CN114106863B - Spinning mesophase pitch and preparation method thereof - Google Patents
Spinning mesophase pitch and preparation method thereof Download PDFInfo
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- CN114106863B CN114106863B CN202210097579.2A CN202210097579A CN114106863B CN 114106863 B CN114106863 B CN 114106863B CN 202210097579 A CN202210097579 A CN 202210097579A CN 114106863 B CN114106863 B CN 114106863B
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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
- C10C3/007—Working-up pitch, asphalt, bitumen winning and separation of asphalt from mixtures with aggregates, fillers and other products, e.g. winning from natural asphalt and regeneration of waste asphalt
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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
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
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Abstract
The invention relates to the technical field of high-quality intermediate phase asphalt production, in particular to intermediate phase asphalt for spinning and a preparation method thereof, wherein the raw material of the intermediate phase asphalt comprises wax oil fraction produced by liquid phase hydrogenation of an ethylene cracking tar suspension bed, the percentage contents of aromatic hydrocarbon and tricyclic and higher aromatic hydrocarbon are respectively 80-90% and 50-70%, and the percentage contents of the wax oil fraction are subjected to reduced pressure distillation to obtain distillate oil rich in the aromatic hydrocarbon, then the distillate oil is subjected to first thermal polymerization reaction to obtain an intermediate product, and then the intermediate phase asphalt for spinning is obtained after second thermal polymerization reaction. The invention avoids the complex processes of raw material treatment, high-pressure hydrogenation process, mixed hydrogen supply reagent and the like, and has the advantages of short process flow, non-harsh reaction conditions, low equipment requirement and the like; meanwhile, aromatic hydrocarbon in the raw material is enriched, the molecular composition is uniform, light components are few, the hydrogen-carbon ratio is high, the advantages of low ash content such as heteroatoms and metals are achieved, the stability of the raw material is higher, the yield of the obtained product is higher, and the performance is better.
Description
Technical Field
The invention relates to the technical field of high-quality mesophase pitch production, and discloses mesophase pitch for spinning and a preparation method thereof.
Background
The mesophase pitch is a polynuclear polycyclic aromatic hydrocarbon polycondensate with high molecular weight gradually formed after a series of chemical reactions such as pyrolysis, dehydrogenation, cyclization, aromatization, polycondensation and the like, which are thermal processing of raw material pitch (coal pitch, petroleum pitch, naphthalene pitch and the like). The processing process actually changes isotropic raw materials into anisotropic products.
The mesophase pitch is a precursor for preparing high-performance carbon materials such as mesophase pitch-based carbon fibers, mesophase carbon microspheres, needle coke, foamy carbon and the like, and the mesophase pitch has high heat resistance/heat conductivity, good chemical stability, higher modulus and the like due to an anisotropic liquid crystal structure; therefore, the mesophase pitch and the downstream products thereof have wide application prospects in the aspects of aerospace, energy field, military industry and the like.
Pitch-based carbon fibers are undoubtedly one of the most technically difficult areas in applications downstream of mesophase pitch. The production of the pitch-based carbon fiber has index requirements on the content, the form, the softening point and the like of the mesophase pitch, generally, the content of the mesophase pitch is required to be more than 98 percent, and the limitation is brought to the raw materials for producing the mesophase pitch, so that the high-mesophase pitch content product can be prepared only by the raw materials with higher polycyclic aromatic hydrocarbon content; the shape of the mesophase pitch is generally required to be wide-area type, which puts requirements on the polymerization process of the mesophase pitch; generally, the softening point of the mesophase pitch is required to be between 250 ℃ and 280 ℃, an excessively high softening point puts higher requirements on a spinning process, uniform and stable carbon fiber precursors are more difficult to spin, and an excessively low softening point has a larger influence on subsequent pre-oxidation and other processes. The requirement of the softening point index has certain requirement on the polymerization degree of the mesophase pitch. In addition, ash content, heteroatoms and the like in the production of the spinning mesophase pitch are also at a low level so as to avoid forming defects and influencing the performance of a spinning product.
Therefore, the preparation technology of the mesophase pitch for spinning has higher index requirements on the production raw materials and the production process of the mesophase pitch. In recent years, the research center of gravity is gradually focused on the processing processes of raw material screening, rectification, separation and the like, so that the aims of improving the content of the mesophase pitch and controlling the softening point are expected to be fulfilled. Thus, a raw material blending method such as pure naphthalene polymerization, catalytic slurry oil rectification polymerization, petroleum residual oil mixed biomass polymerization and the like, and various polymerization processes such as hydrogenation polymerization, thermal polymerization, catalytic polymerization and the like are developed.
At present, chinese patent publication No. CN104152168 discloses a method for preparing high-performance pitch-based carbon fibers from naphthalene compounds. Which uses naphthalene compound as raw material in HF/BF3Preparing mesophase pitch for spinning under the condition of catalyst, and HF/BF3The catalyst has strong acidity, severe corrosion to equipment, higher production requirement, high production cost and risk in safety. Thus, although chinese patent publication No. CN102899061 discloses a method for preparing mesophase pitch by polymerizing naphthalene pitch after preparing naphthalene pitch using refined naphthalene as a raw material, the catalyst is liable to remain in the product of this patent, which affects the performance of the final carbon fiber.
Besides naphthalene compounds, catalytic oil slurry, coal pitch and the like are also intermediate phase pitch raw materials which are used more domestically, the direct thermal polycondensation process has poor control on the polymerization degree, the softening point of the product is higher, and various polymerization processes are developed domestically for controlling the polymerization degree.
Chinese patent publication No. CN106544758 discloses a method for preparing high modulus pitch-based carbon fiber by melt spinning after obtaining a mesophase product from catalytic slurry oil as a raw material through high pressure hydrogenation pretreatment and two-step polycondensation and staged carbonization. Catalytic slurry oil is used as a raw material, and after high-pressure hydrogenation pretreatment, fractions at a temperature of more than or equal to 400 ℃ are separated through reduced pressure distillation, high-quality raw materials rich in aromatic hydrocarbon are obtained through hydrogenation and reduced pressure distillation, and the spinning mesophase pitch is prepared through two-step thermal polymerization.
Chinese patent publication No. CN107189802 discloses a method for preparing mesophase pitch by thermal polycondensation-hydro-upgrading-thermal polycondensation composite process, using fraction with boiling point between 380 ℃ and 540 ℃ in catalytic cracking slurry of naphthenic crude oil as raw material, to produce high quality mesophase pitch with high anisotropic structure content (more than 98%), low softening point (230 ℃ to 250 ℃) and good spinnability, which adopts catalytic slurry vacuum distillation, then prepares high softening point pitch by thermal treatment, then adds hydrogen-supplying agent to react under 5.0MPa spinning mesophase pitch and its preparation method, the process has high reaction pressure, harsh reaction conditions, high requirements for equipment and safety risk.
Chinese patent publication No. CN110776943 discloses a spinnable mesophase pitch prepared by purifying petroleum pitch with high softening point as raw material, reacting with octahydrophenanthrene as high boiling point hydrogen-donating agent under low pressure, and blowing at normal pressure, which is further improved by extracting and filtering petroleum pitch to obtain high softening point pitch, and mixing and reacting with hydrogen-donating agents such as octahydrophenanthrene to obtain the final product.
Disclosure of Invention
The invention provides spinning mesophase pitch and a preparation method thereof, overcomes the defects of the prior art, and can effectively solve the problems of complex raw material treatment process, harsh reaction conditions, high requirements on polymerization equipment and long process flow in the prior art of pitch production.
One of the technical schemes of the invention is realized by the following measures: the intermediate phase asphalt for spinning is prepared from a raw material comprising a wax oil fraction produced by liquid phase hydrogenation of an ethylene cracking tar suspension bed, wherein the mass percentage of aromatic hydrocarbons in the wax oil fraction in the total mass of the wax oil fraction is 80-90%, and the mass percentage of tricyclic and higher aromatic hydrocarbons in the wax oil fraction in the total mass of the wax oil fraction is 50-70%, by the following method: firstly, carrying out reduced pressure distillation on wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed under the conditions of pressure of-0.1 MPa to 0.1MPa and temperature of 250 ℃ to 280 ℃ to obtain distillate oil rich in aromatic hydrocarbon; secondly, stirring distillate oil rich in aromatic hydrocarbon for 1 to 6 hours under the protection of inert gas at the temperature of 360 to 480 ℃ and the pressure of 0.1 to 3.0MPa, and carrying out a first thermal polymerization reaction to obtain an intermediate product; step three, cooling the intermediate product to 10-25 ℃, then heating and pressurizing to 360-480 ℃ and 0.1-3.0 MPa, stirring for 2-10 h for second thermal polymerization reaction to obtain the final product; and fourthly, blowing the final product by inert gas to cool to normal temperature, and unloading the pressure to normal pressure to obtain the spinning mesophase pitch.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
in the first step, the distillate oil rich in aromatic hydrocarbon is ethylene tar-wax oil which is enriched by vacuum distillation, and the ethylene tar-wax oil which is enriched by vacuum distillation is wax oil with the distillation range of 360-460 ℃.
The mass of aromatic hydrocarbon in the ethylene tar-wax oil enriched by reduced pressure distillation accounts for 85-90% of the total mass of the wax oil fraction, and the mass of tricyclic and above aromatic hydrocarbon in the ethylene tar-wax oil enriched by reduced pressure distillation accounts for 55-80% of the total mass of the wax oil fraction.
In the first step, the reduced pressure distillation pressure is 1.0KPa to 3.0KPa, and the temperature is 260 ℃ to 270 ℃.
In the second and third steps, the stirring rate is 100rpm to 400 rpm.
The second technical scheme of the invention is realized by the following measures: a preparation method of spinning mesophase pitch comprises the following steps: firstly, carrying out reduced pressure distillation on wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed under the conditions of pressure of-0.1 MPa to 0.1MPa and temperature of 250 ℃ to 280 ℃ to obtain distillate oil rich in aromatic hydrocarbon; secondly, stirring distillate oil rich in aromatic hydrocarbon for 1 to 6 hours under the protection of inert gas at the temperature of 360 to 480 ℃ and the pressure of 0.1 to 3.0MPa, and carrying out a first thermal polymerization reaction to obtain an intermediate product; step three, cooling the intermediate product to 10-25 ℃, then heating and pressurizing to 360-480 ℃ and 0.1-3.0 MPa, stirring for 2-10 h for second thermal polymerization reaction to obtain the final product; and fourthly, blowing the final product by inert gas to cool to normal temperature, and unloading the pressure to normal pressure to obtain the spinning mesophase pitch.
The following is further optimization or/and improvement of the second technical scheme of the invention:
in the first step, the distillate oil rich in aromatic hydrocarbon is ethylene tar-wax oil which is enriched by vacuum distillation, and the ethylene tar-wax oil which is enriched by vacuum distillation is wax oil with the distillation range of 360-460 ℃.
The mass of aromatic hydrocarbon in the ethylene tar-wax oil enriched by reduced pressure distillation accounts for 85-90% of the total mass of the wax oil fraction, and the mass of tricyclic and above aromatic hydrocarbon in the ethylene tar-wax oil enriched by reduced pressure distillation accounts for 55-80% of the total mass of the wax oil fraction.
In the first step, the reduced pressure distillation pressure is 1.0KPa to 3.0KPa, and the temperature is 260 ℃ to 270 ℃.
In the second and third steps, the stirring rate is 100rpm to 400 rpm.
Compared with the prior art, the mesophase pitch for spinning has the following beneficial effects: the method avoids the complicated processes of raw material treatment process, high-pressure hydrogenation process, mixed hydrogen supply reagent and the like, and has the advantages of short process flow, non-harsh reaction conditions, low equipment requirement and the like. Compared with the raw materials such as catalytic slurry oil, coal tar pitch and the like, the raw materials of the invention are rich in aromatic hydrocarbon, the aromatic hydrocarbon content is 80-90%, the molecular composition is uniform, the aromatic hydrocarbon content of tricyclic and higher aromatic hydrocarbon is 50-70%, the light components are few, only 10-40%, and the hydrogen-carbon ratio is 0.8-1.8; the non-aromatic hydrocarbon heteroatom only accounts for 1 to 10 percent, the ash content of metal and the like is close to 0 percent, the stability of the raw material is higher, the yield of the obtained product is more than 30 percent, and the performance is better.
Drawings
FIG. 1 is a drawing of a polarizing microscope (PC) showing a mesophase pitch for spinning obtained in example 8 of the present invention, and FIG. 1 shows that the mesophase morphology in the present invention is wide-area type.
FIG. 2 is a polarizing microscope (PC) photograph of a mesophase pitch for spinning obtained in example 9 of the present invention, and FIG. 2 shows that the mesophase morphology in the present invention is wide-area type.
FIG. 3 is a polarization microscope (PC) photograph of a mesophase pitch for spinning obtained in example 10 of the present invention, and FIG. 3 shows that the mesophase morphology in the present invention is wide-area type.
FIG. 4 is a polarizing microscope (PC) photograph of a mesophase pitch for spinning obtained in example 11 of the present invention, and FIG. 4 shows that the mesophase morphology in the present invention is wide-area type.
FIG. 5 is a polarization microscope (PC) image of the pitch product obtained in comparative example 1 of the present invention, and FIG. 5 shows that mesocarbon microbeads having a large diameter are clearly visible.
FIG. 6 is a polarization microscope (PC) image of the asphalt product obtained in comparative example 2 of the present invention, and it is apparent from FIG. 6 that a plurality of mesocarbon microbeads are non-uniform in size.
FIG. 7 is a polarization microscope (PC) image of the pitch product obtained in comparative example 3 of the present invention, and FIG. 7 shows apparently unfused mesocarbon microbeads having a large diameter.
FIG. 8 is a polarization microscope (PC) image of the pitch product obtained in comparative example 4 of the present invention, and FIG. 8 shows apparently unfused mesocarbon microbeads having a large diameter.
In fig. 1 to 8, the magnification of the polarizing microscope is 10 × 50.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the raw material of the mesophase pitch for spinning comprises wax oil fraction produced by liquid phase hydrogenation of ethylene pyrolysis tar suspension bed, wherein the mass percentage of aromatic hydrocarbon in the wax oil fraction in the total mass of the wax oil fraction is 80-90%, and the mass percentage of tricyclic and higher aromatic hydrocarbon in the total mass of the wax oil fraction is 50-70%, and the mesophase pitch is prepared by the following method: firstly, carrying out reduced pressure distillation on wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed under the conditions of pressure of-0.1 MPa to 0.1MPa and temperature of 250 ℃ to 280 ℃ to obtain distillate oil rich in aromatic hydrocarbon; secondly, stirring distillate oil rich in aromatic hydrocarbon for 1 to 6 hours under the protection of inert gas at the temperature of 360 to 480 ℃ and the pressure of 0.1 to 3.0MPa, and carrying out a first thermal polymerization reaction to obtain an intermediate product; step three, cooling the intermediate product to 10-25 ℃, then heating and pressurizing to 360-480 ℃ and 0.1-3.0 MPa, stirring for 2-10 h for second thermal polymerization reaction to obtain the final product; and fourthly, blowing the final product by inert gas to cool to normal temperature, and unloading the pressure to normal pressure to obtain the spinning mesophase pitch.
The spinning mesophase pitch is a two-stage polymerization reaction developed based on wax oil fraction after hydrogenation of ethylene cracking tar suspension bed, and can realize efficient and stable production of the spinning mesophase pitch. In the production process, wax oil with the distillation range of 360-480 ℃ as a raw material is subjected to first thermal polymerization reaction, then is further cooled and depressurized, and then is subjected to second thermal polymerization reaction, so that the spinning mesophase pitch can be obtained.
The wax oil fraction produced by liquid phase hydrogenation of the raw material ethylene cracking tar suspension bed in the invention is the wax oil component related in Chinese patent document with application number CN202011138359.7, namely, the wax oil component with the distillation range of 360 ℃ to 480 ℃ which is sent out is obtained by separation when the hydrogenation product is subjected to atmospheric and vacuum separation.
Example 2: as the optimization of the above embodiment, in the first step, the distillate oil rich in aromatic hydrocarbon is ethylene tar-wax oil which is enriched by vacuum distillation, and the ethylene tar-wax oil which is enriched by vacuum distillation is wax oil with the distillation range of 360-460 ℃.
Example 3: as optimization of the embodiment, the mass percentage of the aromatic hydrocarbon in the ethylene tar-wax oil enriched by vacuum distillation accounts for 85-90% of the total mass of the wax oil fraction, and the mass percentage of the aromatic hydrocarbon of three rings or more in the ethylene tar-wax oil enriched by vacuum distillation accounts for 55-80% of the total mass of the wax oil fraction.
Example 4: as optimization of the above embodiment, in the first step, the reduced pressure distillation pressure is 1.0KPa to 3.0KPa, and the temperature is 260 ℃ to 270 ℃.
Example 5: as optimization of the above examples, in the second and third steps, the stirring rate was 100rpm to 400 rpm.
Example 6: the preparation method of the mesophase pitch for spinning comprises the following steps: firstly, carrying out reduced pressure distillation on wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed under the conditions of pressure of-0.1 MPa to 0.1MPa and temperature of 250 ℃ to 280 ℃ to obtain distillate oil rich in aromatic hydrocarbon; secondly, stirring distillate oil rich in aromatic hydrocarbon for 1 to 6 hours under the protection of inert gas at the temperature of 360 to 480 ℃ and the pressure of 0.1 to 3.0MPa, and carrying out a first thermal polymerization reaction to obtain an intermediate product; step three, cooling the intermediate product to 10-25 ℃, then heating and pressurizing to 360-480 ℃ and 0.1-3.0 MPa, stirring for 2-10 h for second thermal polymerization reaction to obtain the final product; and fourthly, blowing the final product by inert gas to cool to normal temperature, and unloading the pressure to normal pressure to obtain the spinning mesophase pitch.
Example 7: the preparation method of the mesophase pitch for spinning comprises the following steps: firstly, carrying out reduced pressure distillation on wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed under the conditions of pressure of-0.1 MPa to 0.1MPa and temperature of 250 ℃ to 280 ℃ to obtain distillate oil rich in aromatic hydrocarbon; secondly, adding distillate oil rich in aromatic hydrocarbon into a reaction kettle, stirring for 1 to 6 hours under the conditions of 360 to 480 ℃ of temperature, 0.1 to 3.0MPa of pressure and 100 to 400rpm of stirring speed under the protection of inert gas, and carrying out primary thermal polymerization reaction to obtain an intermediate product; thirdly, after the temperature and the pressure of the intermediate product in the reaction kettle are reduced to room temperature and approximate to normal pressure, the temperature of the reaction kettle is increased to 360-480 ℃, the pressure is increased to 0.1-3.0 MPa, the stirring speed is 100-400 rpm, and the reaction kettle is stirred for 2-10 hours to carry out second thermal polymerization reaction to obtain a final product; and fourthly, purging the final product in the reaction kettle by inert gas to cool to normal temperature, and unloading the pressure in the reaction kettle to normal pressure to obtain the spinning mesophase pitch.
Example 8: taking a certain amount of wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed, preparing ethylene tar-wax oil under the conditions of 1.0KPa and 265 ℃ reduced pressure distillation, adding the ethylene tar-wax oil into a reaction kettle, maintaining the pressure of 1.5MPa by using inert gas nitrogen, gradually heating to 420 ℃, reacting for 3 hours, wherein the stirring speed is 120r/min, the system pressure in the process is not more than 3.0MPa at most, and carrying out first thermal polymerization reaction to obtain an intermediate product; after an intermediate product is obtained, the temperature of the system is reduced to room temperature, and the pressure is reduced to be close to normal pressure; and then under the protection of inert gas nitrogen, raising the temperature in the kettle to 420 ℃, raising the pressure to 1.5MPa, reacting for 6 hours, stirring at a speed of 100r/min, wherein the system pressure is not more than 3.0MPa at most in the process, carrying out second thermal polymerization reaction to obtain a final product, purging the final product with nitrogen at a flow rate of 10L/min, reducing the temperature of the final product system to about 360 ℃ within 1 hour, stopping stirring, continuously purging, cooling to room temperature, and obtaining the intermediate phase pitch for spinning.
FIG. 1 shows a polarization microscope (PC) image of the mesophase pitch for spinning obtained in example 8, and FIG. 1 shows that the mesophase morphology of the present invention is wide-ranging.
The spinning mesophase pitch product obtained in example 8 has a product yield of 30% to 35% with a mesophase content of > 98%.
Example 9: taking a certain amount of wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed, preparing ethylene tar-wax oil under the conditions of 1.0KPa and 265 ℃ reduced pressure distillation, adding the ethylene tar-wax oil into a reaction kettle, maintaining the pressure of 0.1MPa by using inert gas nitrogen, gradually heating to 360 ℃, reacting for 5 hours, wherein the stirring speed is 120r/min, the system pressure in the process is not more than 3.0MPa at most, and carrying out first thermal polymerization reaction to obtain an intermediate product; after an intermediate product is obtained, the temperature of the system is reduced to room temperature, and the pressure is reduced to be close to normal pressure; and then under the protection of inert gas nitrogen, raising the temperature in the kettle to 360 ℃, raising the pressure to 0.1MPa, reacting for 5 hours, stirring at a speed of 120r/min, wherein the system pressure in the process is not more than 3.0MPa, carrying out a second thermal polymerization reaction to obtain a final product, purging the final product with nitrogen at a flow rate of 10L/min, reducing the temperature of the final product system to about 360 ℃ within 1 hour, stopping stirring, continuously purging, cooling to room temperature, and thus obtaining the intermediate phase pitch for spinning.
FIG. 2 shows a polarization microscope (PC) image of the mesophase pitch for spinning obtained in example 9, and FIG. 2 shows that the mesophase morphology of the present invention is wide-area type.
The spinning mesophase pitch product obtained in example 9 has a product yield of 30% to 35% with a mesophase content of > 98%.
Example 10: taking a certain amount of wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed, preparing ethylene tar-wax oil under the conditions of 1.0KPa and 265 ℃ reduced pressure distillation, adding the ethylene tar-wax oil into a reaction kettle, maintaining the pressure of 0.5MPa by using inert gas nitrogen, gradually heating to 390 ℃, reacting for 5 hours, wherein the stirring speed is 120r/min, the system pressure in the process is not more than 3.0MPa at most, and carrying out first thermal polymerization reaction to obtain an intermediate product; after an intermediate product is obtained, the temperature of the system is reduced to room temperature, and the pressure is reduced to be close to normal pressure; and then under the protection of inert gas nitrogen, raising the temperature in the kettle to 390 ℃, raising the pressure to 0.5MPa, reacting for 5 hours, stirring at a speed of 120r/min, wherein the system pressure in the process is not more than 3.0MPa at most, carrying out second thermal polymerization reaction to obtain a final product, purging the final product with nitrogen at a flow rate of 10L/min, reducing the temperature of the final product system to about 360 ℃ within 1 hour, stopping stirring, continuously purging, cooling to room temperature, and obtaining the intermediate phase pitch for spinning.
FIG. 3 shows a polarization microscope (PC) image of the mesophase pitch for spinning obtained in example 10, and FIG. 3 shows that the mesophase morphology of the present invention is wide-ranging.
The spinning mesophase pitch product obtained in example 10 has a product yield of 30% to 35%. Wherein the content of the mesophase is more than 98 percent.
Example 11: taking a certain amount of wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed, preparing ethylene tar-wax oil under the conditions of 1.0KPa and 265 ℃ reduced pressure distillation, adding the ethylene tar-wax oil into a reaction kettle, maintaining the pressure of 2.5MPa by using inert gas nitrogen, gradually heating to 480 ℃, reacting for 5 hours, stirring at the speed of 120r/min, and carrying out first thermal polymerization reaction to obtain an intermediate product, wherein the system pressure in the process is not more than 3.0MPa at most; after an intermediate product is obtained, the temperature of the system is reduced to room temperature, and the pressure is reduced to be close to normal pressure; and then under the protection of inert gas nitrogen, raising the temperature in the kettle to 480 ℃, raising the pressure to 0.5MPa, reacting for 5 hours, stirring at a speed of 120r/min, wherein the system pressure in the process is not more than 3.0MPa at most, carrying out second thermal polymerization reaction to obtain a final product, purging the final product with nitrogen at a flow rate of 10L/min, reducing the temperature of the final product system to about 360 ℃ within 1 hour, stopping stirring, continuously purging, cooling to room temperature, and obtaining the intermediate phase pitch for spinning.
FIG. 4 shows a polarization microscope (PC) image of the mesophase pitch for spinning obtained in example 11, and FIG. 4 shows that the mesophase morphology of the present invention is wide-ranging.
The spinning mesophase pitch obtained in example 11 gave a product yield of 30% to 35% with a mesophase content of > 98%.
The raw materials in the invention are all wax oil fractions produced by performing liquid phase hydrogenation on ethylene cracking tar of Clarity, which can be produced by Kechuang heavy oil development Limited company in Clarity, in a suspended bed.
Comparative example 1: taking a certain amount of wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed, preparing ethylene tar-wax oil under the conditions of 1.0KPa and 265 ℃ reduced pressure distillation, adding the ethylene tar-wax oil into a reaction kettle, maintaining the pressure of 0.5MPa by using inert gas nitrogen, gradually heating to 420 ℃, reacting for 9 hours, wherein the stirring speed is 120r/min, the highest system pressure in the process is not more than 3.0MPa, carrying out first thermal polymerization reaction, after the reaction time is up, purging the flow at 10L/min, purging by using nitrogen, reducing the system temperature to about 360 ℃ within 1 hour, stopping stirring, continuously purging, cooling to room temperature, and obtaining the asphalt product.
The polarization microscope (PC) image of the pitch product obtained according to comparative example 1 is shown in FIG. 5, where it is evident that the mesophase carbon microspheres with larger diameters do not coalesce into a wide range of mesophases in FIG. 5.
Comparative example 1 gave a bitumen product yield of 30% to 40% with a mesophase content of 20% to 30%.
Comparative example 2: taking a certain amount of wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed, preparing ethylene tar-wax oil under the conditions of 1.0KPa and 265 ℃ reduced pressure distillation, adding the ethylene tar-wax oil into a reaction kettle, maintaining the pressure of 0.5MPa by using inert gas nitrogen, gradually heating to 390 ℃, reacting for 10 hours at the stirring speed of 120r/min, gradually raising the system pressure to no more than 3.0MPa in the process, carrying out first thermal polymerization reaction, after the reaction time is reached, blowing the flow at 10L/min, blowing by using nitrogen, reducing the system temperature to about 360 ℃ within 1 hour, stopping stirring, continuously blowing, cooling to room temperature, and obtaining the asphalt product.
The polarization microscope (PC) image of the pitch product obtained according to comparative example 2 is shown in FIG. 6, and it is apparent from FIG. 6 that a plurality of mesocarbon microbeads are not uniform in size.
Comparative example 2 gave a bitumen product yield of 45% to 50% with a mesophase content of 15% to 20%.
Comparative example 3: adding a certain amount of catalytic slurry oil with the distillation range of 350-400 ℃ into a reaction kettle, maintaining the pressure of 0.5MPa by using inert gas nitrogen, gradually heating to 390 ℃, reacting for 10 hours, wherein the stirring speed is 120r/min, the system pressure in the process is not more than 3.0MPa at most, carrying out the first thermal polymerization reaction, purging with nitrogen at the flow rate of 10L/min after the reaction time is up, reducing the system temperature to about 360 ℃ within 1 hour, stopping stirring, continuously purging, cooling to room temperature, and obtaining the asphalt product.
Wherein the raw catalytic slurry oil in comparative example 3 is a catalytic slurry oil produced by cramaray petrochemicals llc.
The polarization microscope (PC) image of the pitch product obtained according to comparative example 3 is shown in FIG. 7, and the unfused mesocarbon microbeads having a large diameter are clearly seen in FIG. 7.
Comparative example 3 gives a bitumen product yield of 45% to 50% with a mesophase content of 15% to 20%.
Comparative example 4: taking a certain amount of wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed, preparing ethylene tar-wax oil under the conditions of 1.0KPa and 265 ℃ reduced pressure distillation, adding the ethylene tar-wax oil into a reaction kettle, maintaining the pressure of 0.5MPa by using inert gas nitrogen, gradually heating to 480 ℃, reacting for 10 hours, wherein the stirring speed is 120r/min, the highest system pressure in the process is not more than 3.0MPa, carrying out first thermal polymerization reaction, after the reaction time is up, purging the flow at 10L/min, purging with nitrogen, reducing the system temperature to about 360 ℃ within 1 hour, stopping stirring, continuously purging, cooling to room temperature, and obtaining the asphalt product.
The polarization microscope (PC) image of the pitch product obtained according to comparative example 4 is shown in FIG. 8, and it is apparent from FIG. 8 that a plurality of mesocarbon microbeads are not uniform in size.
Comparative example 4 gives a bitumen product yield of 30% to 35% with a mesophase content of 25% to 30%.
Thus, it is understood that the mesophase pitches obtained in comparative examples 1 to 4 have a low mesophase content although the pitch product yield is high, and thus the final mesophase pitch yield is not high.
Therefore, compared with the asphalt products obtained in comparative examples 1 to 4, the spinning mesophase asphalt obtained in examples 8 to 11 of the present invention is a wide range mesophase asphalt, the product yield is 30% to 35%, the mesophase content is more than 98%, the product index is consistent with the product index generally accepted by the industry for preparing carbon fiber, the market value is high, and the product performance is good.
The spinning mesophase pitches obtained in examples 8 to 11 according to the present invention were subjected to spinnability experiments and were single-hole-spun at 330 c, and the spinning results are shown in table 1 below. As can be seen from Table 1, the softening points of the spinning mesophase pitches obtained in examples 8 to 11 are 240 ℃ to 290 ℃ due to the variation of polymerization time and temperature, and the spinning mesophase pitches produced by the method have good spinnability, the continuous spinning length can reach 900m to 1000m, the strand diameter is 15 μm to 17 μm, and the method is suitable for producing mesophase pitch-based carbon fibers. The asphalt products obtained in comparative examples 1 to 4 were subjected to spinnability tests, and because the asphalt products had large fluctuation of softening point, the spinning temperature of 30 to 60 ℃ higher than the softening point was used to reduce energy consumption and ensure that the raw materials were not further thermally polymerized and changed. As can be seen from Table 1, the asphalt products obtained in comparative examples 1 to 4 had poor spinnability, short continuous spinning length and low market value.
In conclusion, the invention avoids the complicated processes of raw material treatment, high-pressure hydrogenation process, mixed hydrogen supply reagent and the like, and has the advantages of short process flow, non-harsh reaction conditions, low equipment requirement and the like; meanwhile, aromatic hydrocarbon in the raw material is enriched, the molecular composition is uniform, light components are few, the hydrogen-carbon ratio is high, the advantages of low ash content such as heteroatoms and metals are achieved, the stability of the raw material is higher, and the obtained product is higher in yield and better in performance.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (10)
1. The spinning mesophase pitch is characterized in that the raw materials comprise wax oil fractions produced by liquid phase hydrogenation of ethylene pyrolysis tar suspension beds, wherein aromatic hydrocarbons in the wax oil fractions account for 80-90% of the total mass of the wax oil fractions, and tricyclic and higher aromatic hydrocarbons account for 50-70% of the total mass of the wax oil fractions, and the spinning mesophase pitch is prepared by the following method: firstly, carrying out reduced pressure distillation on wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed under the conditions of pressure of-0.1 MPa to 0.1MPa and temperature of 250 ℃ to 280 ℃ to obtain distillate oil rich in aromatic hydrocarbon; secondly, stirring distillate oil rich in aromatic hydrocarbon for 1 to 6 hours under the protection of inert gas at the temperature of 360 to 480 ℃ and the pressure of 0.1 to 3.0MPa, and carrying out a first thermal polymerization reaction to obtain an intermediate product; step three, cooling the intermediate product to 10-25 ℃, then heating and pressurizing to 360-480 ℃ and 0.1-3.0 MPa, stirring for 2-10 h for second thermal polymerization reaction to obtain the final product; and fourthly, blowing the final product by inert gas to cool to normal temperature, and unloading the pressure to normal pressure to obtain the spinning mesophase pitch.
2. The spinning mesophase pitch of claim 1, wherein in the first step, the aromatic-rich distillate is an ethylene tar-wax oil enriched by vacuum distillation, and the ethylene tar-wax oil enriched by vacuum distillation is a wax oil having a distillation range of 360 ℃ to 460 ℃.
3. The spinning mesophase pitch according to claim 2, wherein the mass of aromatic hydrocarbons in the vacuum distillation enriched ethylene tar-wax oil accounts for 85 to 90% of the total mass of the wax oil fraction, and the mass of tricyclic and higher aromatic hydrocarbons in the vacuum distillation enriched ethylene tar-wax oil accounts for 55 to 80% of the total mass of the wax oil fraction.
4. The mesophase pitch for spinning according to claim 1, 2 or 3, wherein in the first step, the reduced pressure distillation pressure is 1.0KPa to 3.0KPa, and the temperature is 260 ℃ to 270 ℃.
5. The spinning mesophase pitch of claim 1, 2, or 3, wherein the stirring rate in the second step and the third step is 100rpm to 400 rpm.
6. The preparation method of the spinning mesophase pitch is characterized by comprising the following steps of: firstly, carrying out reduced pressure distillation on wax oil fraction produced by liquid phase hydrogenation of ethylene cracking tar suspension bed under the conditions of pressure of-0.1 MPa to 0.1MPa and temperature of 250 ℃ to 280 ℃ to obtain distillate oil rich in aromatic hydrocarbon; secondly, stirring distillate oil rich in aromatic hydrocarbon for 1 to 6 hours under the protection of inert gas at the temperature of 360 to 480 ℃ and the pressure of 0.1 to 3.0MPa, and carrying out a first thermal polymerization reaction to obtain an intermediate product; step three, cooling the intermediate product to 10-25 ℃, then heating and pressurizing to 360-480 ℃ and 0.1-3.0 MPa, stirring for 2-10 h for second thermal polymerization reaction to obtain the final product; and fourthly, blowing the final product by inert gas to cool to normal temperature, and unloading the pressure to normal pressure to obtain the spinning mesophase pitch.
7. The method of claim 6, wherein the distillate rich in aromatic hydrocarbons in the first step is ethylene tar-wax oil enriched by vacuum distillation, and the ethylene tar-wax oil enriched by vacuum distillation is wax oil with distillation range of 360-460 ℃.
8. The process for producing a spinning mesophase pitch according to claim 7, wherein the aromatic hydrocarbons in the vacuum distillation-enriched ethylene tar-wax oil account for 85 to 90% by mass of the total mass of the wax oil fraction, and the aromatic hydrocarbons in the vacuum distillation-enriched ethylene tar-wax oil account for 55 to 80% by mass of the total mass of the wax oil fraction.
9. The process for producing a mesophase pitch for spinning according to claim 6, 7 or 8, wherein in the first step, the pressure of distillation under reduced pressure is 1.0KPa to 3.0KPa, and the temperature is 260 ℃ to 270 ℃.
10. The process for preparing mesophase pitch for spinning according to claim 6, 7 or 8, wherein the stirring rate is 100rpm to 400rpm in both the second step and the third step.
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| JPS61241392A (en) * | 1985-12-26 | 1986-10-27 | Toa Nenryo Kogyo Kk | Production of mesophase pitch |
| CN102653397A (en) * | 2011-03-01 | 2012-09-05 | 辽宁科技大学 | Preparation method of coal tar-based mesocarbon microbead |
| CN104004536B (en) * | 2013-02-22 | 2017-01-11 | 神华集团有限责任公司 | Mesophase pitch and preparation method thereof |
| CN106929084B (en) * | 2017-04-05 | 2021-11-30 | 中国科学院过程工程研究所 | Preparation method of petroleum series spinnable mesophase pitch |
| RU2668444C1 (en) * | 2017-09-14 | 2018-10-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for obtaining anisotropic petroleum pitch |
| CN108795466A (en) * | 2018-06-11 | 2018-11-13 | 青岛科技大学 | A kind of method that FCC clarified oils induction polycondensation prepares mesophase pitch |
| CN110272756B (en) * | 2019-06-17 | 2021-02-12 | 湖南东映碳材料科技有限公司 | Preparation method of mesophase pitch precursor |
| CN113088313B (en) * | 2019-12-23 | 2022-08-12 | 中国石油化工股份有限公司 | Preparation method of mesophase pitch |
| CN112552946B (en) * | 2020-12-07 | 2021-11-05 | 湖南东映碳材料科技有限公司 | Preparation method of mesophase pitch |
| CN112813538B (en) * | 2021-01-13 | 2022-07-29 | 中国石油大学(华东) | Preparation method of biological intermediate phase and asphalt-based carbon fiber |
| CN112812801B (en) * | 2021-01-13 | 2022-07-29 | 中国石油大学(华东) | Preparation process of mesophase pitch and pitch-based carbon fiber |
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