CN118291166A - Spinnable mesophase pitch using catalytic cracking slurry oil as raw material and preparation method thereof - Google Patents
Spinnable mesophase pitch using catalytic cracking slurry oil as raw material and preparation method thereof Download PDFInfo
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- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 58
- 239000002002 slurry Substances 0.000 title claims abstract description 37
- 239000002994 raw material Substances 0.000 title claims abstract description 30
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 132
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 51
- 239000010426 asphalt Substances 0.000 claims abstract description 48
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000005520 cutting process Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 14
- 238000005829 trimerization reaction Methods 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 8
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000852 hydrogen donor Substances 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 4
- WPDAVTSOEQEGMS-UHFFFAOYSA-N 9,10-dihydroanthracene Chemical compound C1=CC=C2CC3=CC=CC=C3CC2=C1 WPDAVTSOEQEGMS-UHFFFAOYSA-N 0.000 claims description 3
- 239000013043 chemical agent Substances 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011295 pitch Substances 0.000 abstract description 11
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 7
- 239000004917 carbon fiber Substances 0.000 abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 33
- 238000010438 heat treatment Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000009987 spinning Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 6
- 238000004939 coking Methods 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000007431 microscopic evaluation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000011337 anisotropic pitch Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
Abstract
The invention discloses spinnable mesophase pitch taking catalytic cracking slurry oil as a raw material and a preparation method thereof. The preparation method comprises the following steps: carrying out deashing treatment on the catalytic cracking slurry oil raw material, and cutting a fraction at 350-500 ℃ to obtain refined asphalt; performing thermal condensation polymerization on the refined asphalt in an inert gas atmosphere to obtain an asphalt precursor, and extracting and separating toluene soluble TS1 and toluene insoluble TI1 by toluene; carrying out pressurized copolymerization reaction on the refined asphalt and toluene solubles TS1 in an inert gas atmosphere to obtain a secondary polycondensation product; and separating pyridine soluble substance PS2 and pyridine insoluble substance PI2 from the secondary polycondensation product, carrying out three-time polycondensation reaction on toluene insoluble substance TI1 and pyridine insoluble substance PI2 in an inert gas atmosphere, and then carrying out devolatilization under reduced pressure to obtain the spinnable mesophase pitch. The mesophase pitch prepared by the invention has low softening point, high mesophase content and good spinnability, and can be used as a high-quality precursor of high-performance pitch-based carbon fiber.
Description
Technical Field
The invention relates to the technical field of preparation of high-performance carbon material precursors, in particular to spinnable mesophase pitch taking catalytic cracking slurry oil as a raw material and a preparation method thereof.
Background
After 21 st century, the new carbon material developed rapidly, which is an indispensable high-quality material for national defense construction and social development, and is called as "new material king". The mesophase pitch-based carbon fiber has excellent performance, is applied to the fields of aerospace, national defense, military industry, mechanical manufacturing and the like, and takes up an increasingly important position in new materials. Mesophase pitch is a high quality precursor for preparing high-end carbon fibers and carbon fiber composites, and is in short supply in the market.
Mesophase pitch exhibits optical anisotropy under a polarizing microscope, also referred to as anisotropic pitch, and has an average relative molecular weight of about 2000, and is a mixture of flat-disk-shaped polycyclic aromatic hydrocarbons. After the intermediate phase pitch is subjected to non-melting, carbonization and graphitization treatment, advanced carbon materials such as high-performance pitch-based carbon fibers and the like can be obtained.
The intermediate phase asphalt may be prepared from aromatic-rich oil such as atmospheric residue, vacuum residue, slurry oil, ethylene tar, and coal tar. Among them, catalytic cracking (FCC) slurry oil belongs to the refining residual products, is generally recycled or used as ship fuel, and has low economic value. Because the naphthenic base FCC slurry oil is rich in 2-5 ring polycyclic aromatic hydrocarbon, the aromatic hydrocarbon content is high, the weight ratio is about 60-90%, and the slurry oil is a high-quality raw material for preparing carbon materials such as mesophase pitch, needle coke and the like. However, both the light component and the heavy component contained in the slurry oil are unfavorable for the formation of the mesophase, and the middle-stage fraction of the slurry oil needs to be cut as a raw material of the mesophase pitch. The method for preparing the mesophase pitch mainly comprises thermal shrinkage polymerization, pressurized thermal polycondensation, co-carbonization, hydrogenation modification thermal polycondensation, catalytic polycondensation and the like, but the mesophase pitch produced by simple thermal shrinkage polymerization has wide molecular weight distribution range and poor spinning performance, two or more raw materials are needed for the co-carbonization, the difficulty in controlling the quality of products is high, and Lewis acid or solid super acid catalyst used by catalytic polycondensation is not easy to be removed from the products and corrodes equipment.
At present, related preparation methods of mesophase pitch are also disclosed in the prior art, for example, chinese patent CN104610994a provides a preparation method of mesophase pitch with low softening point and high mesophase content, which comprises: under inert atmosphere or nitrogen atmosphere, performing primary co-carbonization treatment on the fraction of naphthenic base atmospheric residuum at 480-560 ℃ and catalytic cracking slurry oil of naphthenic base vacuum distillate oil to obtain primary co-carbonized asphalt; and (3) under inert atmosphere or nitrogen atmosphere, carrying out secondary co-carbonization treatment on the primary co-carbonized asphalt and the catalytic cracking slurry oil of the cycloalkyl vacuum distillate oil to obtain the mesophase asphalt. The optical structure of the mesophase pitch prepared by the secondary co-carbon method is a large-area streamline body, the softening point is low, and the spinnability is good. But adopts two raw materials, and is subjected to two times of co-carbonization processes, and the content of the intermediate phase of partial intermediate phase content products is low.
For another example, chinese patent CN106929084a discloses a method for preparing spinnable mesophase pitch from petroleum asphalt, which uses petroleum asphalt with intermediate temperature almost free of toluene insoluble matter and quinoline insoluble matter as raw material, and carries out hydrotreating in the presence of hydrogen-supplying solvent after heat treatment and reduced pressure distillation, and finally carries out heat treatment again to obtain spinnable mesophase pitch. The mesophase pitch prepared by the method provided by the invention has relatively low softening point and high mesophase content, and is suitable for preparing high-performance carbon fibers. However, the mesophase content of the mesophase pitch prepared by the method can only be increased to more than 90%, and the addition of the hydrogen-supplying solvent increases the cost.
For another example, chinese patent CN102181299a discloses alkylating asphalt with an olefin and a catalyst, and then performing a thermal polycondensation reaction to obtain a mesophase asphalt with a low softening point and a high mesophase content. However, the method adopts the catalyst, and has the defects of high cost and high risk in industrialization of the mesophase pitch because the catalyst has strong corrosiveness, has high requirements on reaction equipment and is difficult to remove.
Therefore, the preparation methods of the mesophase pitch in the prior art have a certain improvement room.
Disclosure of Invention
The invention provides a spinnable mesophase pitch with catalytic cracking slurry oil as a raw material and a preparation method thereof, which can be used for producing the mesophase pitch with good spinnability and high mesophase content at low cost and can be used for producing high-end carbon materials such as high-performance pitch-based carbon fibers and the like.
In a first aspect, the present invention provides a method for preparing spinnable mesophase pitch from catalytic cracking slurry oil, which is implemented by adopting the following technical scheme.
A preparation method of spinnable mesophase pitch by taking catalytic cracking slurry oil as a raw material comprises the following steps:
S1, taking catalytic cracking slurry oil as a raw material, carrying out deashing treatment, and cutting out a fraction at 350-500 ℃ to obtain refined asphalt;
S2, performing thermal polycondensation reaction on the refined asphalt obtained in the step S1 at the reaction temperature of 420-440 ℃ in an inert gas atmosphere to obtain an asphalt precursor, and then performing toluene extraction to separate toluene soluble TS1 and toluene insoluble TI1;
S3, mixing the refined asphalt obtained in the step S1 and the toluene soluble TS1 obtained in the step S2 according to the mass ratio of (0.1-100) to (0.1-100), and carrying out pressurized copolymerization reaction in an inert gas atmosphere at the reaction temperature of 420-440 ℃ to obtain a secondary polycondensation product;
S4, carrying out pyridine extraction on the secondary polycondensation product obtained in the step S3, and separating pyridine soluble substances PS2 and pyridine insoluble substances PI2;
s5, mixing the toluene insoluble matter TI1 obtained in the step S2 and the pyridine insoluble matter PI2 obtained in the step S4 according to the mass ratio of (1-10): 1-10 to obtain a trimerization raw material, mixing the trimerization raw material and a hydrogen donor according to the mass ratio of (1-15), and carrying out three polycondensation reactions in an inert gas atmosphere at the reaction temperature of 410-440 ℃ to obtain a three polycondensation product;
s6, performing reduced pressure devolatilization on the tertiary polycondensation product obtained in the step S5 to obtain spinnable mesophase pitch.
In step S1, the de-ashing treatment is one or more of gravity sedimentation, chemical agent assisted sedimentation, centrifugation, solvent extraction and filtration.
In step S2, the refined asphalt is placed into a reactor, inert gas is introduced at the flow rate of 0.5-5L/(min.kg of refined asphalt), the temperature is raised at the speed of 2-5 ℃/min, the stirring is carried out at the speed of 300-600 rpm, and the thermal polycondensation reaction is carried out on the refined asphalt under normal pressure, wherein the reaction time is 4-6 h.
In step S2, the temperature of toluene extraction is 20-40 ℃ above the boiling point of toluene, and the time of toluene extraction is 0.5-3 h.
Further, in the step S3, refined asphalt and toluene soluble TS1 are put into a reactor, inert gas is introduced to replace air in the reactor, the reactor is closed, the temperature is raised at the speed of 2-5 ℃/min, the reaction is carried out under the closed condition until the pressure in the reactor is 1-6 MPa, and then a gas outlet of the reactor is opened and the pressure in the reactor is maintained to be 1-6 MPa; the pressurized copolymerization reaction time is 3-8 h, and stirring is carried out at the speed of 300-600 rpm in the reaction process.
In step S4, the temperature of pyridine extraction is 20-40 ℃ above the boiling point of pyridine, and the time of pyridine extraction is 1-6 h.
Further, in the step S4, the pyridine soluble PS2 and the refined asphalt and toluene soluble TS1 are mixed according to the mass ratio of (0.1-100): 0.1-100, and the pressurizing copolymerization reaction is carried out together according to the method of the step S3, or the pyridine soluble PS2 and the asphalt precursor are mixed according to the mass ratio of (1-100): 1-100, and then toluene extraction is carried out according to the method of the step S2.
Further, in step S5, the hydrogen donor is one or more selected from tetrahydronaphthalene, methylnaphthalene, decalin and 9, 10-dihydroanthracene.
Further, in step S5, toluene insoluble matter TI1, pyridine insoluble matter PI2 and hydrogen donor are placed into a reactor, inert gas is introduced to replace air in the reactor, the reactor is closed, the temperature is raised at the speed of 2-5 ℃/min, stirring is carried out at the speed of 200-500 rpm in the reaction process, the reaction time is 1-6 h, and after the three-time polycondensation is finished, the pressure in the reactor is released to normal pressure.
In step S6, the temperature of the reduced pressure devolatilization is 350-380 ℃, the time is 0.5-5 h, and the relative pressure of the reduced pressure devolatilization is-0.07-0.05 MPa.
Further, the inert gas is nitrogen or argon.
In a second aspect, the invention provides a spinnable mesophase pitch using catalytic cracking slurry as a feedstock, which is achieved by the following technical scheme.
The spinnable mesophase pitch prepared by the preparation method has the mesophase content of 99 to 100 percent and the softening point of 260 to 310 ℃.
The application has the following beneficial effects.
The method of the invention adopts low price of raw materials and low processing cost, and the prepared spinnable mesophase pitch has low softening point (260-310 ℃) and high mesophase content (99-100%), and has good spinnability, and can be used as a high-quality precursor of high-performance pitch-based carbon fibers.
Detailed Description
The present application is further illustrated below with reference to examples.
The experimental methods used in the following preparation examples and examples are conventional methods unless otherwise specified; materials, reagents and the like used in the following preparation examples and examples are commercially available unless otherwise specified.
Example 1
And (3) carrying out gravity sedimentation on cycloalkyl FCC slurry oil to remove solid phase, carrying out reduced pressure distillation to cut out a fraction at 350-500 ℃ to obtain refined asphalt, placing the refined asphalt into a reactor, then introducing nitrogen at a flow rate of 2L/(min.kg of refined asphalt), heating at a rate of 5 ℃/min, carrying out thermal polycondensation reaction, and stirring in the reaction process, wherein the stirring speed is 300rpm, the reaction temperature is 420 ℃, and the reaction time is 6h, thus obtaining an asphalt precursor.
Crushing the asphalt precursor to a particle size smaller than 0.1cm, extracting toluene at 131 ℃ for 0.5h, and separating toluene soluble TS1 and toluene insoluble TI1.
Example 2
And (3) carrying out gravity sedimentation on cycloalkyl FCC slurry oil to remove solid phase, carrying out reduced pressure distillation to cut out 360-500 ℃ fractions to obtain refined asphalt, mixing the refined asphalt with toluene soluble TS1 obtained in example 1 according to a mass ratio of 100:1, placing the mixture into a reactor, introducing nitrogen to replace air in the reactor, heating at a speed of 5 ℃/min, carrying out closed heating to realize pressure rising and stabilizing at 2MPa, carrying out pressurized copolymerization reaction, and stirring in the reaction process, wherein the stirring speed is 300rpm, the reaction temperature is 420 ℃, and the reaction time is 6h, thus obtaining a secondary polycondensation product.
And crushing the secondary polycondensation product to a particle size smaller than 0.1cm, extracting pyridine at 136 ℃ for 1h, and separating pyridine soluble PS2 and pyridine insoluble PI2.
Mixing toluene insoluble TI1 and pyridine insoluble PI2 according to a mass ratio of 10:1 to obtain a trimerization raw material, mixing the trimerization raw material and tetrahydronaphthalene according to a mass ratio of 1:3, and carrying out three-time polycondensation reaction under a nitrogen atmosphere, wherein stirring is carried out in the reaction process, the stirring speed is 300rpm, heating is carried out according to a speed of 2 ℃/min, the reaction temperature is 410 ℃, and the reaction time is 4 hours, so as to obtain a three-time polycondensation product.
The tertiary polycondensation product is decompressed and devolatilized, the treatment temperature is 380 ℃, the time is 0.5h, the relative pressure is-0.07 MPa, the spinnable mesophase pitch is obtained, the mesophase content of the spinnable mesophase pitch is detected according to a light reflection microscopic analysis method for measuring the mesophase content of GB/T38396-2019 coking pitch products, the softening point of the spinnable mesophase pitch is detected according to a softening point measuring method for GB/T2294-2019 coking solid products, the mesophase content reaches 99.0%, the softening point is 269 ℃, and when the spinning speed is 400m/min, the filament is continuously spun for 30min, and the spinnability is good.
Example 3
Centrifuging cycloalkyl FCC slurry oil, distilling under reduced pressure to cut out a fraction at 350-500 ℃ to obtain refined asphalt, mixing the refined asphalt with toluene soluble TS1 obtained in example 1 according to a mass ratio of 5:1, placing the mixture into a reactor, introducing nitrogen to replace air in the reactor, heating at a speed of 5 ℃/min, raising the pressure by sealing and raising the temperature to be stable at 1MPa, performing pressurized copolymerization reaction, stirring during the reaction process, wherein the stirring speed is 400rpm, the reaction temperature is 420 ℃, and the reaction time is 8h, thus obtaining a secondary polycondensation product.
Crushing the secondary polycondensation product to a particle size smaller than 0.01cm, extracting pyridine at 141 ℃ for 1.5h, and separating pyridine soluble PS2 and pyridine insoluble PI2.
Mixing toluene insoluble TI1 and pyridine insoluble PI2 according to a mass ratio of 6:1 to obtain a trimerization raw material, mixing the trimerization raw material and methylnaphthalene according to a mass ratio of 1:2, and carrying out three-time polycondensation reaction under a nitrogen atmosphere, wherein stirring is carried out in the reaction process, the stirring speed is 300rpm, heating is carried out according to a speed of 5 ℃/min, the reaction temperature is 420 ℃, and the reaction time is 1.5h, so as to obtain a three-time polycondensation product.
The tertiary polycondensation product is decompressed and devolatilized, the treatment temperature is 380 ℃, the time is 1h, the relative pressure is-0.05 MPa, the spinnable mesophase pitch is obtained, the mesophase content of the spinnable mesophase pitch is detected according to a light reflection microscopic analysis method for measuring the mesophase content of GB/T38396-2019 coking pitch products, the softening point of the spinnable mesophase pitch is detected according to a method for measuring the softening point of GB/T2294-2019 coking solid products, the intermediate phase content is 100%, the softening point is 273 ℃, and when the spinning speed is 400m/min, the spinning is continuous for 30min, and the spinnability is good.
Example 4
The catalytic cracking slurry oil is subjected to solvent extraction to remove ash, the distillation is reduced in pressure to cut out a fraction at 350-500 ℃, then membrane filtration and deashing treatment are carried out to obtain refined asphalt, the refined asphalt, toluene soluble TS1 obtained in example 1 and pyridine soluble PS2 obtained in example 3 are mixed according to the mass ratio of 25:1:4 and are put into a reactor, then air in the reactor is replaced by argon, heating is carried out according to the speed of 4 ℃/min, the pressure rise is realized through airtight heating and is stabilized at 4MPa, the slurry oil fraction is subjected to pressurized copolymerization reaction, stirring is carried out in the reaction process, the stirring speed is 450rpm, the reaction temperature is 430 ℃, and the reaction time is 5h, so that a secondary polycondensation product is obtained.
Crushing the secondary polycondensation product to a particle size smaller than 0.01cm, extracting pyridine at 150 ℃ for 3 hours, and separating pyridine soluble PS2 and pyridine insoluble PI2.
Mixing toluene insoluble TI1 and pyridine insoluble PI2 according to a mass ratio of 1:5 to obtain a trimerization raw material, mixing the trimerization raw material and decalin according to a mass ratio of 10:9 under a nitrogen atmosphere to perform three-time polycondensation reaction, stirring in the reaction process, heating at a stirring speed of 300rpm at a speed of 4 ℃/min, and reacting at a temperature of 436 ℃ for 3 hours to obtain a three-time polycondensation product.
And (3) performing reduced pressure devolatilization on the tertiary polycondensation product, wherein the reduced pressure distillation temperature is 350 ℃, the time is 4 hours, the relative pressure is-0.07 MPa, the spinnable mesophase pitch is obtained, the mesophase content of the spinnable mesophase pitch is detected according to a light reflection microscopic analysis method for measuring the mesophase content of GB/T38396-2019 coked pitch products, the softening point of the spinnable mesophase pitch is detected according to a method for measuring the softening point of GB/T2294-2019 coked solid products, the content of the mesophase pitch is 99.5%, the softening point is 304 ℃, and when the spinning speed is 400m/min, the spinning is continuously performed for 30min, so that the spinnability is good.
Example 5
The FCC slurry oil is subjected to chemical agent sedimentation and deashing, the distillate at 350-500 ℃ is cut by reduced pressure distillation to obtain refined asphalt, the refined asphalt and the toluene soluble TS1 obtained in the example 1 are put into a reactor according to the mass ratio of 80:3, then the air in the reactor is replaced by nitrogen, the temperature is raised at the speed of 5 ℃/min, the pressure is raised to 1MPa by sealing the temperature rise, the slurry oil distillate is subjected to pressurized copolymerization reaction, the stirring speed is 500rpm, the reaction temperature is 440 ℃, and the reaction time is 5h, so that the secondary polycondensation product is obtained.
Crushing the secondary polycondensation product to a particle size smaller than 0.02cm, extracting pyridine at 145 ℃ for 6 hours, and separating pyridine soluble PS2 and pyridine insoluble PI2.
Mixing toluene insoluble TI1 and pyridine insoluble PI2 according to a mass ratio of 1:1 to obtain a trimerization raw material, mixing the trimerization raw material and 9, 10-dihydro anthracene according to a mass ratio of 1:2, and carrying out three-time polycondensation reaction under a nitrogen atmosphere, wherein stirring is carried out in the reaction process, the stirring speed is 400rpm, heating is carried out according to a speed of 3 ℃/min, the reaction temperature is 425 ℃, and the reaction time is 3.5h, so as to obtain a three-time polycondensation product.
The tertiary polycondensation product is subjected to reduced pressure devolatilization, the reduced pressure distillation temperature is 380 ℃, the time is 5 hours, the relative pressure is-0.06 MPa, the spinnable mesophase pitch is obtained, the mesophase content of the spinnable mesophase pitch is detected according to a light reflection microscopic analysis method for measuring the mesophase content of GB/T38396-2019 coking pitch products, the softening point of the spinnable mesophase pitch is detected according to a method for measuring the softening point of GB/T2294-2019 coking solid products, the content of the mesophase is 100%, the softening point is 298 ℃, and when the spinning speed is 400m/min, the spinning is continuously carried out for 30min, so that the spinnability is good.
Example 6
And (3) carrying out gravity sedimentation on cycloalkyl FCC slurry oil to remove solid phase, carrying out reduced pressure distillation to cut out a fraction at 350-500 ℃ to obtain refined asphalt, placing the refined asphalt into a reactor, then introducing nitrogen at a flow rate of 2L/(min.kg of refined asphalt), heating at a rate of 5 ℃/min, carrying out thermal polycondensation reaction, and stirring in the reaction process, wherein the stirring speed is 300rpm, the reaction temperature is 420 ℃, and the reaction time is 6h, thus obtaining an asphalt precursor.
The pyridine solubles PS2 obtained in example 5 and the pitch precursor were mixed in a ratio of 1:2, and pulverized to a particle size of less than 0.1cm, and toluene extraction was performed at a temperature of 131℃for 3 hours to separate toluene solubles TS1 and toluene insoluble TI1.
And (3) placing refined asphalt and toluene soluble TS1 into a reactor according to a mass ratio of 80:3, then introducing nitrogen to replace air in the reactor, heating at a speed of 5 ℃/min, raising the pressure to 1MPa by sealing and raising the temperature, carrying out pressurized copolymerization on the slurry oil fraction, and stirring in the reaction process at a stirring speed of 500rpm at a reaction temperature of 440 ℃ for 5 hours to obtain a secondary polycondensation product.
And crushing the secondary polycondensation product to a particle size smaller than 0.02cm, extracting pyridine at 148 ℃ for 5 hours, and separating pyridine soluble PS2 and pyridine insoluble PI2.
Mixing toluene insoluble TI1 and pyridine insoluble PI2 according to a mass ratio of 3:1 to obtain a trimerization raw material, mixing the trimerization raw material and tetrahydronaphthalene according to a mass ratio of 1:2, and carrying out three-time polycondensation reaction under a nitrogen atmosphere, wherein stirring is carried out in the reaction process, the stirring speed is 400rpm, heating is carried out according to a speed of 4 ℃/min, the reaction temperature is 415 ℃, and the reaction time is 5 hours, so that a three-time polycondensation product is obtained.
And (3) performing reduced pressure devolatilization on the tertiary polycondensation product, wherein the reduced pressure distillation temperature is 380 ℃, the time is 3 hours, the relative pressure is-0.06 MPa, the spinnable mesophase pitch is obtained, the mesophase content of the spinnable mesophase pitch is detected according to a light reflection microscopic analysis method for measuring the mesophase content of GB/T38396-2019 coked pitch products, the softening point of the spinnable mesophase pitch is detected according to a method for measuring the softening point of GB/T2294-2019 coked solid products, the content of the mesophase pitch is 99.6%, the softening point is 297 ℃, and when the spinning speed is 400m/min, the spinning is continuously performed for 30min, so that the spinnability is good.
The embodiments of the present invention are all preferred embodiments of the present invention, and are not intended to limit the scope of the present invention in this way, therefore: all equivalent changes in structure, shape and principle of the invention should be covered in the scope of protection of the invention.
Claims (10)
1. A preparation method of spinnable mesophase pitch by taking catalytic cracking slurry oil as a raw material is characterized by comprising the following steps: the method comprises the following steps:
S1, taking catalytic cracking slurry oil as a raw material, carrying out deashing treatment, and cutting out a fraction at 350-500 ℃ to obtain refined asphalt;
S2, performing thermal polycondensation reaction on the refined asphalt obtained in the step S1 at the reaction temperature of 420-440 ℃ in an inert gas atmosphere to obtain an asphalt precursor, and then performing toluene extraction to separate toluene soluble TS1 and toluene insoluble TI1;
S3, mixing the refined asphalt obtained in the step S1 and the toluene soluble TS1 obtained in the step S2 according to the mass ratio of (0.1-100) to (0.1-100), and carrying out pressurized copolymerization reaction in an inert gas atmosphere at the reaction temperature of 420-440 ℃ to obtain a secondary polycondensation product;
S4, carrying out pyridine extraction on the secondary polycondensation product obtained in the step S3, and separating pyridine soluble substances PS2 and pyridine insoluble substances PI2;
s5, mixing the toluene insoluble matter TI1 obtained in the step S2 and the pyridine insoluble matter PI2 obtained in the step S4 according to the mass ratio of (1-10): 1-10 to obtain a trimerization raw material, mixing the trimerization raw material and a hydrogen donor according to the mass ratio of (1-15), and carrying out three polycondensation reactions in an inert gas atmosphere at the reaction temperature of 410-440 ℃ to obtain a three polycondensation product;
s6, performing reduced pressure devolatilization on the tertiary polycondensation product obtained in the step S5 to obtain spinnable mesophase pitch.
2. The method for preparing spinnable mesophase pitch from catalytic cracking slurry oil as set forth in claim 1, wherein: in the step S1, the deashing treatment is selected from one or a combination of more of gravity sedimentation, chemical agent sedimentation, centrifugation, solvent extraction and filtration.
3. The method for preparing spinnable mesophase pitch from catalytic cracking slurry oil as set forth in claim 1, wherein: in the step S2, the refined asphalt is put into a reactor, inert gas is introduced at the flow rate of 0.5-5L/(min.kg of refined asphalt), the temperature is raised at the speed of 2-5 ℃/min, the stirring is carried out at the speed of 300-600 rpm, and the thermal polycondensation reaction is carried out on the refined asphalt under normal pressure, wherein the reaction time is 4-6 h.
4. The method for preparing spinnable mesophase pitch from catalytic cracking slurry oil as set forth in claim 1, wherein: in the step S2, the temperature of toluene extraction is 20-40 ℃ above the boiling point of toluene, and the time of toluene extraction is 0.5-3 h.
5. The method for preparing spinnable mesophase pitch from catalytic cracking slurry oil as set forth in claim 1, wherein: in the step S3, refined asphalt and toluene soluble TS1 are put into a reactor, inert gas is introduced to replace air in the reactor, the reactor is closed and heated at the speed of 2-5 ℃/min, the reaction is carried out under the closed condition until the pressure in the reactor is 1-6 MPa, and then a gas outlet of the reactor is opened and the pressure in the reactor is maintained to be 1-6 MPa; the pressurized copolymerization reaction time is 3-8 h, and stirring is carried out at the speed of 300-600 rpm in the reaction process.
6. The method for preparing spinnable mesophase pitch from catalytic cracking slurry oil as set forth in claim 1, wherein: in the step S4, the temperature of pyridine extraction is 20-40 ℃ above the boiling point of pyridine, and the time of pyridine extraction is 1-6 h.
7. The method for preparing spinnable mesophase pitch from catalytic cracking slurry oil as set forth in claim 1, wherein: in the step S5, the hydrogen donor is one or more of tetrahydronaphthalene, methylnaphthalene, decalin and 9, 10-dihydroanthracene.
8. The method for preparing spinnable mesophase pitch from catalytic cracking slurry oil as set forth in claim 1, wherein: in the step S5, toluene insoluble matter TI1, pyridine insoluble matter PI2 and hydrogen donor are placed into a reactor, inert gas is introduced to replace air in the reactor, the reactor is closed, the temperature is raised at the speed of 2-5 ℃/min, stirring is carried out at the speed of 200-500 rpm in the reaction process, the reaction time is 1-6 h, and after the three-time polycondensation is finished, the pressure in the reactor is released to normal pressure.
9. The method for preparing spinnable mesophase pitch from catalytic cracking slurry oil as set forth in claim 1, wherein: in the step S6, the temperature of the reduced pressure devolatilization is 350-380 ℃, the time is 0.5-5 h, and the relative pressure of the reduced pressure devolatilization is-0.07-0.05 MPa.
10. A spinnable mesophase pitch prepared by the method of any of claims 1-9.
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| Publication Number | Publication Date |
|---|---|
| CN118291166A true CN118291166A (en) | 2024-07-05 |
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