon microspheres, high heat and electrical conductivity materials and the like. As a carbon source of a plurality of high-end carbon-based materials, the structure composition of the intermediate phase pitch has a decisive influence on the structure, the property and the function of a product, and particularly when high-performance intermediate phase pitch-based carbon fibers are prepared, the precursor pitch is required to have high intermediate phase content, narrow molecular weight distribution, low content of impurity elements, proper softening point and the like, so that the high-quality intermediate phase pitch obtained must be refined through proper process treatment on the aromatic-rich distillate oil with complex structure composition.
Patent CN107163970A describes a method for preparing mesophase pitch by FCC slurry oil alkylation modification-settling separation, which comprises the steps of distilling FCC slurry oil under reduced pressure to obtain fractions with the temperature of 380-540 ℃, adding an alkylation modification additive, processing to obtain modified oil, and finally carrying out heat treatment to obtain mesophase pitch. Although the raw oil is subjected to alkylation modification treatment, the method is difficult to maintain the group composition of the refined distillate oil stably, and is easy to cause aromatic carbon ratio CALow, and difficult to prepare the spinnable mesophase pitch with a large watershed structure in the later period.
Patent CN107216903A describes a method for preparing mesophase pitch by FCC clarified oil crosslinking modification-settling separation, which comprises the steps of distilling raw oil under reduced pressure to obtain a fraction at 380-540 ℃, adding a crosslinking agent to treat under certain conditions to obtain modified oil, and finally performing heat treatment to obtain the mesophase pitch. Although the method modifies the feedstock oil with the crosslinking agent, the reaction conversion rate is relatively low, and the purity of the mesophase pitch is relatively low, so that it is difficult to produce high-quality carbon fibers.
Patent CN107163969B discloses a method for preparing mesophase pitch based on mesophase coal pitch as raw material, which comprises subjecting mesophase coal pitch to preheating polycondensation reaction, precise heat filtration and light component cutting treatment to obtain refined coal pitch with extremely low quinoline insoluble content, and performing heat treatment to obtain mesophase pitch. In general, the content of sulfur and nitrogen heteroatoms in coal pitch is high, and the sulfur and nitrogen heteroatoms need to be removed through hydrofining, and the method lacks a hydrofining unit, so that the spinning property of the prepared mesophase pitch is poor, and the softening point is high.
In order to obtain high-quality mesophase pitch, the structural composition of raw oil should be ensured to be uniform, in particular, polycyclic aromatic molecules are suitable for 2-5 rings and have a certain amount of short side chain alkyl groups, the contents of asphaltene and heteroatoms are strictly regulated and controlled, the purpose of refining raw materials is difficult to achieve by adopting a single treatment process aiming at the adverse factors of wide molecular weight distribution, complex structural composition, high asphaltene content and the like of industrial aromatic-rich distillate oil, therefore, the invention develops a filtration deashing coupling enhanced extraction process based on ultrasonic assistance to directly realize the purposes of removing solid impurities in the raw oil, regulating and controlling the structural composition, narrowing the molecular weight distribution and the like, and further realizes the flexible regulation of the structural composition of the refined raw materials by removing strong polar components containing heteroatoms such as S, N and the like by means of an integrated ion exchange chromatography unit.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a continuous preparation process of an oil-based raw material for producing mesophase pitch and pitch-based carbon fibers, wherein one or more heavy distillates rich in aromatic hydrocarbon heavy oil, catalytic slurry oil, coal tar or ethylene tar at the temperature of more than 300 ℃ are segmented into raw materials, a filtration deashing coupling enhanced extraction unit, a sedimentation unit, an oil separation unit and an ion exchange chromatography unit are sequentially processed by four steps of processes to obtain refined raw oil with single structure composition, narrow molecular weight distribution and low content of heteroatoms and solid impurities, and finally the processed refined raw oil is introduced into a catalytic polycondensation unit to prepare the mesophase pitch with the softening point of 270-300 ℃, the content of the mesophase of more than 97 percent and good spinning performance.
In order to achieve the above object, a continuous preparation process of an oil-based raw material for mesophase pitch and pitch-based carbon fiber production, comprising the steps of:
(1) carrying out reduced pressure precise fractionation on one or more heavy fractions of heavy oil rich in aromatic hydrocarbon, catalytic slurry oil, coal tar or ethylene tar at the temperature of more than 300 ℃ to obtain raw materials;
(2) a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound: mixing raw materials and an extracting agent according to a certain proportion, then sending the mixture into a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound through a pipeline pump, and adjusting the ultrasonic power, the filtration extraction temperature and the raw material flow rate according to the properties of the raw materials to realize the simultaneous thermal filtration and solvent extraction treatment under the assistance of ultrasound;
(3) a settling unit: conveying the mixed material treated in the step (2) into a settling device, and separating raffinate oil from extract oil in a standing mode;
(4) an agent oil separation unit: separating the extraction oil separated by the settling unit into solvent oil by a heating distillation mode, and recovering the extractant;
(5) ion exchange chromatography unit: introducing the aromatic-rich distillate oil obtained by the solvent oil separation unit into an ion exchange chromatography unit to remove polar components containing heteroatoms, and finally obtaining refined raw oil with single structural composition, narrow molecular weight distribution and low content of heteroatoms and solid impurities;
(6) a catalytic polycondensation unit: the refined raw oil is subjected to catalytic polycondensation to prepare mesophase pitch with a softening point of 270-300 ℃, a mesophase content of more than 97 percent and good spinning performance.
In the invention, the filtration deashing coupling reinforced extraction unit under ultrasonic assistance comprises an ultrasonic cavitation unit, a thermal filtration 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 sedimentation 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.
In the step (2), the extracting agent is one or more selected from furfural, N-dimethylformamide and N-methylpyrrolidone, the volume ratio of the extracting agent to the raw material oil is 1-5, and the flow rate is 0.5-1m3The filtering and extracting temperature is 60-90 ℃, and the filter membrane is a ceramic membrane with the filter hole aperture of 20-200 nm; the power of the ultrasonic cavitation is set to 600 and 900W.
In the step (5), the height of the ion exchange chromatographic column is 600-1000mm, the diameter of the column is 50-100mm, the stationary phase is sulfonic acid type cation exchange resin and quaternary amine type anion exchange resin, and the mobile phase is mixed solution of n-heptane, toluene and toluene-ethanol with the volume ratio of 1: 1.
In the step (6), the temperature of the catalytic polycondensation reaction is 300-3、BF3Or the mixture of the two is used as a catalyst, and the mesophase pitch with the softening point of 270-300 ℃, the mesophase content of more than 97 percent and good spinning performance is obtained.
Aiming at the complex structure composition characteristic of heavy distillate oil, the invention develops a filtration deashing coupling reinforced extraction process based on ultrasonic assistance, and an extractant is used for extracting polycyclic aromatic hydrocarbon components, realizes the reduction of crude oil viscosity and is beneficial to reducing transmembrane pressure difference of a filter membrane; meanwhile, under the assistance of ultrasonic waves, the cavitation effect of the ultrasonic vibration can be utilized to break the association structure of supramolecules 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 of cavitation, disturbance and the like brought by the ultrasonic waves promote the solvent penetrating power of the extracting agent, and the extracting 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 and the ion exchange chromatography are further integrated, and the polycyclic aromatic hydrocarbon component containing S, N heteroatoms in the raw oil is efficiently removed by utilizing the combination and matching of sulfonic acid type cation exchange resin and quaternary amine type anion exchange resin, so that the fine separation treatment of the aromatic hydrocarbon component is realized, the polycyclic aromatic hydrocarbon with stronger polarity, such as sulfur and nitrogen heteroatoms, is removed, and the high-quality raw material is obtained.
The refined raw oil obtained by the ultrasonic-assisted filtration deashing coupling enhanced extraction process and ion exchange treatment of the raw oil has the molecular weight distribution of 300-650 and the aromatic carbon rate (C)A) And a naphthenic carbon ratio (C)N) The sum of them is 55-80%, the absolute change rate of the number of naphthenic rings and the number of aromatic rings>3.5 percent and ash content less than or equal to 20 mu g/g. Therefore, aiming at the complex structure composition characteristic of the industrial aromatic-rich distillate oil, a plurality of process units are combined to refine the aromatic-rich distillate oil, and a solid foundation is laid for obtaining high-quality anisotropic asphalt with high mesophase content and low softening point.
Compared with the existing process route, the invention has the advantages that:
1. the invention can adopt the filtration deashing coupling reinforced extraction process under the assistance of ultrasound according to the characteristics of the raw oil, flexibly regulate and control process parameters, greatly improve the production efficiency and is easier to realize industrialized amplification production.
2. The invention adopts the filtration deashing coupling strengthening extraction process integrated ion adsorption treatment method under the assistance of ultrasound, can pertinently remove polycyclic aromatic hydrocarbon containing sulfur and nitrogen heteroatom, realizes high purification of raw oil, and can effectively solve the problems of low content of mesophase pitch, high softening point, poor spinnability and non-uniform composition, thereby improving the mechanical property of carbon fiber to a great extent.
Drawings
FIG. 1 is a flow chart of the continuous preparation process of oil-based raw materials for mesophase pitch and pitch-based carbon fiber production according to the present invention,
wherein: 1. heating furnace; 2. a reduced pressure precision fractionation unit; 3. a pipeline pump; 4. a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound; 5. a sedimentation unit; 6. an agent oil separation unit; 7. an ion exchange unit; 8. a catalytic polycondensation reaction unit.
FIG. 2 is a schematic view of a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound,
wherein, 1 is supersonic generator, 2 is the filter membrane, 3 is the draw-in groove, 4 is the stirring thick liquids, 5 is that material import 6 is the feed liquid export, 7 is buckle connecting device.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional procedures described in the literature in the field. The continuous preparation process flow is as follows: the device is sequentially connected with a heating furnace 1, a reduced pressure precise fractionation unit 2, a pipeline pump 3, a filtration deashing coupling strengthening extraction unit 4 under the assistance of ultrasound, a sedimentation unit 5, an agent oil separation unit 6, an ion exchange unit 7 and a catalytic polycondensation reaction unit 8. Wherein, the outlet of the heating furnace 1 is communicated with the feed inlet of the reduced pressure precise fractionation unit 2; each outlet of the decompression precise fractionating unit 2 is provided with a valve, and different fractions can be combined. The discharge hole of the decompression precise fractionating unit 2 is communicated with the feed hole of the filtration deashing coupling strengthening extraction unit 4 under the assistance of ultrasound through the delivery of a pipeline pump; the discharge hole of the filtration deashing coupling strengthening extraction unit 4 under the assistance of ultrasound is communicated with the feed hole of the sedimentation unit 5; the discharge hole of the settling unit 5 is communicated with the feed inlet of the agent oil separating unit 6; a discharge port of the agent oil separation unit 6 and an ion exchange unit 7; the discharge hole of the ion exchange unit 7 is communicated with the feed inlet of the thermal polycondensation reaction unit 8. The deep-drawing unit 2 is equipped with an internal and external heating device, and the catalytic polycondensation unit 8 is equipped with an electromagnetic heating device.
Detailed Description
The continuous preparation process of oil-based raw material for mesophase pitch and pitch-based carbon fiber production according to the present invention will be further described with reference to the following examples.
Example 1:
adding 3.5kg of ethylene tar into a vacuum precise fractionation unit, feeding into the tower at 200 deg.C and absolute pressure of 5KPa, vacuum precisely and deeply separating distillate oil with temperature higher than 300 deg.C, opening corresponding valve, introducing the distillate oil and extractant into a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound, wherein the extractant is Dimethylformamide (DMF) and the ratio of solvent to oil is 5:1, and adjusting ultrasonic wave generationThe power of a generator is 700W, the temperature of the mixed material is 90 ℃, a ceramic membrane with the aperture of 20nm is used as a filter medium, then the filtrate is subjected to standing sedimentation and separation of solvent and oil, then the treated raw oil is introduced into an ion exchange device, a solvent with the volume ratio of n-heptane, toluene and toluene-ethanol being 1:1 is introduced, the temperature of the ion exchange unit is maintained at 100 ℃, and the compounds containing sulfur and nitrogen heteroatom in the raw oil are removed, thus obtaining the refined raw material. Finally, the refined raw oil is led into a catalytic polycondensation unit, and 3g of AlCl is added3The particles are used as a catalyst and react for 70min at the temperature of 350 ℃ and the pressure of 3MPa to obtain the mesophase pitch, the content of which is about 99 percent, and the softening point of which is 280 ℃.
The intermediate phase pitch is used as a raw material to carry out melt spinning at 330 ℃, preoxidation at 230 ℃ in an air atmosphere and carbonization at 1200 ℃ in a nitrogen atmosphere to obtain the pitch-based carbon fiber with the tensile modulus of 410GPa and the tensile strength of 1.9 GPa.
Example 2:
adding 3.5kg of ethylene tar into a reduced pressure precise fractionation unit, feeding the ethylene tar into the reduced pressure precise fractionation unit, separating distillate oil with the temperature of 200 ℃ and the absolute pressure of 5KPa at a reduced pressure precise deep drawing, opening a corresponding valve, simultaneously introducing the distillate oil and an extracting agent into a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound, wherein the extracting agent adopts N-methyl pyrrolidone (NMP), the agent-oil ratio is 5:1, adjusting the power of an ultrasonic generator to 900W, the temperature of a mixed material is 90 ℃, adopting a ceramic membrane with the aperture of 20nm as a filtration medium, then, standing the filtrate, settling, separating oil, introducing the treated raw oil into an ion exchange device, introducing a solvent of N-heptane, toluene and toluene-ethanol with the volume ratio of 1:1, maintaining the temperature of the ion exchange unit at 100 ℃, removing compounds containing sulfur and nitrogen heteroatoms in the raw oil, obtaining the refined raw material. Recently, the refined feed oil was introduced into the catalytic polycondensation unit and 1g of AlCl was added3The particles are used as a catalyst and react for 70min at the temperature of 340 ℃ and the pressure of 2.5MPa to obtain the mesophase pitch, the content of which is about 99 percent, and the softening point of which is 285 ℃.
The intermediate phase pitch is taken as a raw material to be subjected to melt spinning at 340 ℃, pre-oxidized at 250 ℃ in an air atmosphere and carbonized at 1200 ℃ in a nitrogen atmosphere to obtain the pitch-based carbon fiber, wherein the tensile modulus of the pitch-based carbon fiber is 440GPa, and the tensile strength of the pitch-based carbon fiber is 2.1 GPa.
Example 3:
adding 3.5kg of ethylene tar into a reduced pressure precise fractionation unit, feeding the ethylene tar into the reduced pressure precise fractionation unit, separating distillate oil with the temperature of 200 ℃ and the absolute pressure of 5KPa at a reduced pressure precise deep drawing, opening a corresponding valve, simultaneously introducing the distillate oil and an extracting agent into a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound, wherein the extracting agent is furfural with the agent-oil ratio of 4:1, adjusting the power of an ultrasonic generator to 800W, adjusting the temperature of a mixed material to 80 ℃, adopting a ceramic membrane with the pore diameter of 50nm as a filter medium, then performing standing sedimentation on the filtrate to separate a neutralizer oil, introducing the treated raw oil into an ion exchange device, introducing n-heptane, toluene and toluene-ethanol (volume ratio) as a solvent, maintaining the temperature of the ion exchange unit at 100 ℃, and removing compounds containing sulfur and nitrogen heteroatoms in the raw oil to obtain a refined raw material. Recently, refined feed oil was introduced into the catalytic polycondensation unit, and 2g of AlCl was added3The particles are used as a catalyst and react for 60min at 330 ℃ and 2MPa to obtain the mesophase pitch with the content of about 99 percent and the softening point of 270 ℃.
The pitch-based carbon fiber is obtained by melt spinning at 345 ℃, pre-oxidizing at 270 ℃ in air atmosphere and carbonizing at 1200 ℃ in nitrogen atmosphere by taking the mesophase pitch as a raw material, and has the tensile modulus of 420GPa and the tensile strength of 1.9 GPa.
Example 4:
adding 3.5kg of ethylene tar into a reduced pressure precise fractionation unit, feeding the ethylene tar into the reduced pressure precise fractionation unit, performing reduced pressure precise deep drawing separation on distillate oil with the temperature of 200 ℃ and the absolute pressure of 5KPa, opening a corresponding valve, simultaneously introducing the distillate oil and an extracting agent into a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound, wherein the extracting agent adopts dimethyl formamide (DMF) and the agent-oil ratio is 5:1, adjusting the power of an ultrasonic generator to 700W, the temperature of a mixed material is 70 ℃, adopting a ceramic membrane with the pore diameter of 50nm as a filtration medium, then performing standing sedimentation on the filtrate to separate the solvent and the oil, then introducing the treated raw oil into an ion exchange device, introducing n-heptane, toluene and toluene-ethanol (volume ratio) into the ion exchange unit, and allowing the ion exchange unit to obtain a solvent with the volume ratio of 1:1Maintaining the temperature at 100 deg.C, and removing sulfur and nitrogen heteroatom compounds from the raw oil to obtain refined raw material. Recently, the refined feed oil was introduced into the catalytic polycondensation unit, and 1g of AlCl was added3The particles are used as a catalyst and react for 40min at the temperature of 310 ℃ and the pressure of 1MPa to obtain the mesophase pitch, the content of which is about 99 percent, and the softening point of which is 275 ℃.
The pitch-based carbon fiber is obtained by melt spinning at 330 ℃, pre-oxidizing at 230 ℃ in air atmosphere and carbonizing at 1200 ℃ in nitrogen atmosphere by taking the mesophase pitch as a raw material, and has the tensile modulus of 400GPa and the tensile strength of 1.7 GPa.
Example 5:
adding 3.5kg of ethylene tar into a reduced pressure precise fractionation unit, feeding the ethylene tar into the reduced pressure precise fractionation unit, separating distillate oil with the temperature of 200 ℃ and the absolute pressure of 5KPa at a reduced pressure precise deep drawing, opening a corresponding valve, simultaneously introducing the distillate oil and an extracting agent into a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound, wherein the extracting agent adopts N-methyl pyrrolidone (NMP), the agent-oil ratio is 5:1, adjusting the power of an ultrasonic generator to 600W, the temperature of a mixed material is 60 ℃, adopting a ceramic membrane with the aperture of 30nm as a filtration medium, then, standing the filtrate, settling, separating oil, introducing the treated raw oil into an ion exchange device, introducing a solvent of N-heptane, toluene and toluene-ethanol with the volume ratio of 1:1, maintaining the temperature of the ion exchange unit at 100 ℃, removing compounds containing sulfur and nitrogen heteroatoms in the raw oil, obtaining the refined raw material. Recently, the refined feed oil was introduced into the catalytic polycondensation unit, and 1.5g of AlCl was added3The particles are used as a catalyst and react for 30min at the temperature of 300 ℃ and the pressure of 0.1MPa to obtain the mesophase pitch, the content of which is about 99 percent, and the softening point of which is 280 ℃.
The intermediate phase pitch is used as a raw material to carry out melt spinning at 330 ℃, preoxidation at 230 ℃ in an air atmosphere and carbonization at 1200 ℃ in a nitrogen atmosphere to obtain the pitch-based carbon fiber with the tensile modulus of 410GPa and the tensile strength of 1.9 GPa.

Claims (3)

1. A process for the continuous preparation of oil-based raw materials for the production of mesophase pitch and pitch-based carbon fibers, comprising the steps of:
(1) carrying out reduced pressure precise fractionation on one or more heavy fractions of heavy oil rich in aromatic hydrocarbon, catalytic slurry oil, coal tar or ethylene tar at the temperature of more than 300 ℃ to obtain raw materials;
(2) a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound: mixing raw materials and an extracting agent according to a certain proportion, sending the mixture into a filtration deashing coupling reinforced extraction unit under the assistance of ultrasound through a pipeline pump for treatment, and adjusting the ultrasonic power, the filtration extraction temperature and the raw material flow rate according to the properties of the raw materials to realize the simultaneous thermal filtration and solvent extraction treatment under the assistance of ultrasound;
(3) a settling unit: conveying the mixed material treated in the step (2) into a settling device, and separating raffinate oil from extract oil in a standing mode;
(4) an agent oil separation unit: separating the extraction oil separated by the settling unit into solvent oil by a heating distillation mode, and recovering the extractant;
(5) ion exchange chromatography unit: introducing the aromatic-rich distillate oil obtained by the agent oil separation unit into an ion exchange chromatography unit to remove polar components containing heteroatoms, and finally obtaining refined raw oil with single structural composition, narrow molecular weight distribution and low content of heteroatoms and solid impurities; the stationary phase of the ion exchange chromatography unit selects sulfonic acid type cation exchange resin and quaternary amine type anion exchange resin, the molecular weight distribution of the refined raw material oil is 300-650, the sum of the aromatic carbon rate and the naphthenic carbon rate is 55-80%, the absolute change rate of the naphthenic ring number and the aromatic ring number is more than 3.5%, and the ash content is less than or equal to 20 mu g/g;
(6) a catalytic polycondensation unit: carrying out catalytic polycondensation on the refined raw oil to prepare mesophase pitch with a softening point of 270-300 ℃, a mesophase content of more than 97 percent and good spinning performance; the temperature of the catalytic polycondensation reaction is 300-350 ℃, the reaction pressure is 0-3MPa, the reaction time is 30-90min, and AlCl is selected3、BF3Or the mixture of the two is used as a catalyst;
the filtration deashing coupling reinforced extraction unit under the ultrasonic assistance in the step (2) comprises an ultrasonic cavitation unit, a thermal filtration 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 sedimentation 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 process for the continuous preparation of oil-based raw materials for the production of mesophase pitch and pitch-based carbon fibers according to claim 1, wherein: in the step (2), the extracting agent is selected from one or more of furfural, N-dimethylformamide and N-methylpyrrolidone, the volume ratio of the extracting agent to the raw material is 1-5, and the flow rate is 0.5-1m3The filtering and extracting temperature is 60-90 ℃, and the filter membrane is a ceramic membrane with the filter pore diameter of 20-200 nm; the power of the ultrasonic cavitation is set to 600-900W.
3. The process for the continuous preparation of oil-based raw materials for the production of mesophase pitch and pitch-based carbon fibers according to claim 1, wherein: the height of the ion exchange chromatographic column of the ion exchange chromatographic unit in the step (5) is 600-1000mm, the diameter of the column is 50-100mm, and the mobile phase is a mixed solution of n-heptane, toluene and toluene-ethanol with the volume ratio of 1:1 in sequence.
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