CN110699107A - Method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment - Google Patents
Method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment Download PDFInfo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
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Abstract
The invention discloses a method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment, which comprises the following steps: (1) adding an auxiliary agent into the coal pitch, promoting the primary inorganic mineral to form a dispersion catalyst in situ under the high-temperature hydrogen condition, carrying out hydrogen catalysis treatment on the coal pitch, and carrying out reduced pressure distillation after reaction to remove low-boiling-point fractions to obtain primary hydrogenated pitch; (2) adding a hydrogen donor into the primary hydrogenated asphalt, performing hydrocatalysis-hydrogen donor synergistic treatment under a high-temperature hydrocatalysis condition, and performing reduced pressure distillation to remove low-boiling-point fractions to obtain secondary hydrogenated asphalt; (3) removing quinoline insoluble substances from the secondary hydrogenated asphalt to obtain refined hydrogenated asphalt; (4) the refined hydrogenated asphalt is subjected to thermal polymerization to prepare spinnable mesophase asphalt. The hydro-catalysis-hydrogen supply combined treatment can effectively regulate and control the formation and conversion of the mesophase pitch, and the obtained spinnable mesophase pitch has excellent quality, moderate softening point and high mesophase content and can be applied to the preparation of high-performance pitch-based carbon fibers.
Description
Technical Field
The invention relates to the field of preparation and processing of carbon materials, in particular to a method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment.
Background
The mesophase pitch is an anisotropic carbonaceous material consisting of a plurality of flat disc-shaped fused ring aromatic hydrocarbons, is often used as an excellent carbon precursor to be applied to high-performance carbon materials, and is prepared from coal pitch, petroleum pitch, heavy aromatic hydrocarbon compounds and the like. The high-quality mesophase pitch is a precursor for preparing high-performance pitch-based carbon fibers, and the mesophase pitch-based carbon fibers have the remarkable advantages of high heat conductivity, high modulus and the like and are widely applied to the fields of aerospace, aviation, sports entertainment, leisure, transportation and the like.
The regulation and control of the molecular structure and the composition of the raw material asphalt are key factors influencing the preparation of the mesophase asphalt and directly influence indexes such as the softening point, the spinnability and the mesophase content of the mesophase asphalt. The raw material asphalt is generally adjusted by methods such as hydrotreating, co-carbonization, catalytic modification and the like, so that a more ideal molecular structure and composition are obtained, and the formation and conversion of the raw material asphalt are promoted to high-quality mesophase asphalt. (1) The hydrocatalysis refers to a process of hydrogenating and modifying raw material asphalt under the condition of high temperature and hydrogen. Research of Wangzongxian and other people in China Petroleum university (east China) finds that in the hydro-catalysis process of the dispersive catalyst, the primary metal contained in the asphalt has catalytic activity after vulcanization, so that hydrogen molecules are activated, polycyclic aromatic hydrocarbon is partially hydrogenated in a hydrogen atmosphere to form a naphthenic aromatic structure with a hydrogen supply effect, and then hydrogen is supplied to the system to play a role of 'hydrogen shuttle', and hydrogen sulfide generated by desulfurization in the hydro-catalysis process can play a certain catalytic role or play a role of 'hydrogen shuttle' to transfer hydrogen free radicals. (2) The hydrogen donor modification means that the raw material asphalt is subjected to hydrogenation modification by a reaction such as hydrogen transfer under a high temperature condition. Research shows that the hydrogen donor raw material asphalt is subjected to hydrocracking reaction under the high-temperature condition, so that aromatic ring hydrogenation is facilitated to form an alicyclic structure; compared with adjacent nitrogen, the alicyclic structure is easier to form under the hydrogen condition. (3) The dispersive catalyst and the hydrogen donor generate synergistic effect when existing simultaneously, which is more beneficial to the optimization of the molecular structure and the composition of the raw material asphalt. The research of the stone bin and the like of the petroleum university (Beijing) in China finds that the dispersive catalyst mainly plays a role in hydrogenating polycyclic aromatic hydrocarbon and stabilizing macromolecular free radicals in the hydrocracking of raw material asphalt, the hydrogen donor plays a role in transferring gas-phase hydrogen to liquid phase, and the existence of the catalyst is helpful for realizing the reversible reaction of the hydrogen donor and the polycyclic aromatic hydrocarbon and accelerating the transfer of the gas-phase hydrogen to a free radical intermediate phase body.
Due to the problems of complex structure, poor performance and the like of coal tar pitch components, the preparation and performance improvement of coal tar pitch-based mesophase pitch are limited by a plurality of technologies, so that the industrialization process is slow. Patent CN103205271A proposes a method for producing mesophase pitch from high-temperature coal tar, which comprises the steps of removing salt and quinoline insoluble substances from the high-temperature coal tar to obtain clarified oil, blending the clarified oil, performing catalytic hydrogenation treatment, filtering particles with the particle size of more than 10 mu m, performing distillation treatment to obtain hydrogenated pitch, and performing thermal polycondensation on the hydrogenated pitch to obtain the mesophase pitch. The method has the problems that quinoline insoluble substances need to be removed for many times, the catalytic hydrogenation severity is high, carbon deposition is difficult to avoid by a solid catalyst, and the like. Patent CN85105609A proposes a method for coal pitch hydrogenation, which adopts a fixed bed metal-supported solid catalyst, has low catalytic hydrogenation activity and weak hydrogenation capability, is difficult to effectively improve the molecular structure and composition of pitch, and simultaneously has the step of removing quinoline insoluble substances for many times. Patent CN107760348A discloses that the refined coal liquefaction residue is subjected to thermal polymerization in the presence of hydrogen donor and under the protection of nitrogen to obtain mesophase pitch, but because the coal liquefaction residue is composed of polycyclic aromatic hydrocarbons with high polymerization degree and condensation degree, it is difficult to control the formation and conversion of mesophase pitch by hydrogenation modification of hydrogen donor.
The invention aims to overcome the defects of the prior art, provides a new idea for coal pitch hydrogenation modification and simplifying the times of the steps of removing quinoline insoluble substances, provides a method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment and thermal polycondensation, and is expected to promote the coal pitch-based mesophase pitch industrialization process.
Disclosure of Invention
The invention provides a method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment, which can effectively regulate and control the conversion and formation of the mesophase pitch, and the obtained spinnable mesophase pitch has excellent quality, moderate softening point and high mesophase content and can be applied to the preparation of high-performance pitch-based carbon fibers.
The technical scheme for realizing the invention is as follows:
a method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment comprises the following steps:
(1) adding a certain mass ratio of the auxiliary agent and the coal pitch into a stirring reaction kettle, promoting the primary inorganic mineral to form a dispersion catalyst in situ under the condition of high temperature and hydrogen, carrying out hydrogen catalysis treatment on the coal pitch, and carrying out reduced pressure distillation after reaction to remove low-boiling fraction to obtain primary hydrogenated pitch;
(2) adding a hydrogen donor and primary hydrogenated asphalt in a certain mass ratio into a stirring reaction kettle, carrying out hydrocatalysis-hydrogen donor synergistic treatment on the asphalt under the condition of high temperature and hydrogen, and carrying out reduced pressure distillation to remove low-boiling fraction to obtain secondary hydrogenated asphalt;
(3) removing quinoline insoluble substances from the secondary hydrogenated asphalt to obtain refined hydrogenated asphalt;
(4) the refined hydrogenated asphalt is subjected to thermal polymerization reaction in a stirring reaction kettle to prepare spinnable mesophase asphalt.
The auxiliary agent in the step (1) is any one or combination of sublimed sulfur, carbon disulfide and mercaptan, and the coal pitch comprises any one or combination of coal tar, medium-low temperature coal pitch, high-temperature coal pitch, secondary coal pitch, tar residue, coal liquefaction pitch and coal liquefaction residue.
The mass ratio of the coal pitch and the auxiliary agent in the step (1) is 100 (0.1-2), the high-temperature hydrogen condition is that the reaction temperature is 380-440 ℃, the reaction hydrogen pressure is 1-5MPa, the reaction time is 1-4h, the stirring speed is 50-200rpm, the reduced pressure distillation temperature is 320-380 ℃, and the absolute pressure is 0-40 kPa.
The hydrogen donor in the step (2) is any one or combination of tetrahydronaphthalene, decahydronaphthalene, tetrahydroquinoline, tetrahydrofuran, indane and 9, 10-dihydroanthracene, and the mass ratio of the primary hydrogenated asphalt to the hydrogen donor is 1 (0.5-5).
The temperature of the hydrocatalysis-hydrogen supply synergistic treatment reaction in the step (2) is 390-450 ℃, the pressure of the reaction hydrogen is 0.5-10MPa, the reaction time is 1-8h, the stirring speed is 50-200rpm, the temperature of the reduced pressure distillation is 320-380 ℃, and the absolute pressure is 0-40 kPa.
In the step (3), the secondary hydrogenated asphalt and the solvent are mixed according to a mass ratio of 1: (1-5) heating, mixing, filtering and removing quinoline insoluble substances, and distilling the filtrate under reduced pressure to obtain refined hydrogenated asphalt, wherein the quinoline insoluble substances are less than 0.05 percent, the reduced pressure distillation temperature is 320-380 ℃, and the absolute pressure is 0-40 kPa; the solvent is aromatic hydrocarbon solvent of toluene, benzene, pyridine, quinoline, tetrahydrofuran and wash oil.
The temperature of the thermal polymerization reaction in the step (4) is 380-450 ℃, the reaction pressure is 0.5-6MPa, the reaction time is 1-12h, the stirring speed is 50-200rpm, and the protective gas is nitrogen or argon.
The invention takes coal tar pitch as raw material, and the coal tar pitch usually contains a certain content of inorganic mineral. Firstly, the primary inorganic minerals are promoted to form a dispersion catalyst in situ under the condition of high temperature hydrogenation by adding an auxiliary agent, such as metal iron sulfide and the like, the coal pitch is subjected to primary hydrogenation catalytic treatment, and low boiling point fractions are removed by reduced pressure distillation to reduce unnecessary consumption of subsequent hydrogenation, so that primary hydrogenated pitch is obtained. Secondly, adding a hydrogen donor, carrying out hydrogen catalysis-hydrogen donor synergistic treatment on the primary hydrogenated asphalt under the high-temperature hydrogen condition, and carrying out reduced pressure distillation to remove low-boiling-point fractions to obtain secondary hydrogenated asphalt. The hydrogenation mechanism of the dispersive catalyst and the hydrogen donor is different, which is beneficial to enriching the hydrogenation modification of asphalt molecules, and the dispersive catalyst and the hydrogen donor have synergistic effect, which is beneficial to the controllability of the asphalt hydrogenation process, improves various performance indexes of refined hydrogenated asphalt, and is beneficial to forming and converting high-quality mesophase asphalt, and the step effectively inhibits the coking problem of the traditional hydrogenation process, especially the coking problem of the reactor wall. And finally, removing quinoline insoluble substances from the secondary hydrogenated asphalt to obtain refined hydrogenated asphalt, and further performing thermal polymerization on the refined hydrogenated asphalt to obtain spinnable mesophase asphalt which can be applied to the preparation of high-performance asphalt-based carbon fibers. The process simplifies the traditional two-time or multiple separation process into a separation process for removing the quinoline insoluble substances once, thereby effectively reducing the treatment difficulty and the processing energy consumption.
The invention has the beneficial effects that:
(1) according to the invention, the primary inorganic mineral is promoted to form the dispersive catalyst in situ under the high-temperature hydrogen condition by adding the auxiliary agent, and the primary inorganic mineral is effectively utilized to carry out hydrogen catalytic pretreatment on the coal pitch, so that the raw material pitch is subjected to preliminary hydrogenation modification.
(2) The invention utilizes the synergistic effect of the primary dispersion catalyst and the hydrogen donor, enhances the controllability of the asphalt hydrogenation process, improves various performance indexes of the refined hydrogenated asphalt, and is beneficial to the formation and conversion of the coal asphalt into high-quality mesophase asphalt.
(3) The method effectively inhibits the coking problem in the traditional hydrogenation process, in particular the coking problem of the wall of the reactor; in addition, compared with the traditional two-time or multi-time separation, the process is simplified into the one-time removal of quinoline insoluble substances, and the treatment difficulty and the processing energy consumption are effectively reduced.
(4) The invention has simplified process flow and short production period. The obtained mesophase pitch has moderate softening point of 220-.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment comprises the following steps:
(1) mixing medium temperature coal tar pitch and sublimed sulfur according to the mass ratio of 100: 0.1, adding the mixture into a stirring reaction kettle, carrying out hydrocatalysis treatment on the coal pitch under the conditions of reaction temperature of 380 ℃, reaction hydrogen pressure of 1MPa, reaction time of 4h and stirring speed of 200rpm, carrying out reduced pressure distillation after the reaction to remove low-boiling fraction to obtain primary hydrogenated pitch, and carrying out reduced pressure distillation at the heating temperature of 380 ℃ and the absolute pressure of 0.5 kPa.
(2) Mixing the primary hydrogenated asphalt and the tetrahydronaphthalene according to a mass ratio of 1: 5, adding the asphalt into a stirring reaction kettle, carrying out hydrocatalysis-hydrogen supply synergistic treatment on the asphalt under the conditions of reaction temperature of 390 ℃, reaction hydrogen pressure of 0.5MPa, reaction time of 8h and stirring speed of 200rpm, carrying out reduced pressure distillation after the reaction to remove low-boiling-point fractions to obtain secondary hydrogenated asphalt, wherein the heating temperature of the reduced pressure distillation is 320 ℃, the absolute pressure is 40kPa, and hydrogen supply agents in the low-boiling-point fractions can be recycled through rectification extraction.
(3) Mixing secondary hydrogenated asphalt and wash oil in a mass ratio of 1: heating to 180 deg.C, mixing, stirring, heat filtering to remove insoluble substance, and distilling the filtrate under reduced pressure to obtain refined hydrogenated pitch with quinoline insoluble substance less than 0.05%, reduced pressure distillation temperature of 380 deg.C, and absolute pressure of 40 kPa; refining hydrogenated asphalt in a stirring reaction kettle, carrying out thermal polymerization reaction to obtain spinnable mesophase asphalt, wherein the thermal polycondensation reaction temperature is 380 ℃, the reaction pressure is 0.1MPa, the reaction time is 12h, the stirring speed is 50rpm, and the protective gas is nitrogen.
The prepared mesophase pitch has a softening point of 270 ℃ and a mesophase content of more than 95%, has a wide-area streamlined body optical texture, and can melt spun filaments.
Detecting the mesophase content and the optical characteristics of the mesophase pitch by a Leica-Leica polariscope; the softening point was measured by conventional needle penetration and the following examples were measured by the same method.
Example 2
A method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment comprises the following steps:
(1) mixing high-temperature coal tar pitch and mercaptan according to a mass ratio of 100: 2, adding the mixture into a stirring reaction kettle, carrying out hydrocatalysis treatment on the coal pitch under the conditions of reaction temperature of 440 ℃, reaction hydrogen pressure of 4MPa, reaction time of 1h and stirring speed of 50rpm, carrying out reduced pressure distillation after the reaction to remove low-boiling-point fractions to obtain primary hydrogenated pitch, and carrying out reduced pressure distillation at the heating temperature of 320 ℃ and the absolute pressure of 1 kPa.
(2) Mixing the primary hydrogenated asphalt and the tetrahydronaphthalene according to a mass ratio of 1: 0.5, adding the mixture into a stirring reaction kettle, carrying out hydrocatalysis-hydrogen supply synergistic treatment on the asphalt under the conditions of reaction temperature of 450 ℃, reaction hydrogen pressure of 6MPa, reaction time of 1h and stirring speed of 150rpm, carrying out reduced pressure distillation after the reaction to remove low-boiling-point fractions to obtain secondary hydrogenated asphalt, wherein the heating temperature of the reduced pressure distillation is 380 ℃, the absolute pressure is 30kPa, and the hydrogen supply agent in the low-boiling-point fractions can be recycled through rectification extraction.
(3) Mixing the secondary hydrogenated asphalt and quinoline in a mass ratio of 1: 1 heating to 160 ℃, mixing, stirring, carrying out hot filtration to remove insoluble substances, and carrying out reduced pressure distillation on the filtrate to obtain refined hydrogenated asphalt, wherein the content of quinoline insoluble substances is less than 0.05%, the reduced pressure distillation temperature is 320 ℃, and the absolute pressure is 1 kPa; refining hydrogenated asphalt in a stirring reaction kettle, carrying out thermal polymerization reaction to obtain spinnable mesophase asphalt, wherein the thermal polycondensation reaction temperature is 450 ℃, the reaction pressure is 2MPa, the reaction time is 1h, the stirring speed is 200rpm, and the protective gas is nitrogen.
The prepared mesophase pitch has a softening point of 280 ℃ and a mesophase content of more than 95 percent, has a wide-area streamlined body optical texture and can melt spun filaments.
Example 3
A method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment comprises the following steps:
(1) mixing medium temperature coal pitch and carbon disulfide according to a mass ratio of 100: 0.5, adding the mixture into a stirring reaction kettle, carrying out hydrocatalysis treatment on the coal pitch under the conditions of reaction temperature of 400 ℃, reaction hydrogen pressure of 2MPa, reaction time of 3h and stirring speed of 150rpm, carrying out reduced pressure distillation after the reaction to remove low-boiling fraction to obtain primary hydrogenated pitch, and carrying out reduced pressure distillation at the heating temperature of 360 ℃ and the absolute pressure of 10 kPa.
(2) Mixing primary hydrogenated asphalt and decahydronaphthalene according to a mass ratio of 1: 3, adding the mixture into a stirring reaction kettle, carrying out hydrocatalysis-hydrogen supply synergistic treatment on the asphalt under the conditions of reaction temperature of 400 ℃, reaction hydrogen pressure of 3MPa, reaction time of 4h and stirring speed of 50rpm, carrying out reduced pressure distillation after the reaction to remove low-boiling-point fractions to obtain secondary hydrogenated asphalt, wherein the heating temperature of the reduced pressure distillation is 360 ℃, the absolute pressure is 10kPa, and the hydrogen supply agent in the low-boiling-point fractions can be recycled through rectification extraction.
(3) Mixing secondary hydrogenated asphalt and wash oil in a mass ratio of 1: 3 heating to 150 ℃, mixing, stirring, carrying out hot filtration to remove insoluble substances, and carrying out reduced pressure distillation on the filtrate to obtain refined hydrogenated asphalt, wherein the quinoline insoluble substances are less than 0.05 percent, the reduced pressure distillation temperature is 360 ℃, and the absolute pressure is 30 kPa; refining hydrogenated asphalt in a stirring reaction kettle, carrying out thermal polymerization reaction to obtain spinnable mesophase asphalt, wherein the thermal polycondensation reaction temperature is 400 ℃, the reaction pressure is 6MPa, the reaction time is 4h, the stirring speed is 100rpm, and the protective gas is argon.
The prepared mesophase pitch has the softening point of 265 ℃ and the mesophase content of more than 95 percent, has a wide-area streamlined body optical texture and can melt spun filaments.
Example 4
A method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment comprises the following steps:
(1) mixing high-temperature coal tar pitch and sublimed sulfur according to the mass ratio of 100: 0.2, adding the mixture into a stirring reaction kettle, carrying out hydrocatalysis treatment on the coal pitch under the conditions of reaction temperature of 420 ℃, reaction hydrogen pressure of 3MPa, reaction time of 2h and stirring speed of 100rpm, carrying out reduced pressure distillation after the reaction to remove low-boiling fraction to obtain primary hydrogenated pitch, and carrying out reduced pressure distillation at the heating temperature of 350 ℃ and the absolute pressure of 20 kPa.
(2) Mixing primary hydrogenated asphalt and 9, 10-dihydroanthracene according to a mass ratio of 1: 1, adding the asphalt into a stirring reaction kettle, carrying out hydrocatalysis-hydrogen supply synergistic treatment on the asphalt under the conditions of reaction temperature of 410 ℃, reaction hydrogen pressure of 4MPa, reaction time of 4h and stirring speed of 100rpm, carrying out reduced pressure distillation after the reaction to remove low-boiling fraction to obtain secondary hydrogenated asphalt, wherein the heating temperature of the reduced pressure distillation is 370 ℃, the absolute pressure is 20kPa, and the hydrogen supply agent in the low-boiling fraction can be recycled through rectification extraction.
(3) Mixing secondary hydrogenated asphalt and wash oil in a mass ratio of 1: 2 heating to 200 ℃, mixing, stirring, carrying out hot filtration to remove insoluble substances, and carrying out reduced pressure distillation on the filtrate to obtain refined hydrogenated asphalt, wherein the quinoline insoluble substances are less than 0.05 percent, the reduced pressure distillation temperature is 340 ℃, and the absolute pressure is 20 kPa; refining hydrogenated asphalt in a stirring reaction kettle, carrying out thermal polymerization reaction to obtain spinnable mesophase asphalt, wherein the thermal polycondensation reaction temperature is 420 ℃, the reaction pressure is 1MPa, the reaction time is 8h, the stirring speed is 150rpm, and the protective gas is nitrogen.
The prepared mesophase pitch has the softening point of 275 ℃, the mesophase content of more than 95 percent, has a wide-area streamlined body optical texture and can melt and spin filaments.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment is characterized by comprising the following steps:
(1) adding the auxiliary agent and the coal pitch in a certain mass ratio into a stirring reaction kettle, carrying out hydrogenation catalytic treatment on the coal pitch under the condition of high temperature and hydrogenation, and carrying out reduced pressure distillation after reaction to remove low-boiling-point fractions to obtain primary hydrogenated pitch;
(2) adding a hydrogen donor and primary hydrogenated asphalt in a certain mass ratio into a stirring reaction kettle, carrying out hydrocatalysis-hydrogen donor synergistic treatment on the asphalt under the condition of high temperature and hydrogen, and carrying out reduced pressure distillation to remove low-boiling fraction to obtain secondary hydrogenated asphalt;
(3) removing quinoline insoluble substances from the secondary hydrogenated asphalt to obtain refined hydrogenated asphalt;
(4) the refined hydrogenated asphalt is subjected to thermal polymerization reaction in a stirring reaction kettle to prepare spinnable mesophase asphalt.
2. The method for preparing spinnable mesophase pitch by coal pitch hydrocatalysis-hydrogen supply treatment according to claim 1, which is characterized in that: the auxiliary agent in the step (1) is any one or combination of sublimed sulfur, carbon disulfide and mercaptan, and the coal pitch comprises any one or combination of coal tar, medium-low temperature coal pitch, high-temperature coal pitch, secondary coal pitch, tar residue, coal liquefaction pitch and coal liquefaction residue.
3. The method for preparing spinnable mesophase pitch by coal pitch hydrocatalysis-hydrogen supply treatment according to claim 1, which is characterized in that: the mass ratio of the coal pitch and the auxiliary agent in the step (1) is 100 (0.1-2), the high-temperature hydrogen condition is that the reaction temperature is 380-440 ℃, the reaction hydrogen pressure is 1-5MPa, the reaction time is 1-4h, the stirring speed is 50-200rpm, the reduced pressure distillation temperature is 320-380 ℃, and the absolute pressure is 0-40 kPa.
4. The method for preparing spinnable mesophase pitch by coal pitch hydrocatalysis-hydrogen supply treatment according to claim 1, which is characterized in that: the hydrogen donor in the step (2) is any one or combination of tetrahydronaphthalene, decahydronaphthalene, tetrahydroquinoline, tetrahydrofuran, indane and 9, 10-dihydroanthracene, and the mass ratio of the primary hydrogenated asphalt to the hydrogen donor is 1 (0.5-5).
5. The method for preparing spinnable mesophase pitch by coal pitch hydrocatalysis-hydrogen supply treatment according to claim 1, which is characterized in that: the temperature of the hydrocatalysis-hydrogen supply synergistic treatment reaction in the step (2) is 390-450 ℃, the pressure of the reaction hydrogen is 0.5-10MPa, the reaction time is 1-8h, the stirring speed is 50-200rpm, the temperature of the reduced pressure distillation is 320-380 ℃, and the absolute pressure is 0-40 kPa.
6. The method for preparing spinnable mesophase pitch by coal pitch hydrocatalysis-hydrogen supply treatment according to claim 1, which is characterized in that: in the step (3), the secondary hydrogenated asphalt and the solvent are mixed according to a mass ratio of 1: (1-5) heating, mixing, filtering and removing quinoline insoluble substances, and distilling the filtrate under reduced pressure to obtain refined hydrogenated asphalt, wherein the quinoline insoluble substances are less than 0.05 percent, the reduced pressure distillation temperature is 320-380 ℃, and the absolute pressure is 0-40 kPa; the solvent is aromatic hydrocarbon solvent of toluene, benzene, pyridine, quinoline, tetrahydrofuran and wash oil.
7. The method for preparing spinnable mesophase pitch by coal pitch hydrocatalysis-hydrogen supply treatment according to claim 1, which is characterized in that: the temperature of the thermal polymerization reaction in the step (4) is 380-450 ℃, the reaction pressure is 0.5-6MPa, the reaction time is 1-12h, the stirring speed is 50-200rpm, and the protective gas is nitrogen or argon.
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| CN111718232A (en) * | 2020-05-26 | 2020-09-29 | 中钢集团鞍山热能研究院有限公司 | Method for preparing anthracene and phenanthrene by co-carbonizing hydrogenated anthracene oil and refined asphalt |
| CN112281260A (en) * | 2020-11-14 | 2021-01-29 | 北京化工大学 | Spinnable asphalt prepared by controlling raw material fraction, method and application of spinnable asphalt in preparation of carbon fibers |
| CN112538362A (en) * | 2020-12-10 | 2021-03-23 | 武汉科技大学 | Method for improving rheological property of coal tar pitch |
| CN113956901A (en) * | 2021-11-19 | 2022-01-21 | 神木富油能源科技有限公司 | Method for preparing mesophase pitch from medium-low temperature coal tar and application |
| CN114214758A (en) * | 2022-01-13 | 2022-03-22 | 中国矿业大学(北京) | Method for preparing general-grade carbon fiber from coal liquefaction residues |
| CN114763480A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Mesophase pitch and preparation method and application thereof |
| CN114940918A (en) * | 2022-04-18 | 2022-08-26 | 郑州中科新兴产业技术研究院 | Mesophase pitch prepared from hydrogenated tail oil and method thereof |
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