CN112625722A - Method for preparing spinnable asphalt by combining raw materials and application of spinnable asphalt in preparation of carbon fibers - Google Patents
Method for preparing spinnable asphalt by combining raw materials and application of spinnable asphalt in preparation of carbon fibers Download PDFInfo
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- CN112625722A CN112625722A CN202011275139.9A CN202011275139A CN112625722A CN 112625722 A CN112625722 A CN 112625722A CN 202011275139 A CN202011275139 A CN 202011275139A CN 112625722 A CN112625722 A CN 112625722A
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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
- C10C3/026—Working-up pitch, asphalt, bitumen by chemical means reaction with organic compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
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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
- C10C3/10—Melting
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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
- C10C3/14—Solidifying, Disintegrating, e.g. granulating
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
- D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
- D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Inorganic Fibers (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
A method for preparing spinnable asphalt by combining raw materials and an application of the spinnable asphalt in preparing carbon fibers belong to the technical field of asphalt and carbon fiber preparation. The raw materials for preparing the asphalt are filtered and refined, the group compositions of the raw materials are grouped by adopting solvent extraction, then the group compositions of all the groups are combined and mixed, the obtained mixture is further mixed and reacted, then the asphalt-based carbon fiber is obtained by further melt spinning, pre-oxidation treatment and carbonization treatment, and the asphalt-based graphite fiber is obtained by further graphitization treatment.
Description
Technical Field
The invention relates to a method for preparing spinnable asphalt by combining raw materials and application of the spinnable asphalt to preparation of carbon fibers, and belongs to the technical field of asphalt and carbon fiber preparation.
Background
Pitch is a good raw material for preparing a variety of carbon materials, and has been widely used, such as pitch-based carbon fibers and graphite fibers, carbon foams, mesocarbon microbeads, activated carbon, needle coke, electrodes, binders for carbon/carbon composites, and matrix materials. The properties and stability of pitch play a critical role in the structure, performance, and performance stability of carbon materials. The special structure and performance of the pitch-based carbon fiber and graphite fiber, as novel carbon materials, enable the carbon fiber and graphite fiber to have wide application, including the fields of environmental protection, thermal insulation and protection, robots, aerospace and aviation, national defense and military industry and the like, and therefore, the carbon fiber and graphite fiber are one of the key application fields of pitch.
The raw materials for preparing the spinning asphalt have wide sources, including petroleum refining residual oil, ethylene cracking residual oil, polycyclic aromatic hydrocarbon, coal tar, biomass asphalt and the like, and a large number of related documents are reported. The great university of Beijing chemical industry thesis (Linxili, 2011, research on preparation of spinnable mesophase pitch from petroleum residue) reports that mesophase pitch is prepared from petroleum residue by two pressure-vacuum thermal polycondensation experimental schemes preferentially, and carbon fiber is obtained by melt spinning, pre-oxidation and carbonization. The university of medical science and technology university of Anhui university's Master academic thesis (Hanxiao, 2011, preparation and characterization of coal pitch-based carbon fiber) reports that a quinoline extract of coal pitch is used as a raw material to prepare a pitch precursor by a catalytic polycondensation method, and then the pitch precursor is used for preparing the pitch-based carbon fiber. The Chinese patent application CN103361096A discloses a preparation method of high-softening-point asphalt for producing general-grade carbon fibers, which takes refined soft asphalt as a raw material, adjusts the softening point through distillation, secondary oxidation and vacuum film evaporation, prepares the high-softening-point asphalt raw material for the general-grade carbon fibers, and further prepares asphalt-based carbon fibers. The Chinese patent application CN102733008A discloses a method for preparing carbon fibers by using coal direct liquefaction residue-based asphalt vinyl substances, which takes the coal direct liquefaction residue-based asphalt vinyl substances as raw materials, firstly grinds the asphalt vinyl substances, then places the ground asphalt vinyl substances in a high-temperature tube furnace or a high-pressure reaction kettle protected by inert gas for polycondensation reaction to prepare spinnable mesophase asphalt, and further prepares asphalt-based carbon fibers. Chinese patent application CN106929083A discloses a method for preparing petroleum-based isotropic carbon fiber spinnable asphalt, which is characterized in that ethylene pyrolysis tar is used as a raw material, the raw material is subjected to sedimentation, filtration, flash evaporation and reduced pressure flash evaporation, and the obtained material is further mixed with medium-temperature asphalt to perform polycondensation reaction to obtain spinnable asphalt, so that asphalt-based carbon fiber is prepared. The literature (carbon, 2005, 123: 3-11) reports the research on the preparation of general-purpose pitch carbon fiber from naphtha pyrolysis tar, and the asphalt-based carbon fiber is prepared from the naphtha pyrolysis tar as a raw material by obtaining four kinds of pitches with different softening points through a thermal modification method. The literature (chemical novel materials, 2011, 39: 100-102) reports the research on the influence of asphalt components on the radial structure of carbon fibers, and the physical modification method of mixed isotropic and anisotropic asphalt is used for obtaining the mixed asphalt as a spinning raw material so as to prepare the asphalt-based carbon fibers. There are many researches on the preparation of pitch and pitch-based carbon fiber by various methods, and the research contents include the influence of pitch raw material, pitch refining, preparation method and process of spinning pitch, etc. on the properties of pitch and the properties and performance of prepared carbon fiber, and thus are not described in detail. At present, related researches generally treat a certain asphalt raw material to obtain asphalt with good spinnability, and then the asphalt is used for preparing asphalt-based carbon fibers, and little attention is paid to the influence of raw materials of different batches, or raw materials of the same batch and different storage times and modes, or raw materials of different sources on the properties and the composition of the prepared spinnable asphalt, and further on the properties and the structure of the prepared carbon fibers or graphite fibers. Meanwhile, the method reported at present has the problems of long high-temperature reaction time, poor controllability and the like. The raw materials for preparing the spinnable asphalt have wide sources, usually have large property difference, even if the composition of the raw materials at the same part of the same unit has large fluctuation, the difference between raw material batches for preparing the spinning asphalt is easily large, troubles are brought to the preparation process adjustment, the performance stability and the like of the spinnable asphalt and the carbon fiber, and the actual application of the product is finally influenced. The decisive factor for obtaining high-performance asphalt-based carbon fiber is the composition and structure of the spinning asphalt, and the properties and structure of the spinning asphalt depend on the composition, structure and properties of the raw materials. Therefore, how to regulate and control the composition and the property of the raw material for preparing the spinning asphalt realizes the relative stability and reliability of the composition, the structure and the property of the raw material, thereby facilitating the regulation and control of the property of the spinning asphalt and ensuring the excellent performance and the stable property of the batch of products. Therefore, it is of great significance to find a preparation method with short high-temperature reaction time, high process regulation and control performance, controllable asphalt composition, high stability of batch product properties and small discreteness.
Disclosure of Invention
The invention provides a method for preparing spinnable asphalt by combining raw materials and application thereof in preparing carbon fibers, aiming at the problems that the process fluctuation of preparing the spinning asphalt in batches is large, the property difference of the prepared spinning asphalt in batches is large, the dispersion degree is high, the regulation and control effect of the preparation on the properties of the spinnable asphalt is low and the like caused by wide raw material sources, large property difference and large group composition difference of the raw materials in the prior art. Compared with the prior art for preparing the spinning asphalt, the invention has the beneficial effects that: 1) the family composition of the raw materials for preparing the spinnable asphalt has high controllability and can be effectively adjusted according to the performance requirement of the carbon fiber; 2) the prepared spinning asphalt has small performance difference of batch products, low dispersion and high property stability; 3) the high-temperature reaction process time is shortened; 4) the reaction process has high controllability, and the prepared spinning asphalt has convenient property regulation and control; 3) the performance of the pitch-based carbon fiber is convenient to regulate and control, and the batch performance is stable.
Specifically, the preparation method comprises the following steps:
(1) selecting raw materials required for preparing spinnable asphalt, and carrying out hot filtration on the raw materials to remove catalysts, other impurities and the like in the raw materials so as to obtain refined raw materials;
(2) extracting the hot filtration refining raw material obtained in the step (1) by adopting n-heptane to obtain an n-heptane solution and an n-Heptane Insoluble (HI) solution; evaporating the solvent from the n-heptane solution to obtain n-heptane soluble material (HS);
(3) extracting the n-heptane insoluble substance (HI) obtained in the step (2) with toluene to obtain a toluene solution and a toluene insoluble substance (TI); evaporating the solvent from the toluene solution to obtain toluene soluble matter (TS);
(4) extracting the toluene insoluble substance (TI) obtained in the step (3) by using pyridine to obtain a pyridine solution and a pyridine insoluble substance (PI); evaporating the solvent from the pyridine solution to obtain pyridine soluble matter (PS);
(5) extracting the pyridine insoluble substance (PI) obtained in the step (4) by using quinoline to obtain a quinoline solution and a quinoline insoluble substance (QI); evaporating the solvent of the quinoline solution to obtain quinoline soluble substance (QS);
(6) grouping the raw material family compositions obtained in the steps (1) to (5), wherein the composition of the component 1: step (2) n-Heptane Solubles (HS); and (2) component: step (3) Toluene Solubles (TS); and (3) component: step (4) Pyridine Soluble (PS); and (4) component: step (5) Quinoline Solubles (QS); and (5) component: step (6) quinoline insoluble matter (QI);
(7) mixing the grouped component 1, the component 2, the component 3, the component 4 and the component 5 obtained in the steps (1) to (6) according to a certain proportion, putting the mixture into a reaction kettle, heating the mixture to a proper temperature under the protection of nitrogen, completely melting the components, uniformly mixing the components under the stirring action, and keeping stirring, mixing and reacting for a period of time; then cooling to obtain spinnable asphalt;
(8) preparing the spinnable asphalt obtained in the step (7) into asphalt fibers by a melt spinning method, and further performing pre-oxidation treatment and carbonization treatment to obtain asphalt-based carbon fibers; further, the obtained pitch-based carbon fiber is subjected to a high-temperature graphitization treatment to obtain a graphitized pitch-based carbon fiber.
Preferably, in the method of the present invention, the raw material required for preparing the spinnable asphalt is one or more of petroleum cracking residual oil, ethylene cracking residual oil, solvent extraction oil of petroleum residual oil, coal tar pitch, biomass pitch, etc. as the initial raw material, and preferably one or more of petroleum cracking residual oil, ethylene cracking residual oil, solvent extraction oil of petroleum residual oil, coal tar pitch, etc. as the initial raw material.
Preferably, in the process of the present invention, the raw material is subjected to thermal filtration using a filter pore size of less than 10 microns, an optimized filter pore size of less than 5 microns, and more preferably a filter pore size of less than 1 micron.
Preferably, in the method of the present invention, the ratio of component 1, component 2, component 3, component 4 and component 5 is: HS 0-30%, HI-TS 5-30%, TI-PS 30-70%, PI-QS 20-60%, QI 0-40%; the optimized proportion is as follows: HS 0-10%, HI-TS 10-20%, TI-PS 35-50%, PI-QS 25-40%, QI 0-20%.
Preferably, in the method of the invention, the components obtained in the step (6) are placed in a reaction kettle according to a certain proportion, nitrogen is introduced, the mixture is heated and melted and stirred, the temperature is 250-450 ℃, the optimized temperature is 300-420 ℃, and the more preferable temperature is 340-420 ℃; mixing and reacting under stirring for 0.1-40h, optimally for 0.5-20h, more optimally for 2-10 h; after mixing and reacting, cooling to room temperature under the protection of nitrogen to obtain the spinnable asphalt.
Preferably, in the method of the invention, the spinnable asphalt obtained in the step (7) is used for preparing the asphalt fiber by a melt spinning method, the spinning condition temperature is 280-400 ℃, the spinning condition temperature is 300-360 ℃, the spinning pressure is 0-0.5MPa, the spinning pressure is 0.01-0.1MPa, the rotating speed of a winding roller is 100-2000r/min, and the rotating speed is 400-800 r/min; further, pre-oxidizing the asphalt fiber, wherein the pre-oxidizing temperature is 380 ℃ in 240-; further, carrying out carbonization treatment on the fiber at the temperature of 1000-1600 ℃ for 0.5-5h to obtain the pitch-based carbon fiber; further, graphitizing the fiber at the temperature of 2000-3000 ℃, and optimally 2600-3000 ℃, so as to obtain the graphitized asphalt-based carbon fiber.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the side surface of the pitch-based carbon fiber obtained in example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) image of a cross section of the graphitized pitch-based carbon fiber obtained in example 1.
Fig. 3 is an X-ray diffraction (XRD) pattern of the pitch-based carbon fiber obtained in example 1.
Fig. 4 is an X-ray diffraction (XRD) pattern of the graphitized pitch-based carbon fiber obtained in example 2.
Fig. 5 is an X-ray diffraction (XRD) pattern of the graphitized pitch-based carbon fiber obtained in example 4.
Fig. 6 is an X-ray diffraction (XRD) pattern of the graphitized pitch-based carbon fiber obtained in example 5.
Fig. 7 is an X-ray diffraction (XRD) pattern of the graphitized pitch-based carbon fiber obtained in example 6.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Specifically, the preparation method comprises the following steps:
(1) selecting raw materials required for preparing spinnable asphalt, and carrying out hot filtration on the raw materials to remove catalysts, other impurities and the like in the raw materials so as to obtain refined raw materials;
(2) extracting the hot filtration refining raw material obtained in the step (1) by adopting n-heptane to obtain an n-heptane solution and an n-Heptane Insoluble (HI) solution; evaporating the solvent from the n-heptane solution to obtain n-heptane soluble material (HS);
(3) extracting the n-heptane insoluble substance (HI) obtained in the step (2) with toluene to obtain a toluene solution and a toluene insoluble substance (TI); evaporating the solvent from the toluene solution to obtain toluene soluble matter (TS);
(4) extracting the toluene insoluble substance (TI) obtained in the step (3) by using pyridine to obtain a pyridine solution and a pyridine insoluble substance (PI); evaporating the solvent from the pyridine solution to obtain pyridine soluble matter (PS);
(5) extracting the pyridine insoluble substance (PI) obtained in the step (4) by using quinoline to obtain a quinoline solution and a quinoline insoluble substance (QI); evaporating the solvent of the quinoline solution to obtain quinoline soluble substance (QS);
(6) grouping the raw material family compositions obtained in the steps (1) to (5), wherein the composition of the component 1: step (2) n-Heptane Solubles (HS); and (2) component: step (3) Toluene Solubles (TS); and (3) component: step (4) Pyridine Soluble (PS); and (4) component: step (5) Quinoline Solubles (QS); and (5) component: step (6) quinoline insoluble matter (QI);
(7) mixing the grouped component 1, the component 2, the component 3, the component 4 and the component 5 obtained in the steps (1) to (6) according to a certain proportion, putting the mixture into a reaction kettle, heating the mixture to a proper temperature under the protection of nitrogen, completely melting the components, uniformly mixing the components under the stirring action, and keeping stirring, mixing and reacting for a period of time; then cooling to obtain spinnable asphalt;
(8) preparing the spinnable asphalt obtained in the step (7) into asphalt fibers by a melt spinning method, and further performing pre-oxidation treatment and carbonization treatment to obtain asphalt-based carbon fibers; further, the obtained pitch-based carbon fiber is subjected to a high-temperature graphitization treatment to obtain a graphitized pitch-based carbon fiber.
Example 1
Two catalytic cracking residual oils of two refineries are used as raw materials; mixing the two raw materials according to the mass ratio of 1: 1, and then carrying out hot filtration through a filter with the filter pore size of less than 5 microns to obtain a refined raw material; adopting n-heptane, toluene, pyridine and quinoline to respectively extract according to the steps to obtain components of each level: n-Heptane Solubles (HS), n-heptane insoluble-toluene solubles (HI-TS) corresponding to toluene solubles, toluene insoluble-pyridine solubles (TI-PS) corresponding to pyridine solubles, pyridine insoluble-quinoline solubles (PI-QS) corresponding to quinoline solubles, and Quinoline Insoluble (QI); adding HS, HI-TS, TI-PS, PI-QS and QI into a reaction kettle according to the mass ratio of 5: 25: 40: 30: 0 for mixing; then, under the conditions of nitrogen protection and stirring, carrying out self-boosting polymerization reaction for 8 hours at the temperature of 420 ℃, and further carrying out reaction for 5 hours under the pressure reduction condition at the temperature of 400 ℃ to obtain spinning asphalt; preparing asphalt fiber from the obtained asphalt under the conditions of the spinning temperature of 340 ℃, the spinning pressure of 0.02MPa and the rotating speed of a winding roller of 500 r/min; pre-oxidizing the asphalt fiber at the pre-oxidation temperature of 280 ℃ and the heating rate of 2 ℃/min; and further treating for 2 hours at the carbonization temperature of 1000 ℃ to obtain the pitch-based carbon fiber.
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the side of the pitch-based carbon fiber obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) picture of a cross section of the pitch-based carbon fiber obtained in example 1;
fig. 3 is an X-ray diffraction (XRD) pattern of the pitch-based carbon fiber obtained in example 1.
Example 2
Two catalytic cracking residual oils of another two refineries are used as raw materials; mixing the two raw materials according to the mass ratio of 1: 1, and then carrying out hot filtration through a filter with the pore diameter smaller than 5 microns to obtain a refined raw material; extracting with n-heptane, toluene, pyridine and quinoline according to the steps to obtain components of different families: n-Heptane Solubles (HS), n-heptane insoluble-toluene solubles (HI-TS), toluene insoluble-pyridine solubles (TI-PS), pyridine insoluble-quinoline solubles (PI-QS), Quinoline Insoluble (QI); adding HS, HI-TS, TI-PS, PI-QS and QI into a reaction kettle according to the mass ratio of 5: 25: 40: 30: 0 for mixing; then, under the conditions of nitrogen protection and stirring, carrying out self-boosting polymerization reaction for 8 hours at the temperature of 420 ℃, and further carrying out reaction for 5 hours under the pressure reduction condition at the temperature of 400 ℃ to obtain spinning asphalt; preparing asphalt fiber from the obtained asphalt under the conditions of the spinning temperature of 340 ℃, the spinning pressure of 0.02MPa and the rotating speed of a winding roller of 500 r/min; pre-oxidizing the asphalt fiber at the pre-oxidation temperature of 280 ℃ and the heating rate of 2 ℃/min; further, processing for 2 hours at the carbonization temperature of 1000 ℃ to obtain pitch-based carbon fiber; further, the fiber was treated at a graphitization temperature of 2500 ℃ for 1 hour under argon gas to obtain a graphitized pitch-based carbon fiber.
Fig. 4 is an X-ray diffraction (XRD) pattern of the graphitized pitch-based carbon fiber obtained in example 2.
Example 3
Taking a certain refinery catalytic cracking residual oil and coal tar pitch of a certain company as raw materials; mixing the two raw materials according to the mass ratio of 1: 1, and then carrying out hot filtration through a filter with the pore diameter smaller than 5 microns to obtain a refined raw material; extracting with n-heptane, toluene, pyridine and quinoline according to the steps to obtain components of different families: n-Heptane Solubles (HS), n-heptane insoluble-toluene solubles (HI-TS), toluene insoluble-pyridine solubles (TI-PS), pyridine insoluble-quinoline solubles (PI-QS), Quinoline Insoluble (QI); adding HS, HI-TS, TI-PS, PI-QS and QI into a reaction kettle according to the mass ratio of 4: 20: 40: 36: 0 for mixing; then, under the conditions of nitrogen protection and stirring, carrying out self-boosting polymerization reaction for 8 hours at the temperature of 420 ℃, and further carrying out reaction for 5 hours under the pressure reduction condition at the temperature of 400 ℃ to obtain spinning asphalt; preparing asphalt fiber from the obtained asphalt under the conditions of the spinning temperature of 354 ℃, the spinning pressure of 0.02MPa and the rotating speed of a winding roller of 500 r/min; pre-oxidizing the asphalt fiber at 282 deg.c and 2 deg.c/min; further, processing for 2 hours at the carbonization temperature of 1000 ℃ to obtain pitch-based carbon fiber; further, the fiber was treated at a graphitization temperature of 2500 ℃ for 1 hour under argon gas to obtain a graphitized pitch-based carbon fiber.
Example 4
Taking a certain refinery catalytic cracking residual oil as a raw material; then, carrying out hot filtration through a filter with the pore diameter smaller than 5 microns to obtain a refined raw material; extracting with n-heptane, toluene, pyridine and quinoline according to the steps to obtain components of different families: n-Heptane Solubles (HS), n-heptane insoluble-toluene solubles (HI-TS), toluene insoluble-pyridine solubles (TI-PS), pyridine insoluble-quinoline solubles (PI-QS), Quinoline Insoluble (QI); adding HS, HI-TS, TI-PS, PI-QS and QI into a reaction kettle according to the mass ratio of 5: 15: 45: 35: 0 for mixing; then, under the conditions of nitrogen protection and stirring, carrying out self-boosting polymerization reaction for 8 hours at the temperature of 420 ℃, and further carrying out reaction for 5 hours under the pressure reduction condition at the temperature of 400 ℃ to obtain spinning asphalt; preparing asphalt fiber from the obtained asphalt under the conditions of spinning temperature of 350 ℃, spinning pressure of 0.02MPa and winding roller rotating speed of 500 r/min; pre-oxidizing the asphalt fiber at 282 deg.c and 2 deg.c/min; further, processing for 2 hours at the carbonization temperature of 1000 ℃ to obtain pitch-based carbon fiber; further, the fiber was treated at a graphitization temperature of 2500 ℃ for 1 hour under argon gas to obtain a graphitized pitch-based carbon fiber.
Fig. 5 is an X-ray diffraction (XRD) pattern of the graphitized pitch-based carbon fiber obtained in example 4.
Example 5
Taking a certain refinery catalytic cracking residual oil as a raw material; then, carrying out hot filtration through a filter with the pore diameter smaller than 5 microns to obtain a refined raw material; extracting with n-heptane, toluene, pyridine and quinoline according to the steps to obtain components of different families: n-Heptane Solubles (HS), n-heptane insoluble-toluene solubles (HI-TS), toluene insoluble-pyridine solubles (TI-PS), pyridine insoluble-quinoline solubles (PI-QS), Quinoline Insoluble (QI); adding HS, HI-TS, TI-PS, PI-QS and QI into a reaction kettle according to the mass ratio of 5: 15: 45: 35: 0 for mixing; then, under the conditions of nitrogen protection and stirring, carrying out self-boosting polymerization reaction for 8 hours at the temperature of 420 ℃, and further carrying out reaction for 5 hours under the pressure reduction condition at the temperature of 400 ℃ to obtain spinning asphalt; preparing asphalt fiber from the obtained asphalt under the conditions of spinning temperature of 350 ℃, spinning pressure of 0.02MPa and winding roller rotating speed of 500 r/min; pre-oxidizing the asphalt fiber at the pre-oxidation temperature of 300 ℃ and the heating rate of 2 ℃/min; further, processing for 2 hours at the carbonization temperature of 1000 ℃ to obtain pitch-based carbon fiber; further, the fiber was treated at a graphitization temperature of 2500 ℃ for 1 hour under argon gas to obtain a graphitized pitch-based carbon fiber.
Fig. 6 is an X-ray diffraction (XRD) pattern of the graphitized pitch-based carbon fiber obtained in example 5.
Example 6
Taking a certain refinery catalytic cracking residual oil as a raw material; then, carrying out hot filtration through a filter with the pore diameter smaller than 5 microns to obtain a refined raw material; extracting with n-heptane, toluene, pyridine and quinoline according to the steps to obtain components of different families: n-Heptane Solubles (HS), n-heptane insoluble-toluene solubles (HI-TS), toluene insoluble-pyridine solubles (TI-PS), pyridine insoluble-quinoline solubles (PI-QS), Quinoline Insoluble (QI); adding HS, HI-TS, TI-PS, PI-QS and QI into a reaction kettle according to the mass ratio of 5: 15: 45: 35: 0 for mixing; then, under the conditions of nitrogen protection and stirring, carrying out self-boosting polymerization reaction for 8 hours at the temperature of 420 ℃, and further carrying out reaction for 5 hours under the pressure reduction condition at the temperature of 400 ℃ to obtain spinning asphalt; preparing asphalt fiber from the obtained asphalt under the conditions of spinning temperature of 350 ℃, spinning pressure of 0.02MPa and winding roller rotating speed of 500 r/min; pre-oxidizing the asphalt fiber at the pre-oxidation temperature of 320 ℃ and the heating rate of 2 ℃/min; further, processing for 2 hours at the carbonization temperature of 1000 ℃ to obtain pitch-based carbon fiber; further, the fiber was treated at a graphitization temperature of 2500 ℃ for 1 hour under argon gas to obtain a graphitized pitch-based carbon fiber.
Fig. 7 is an X-ray diffraction (XRD) pattern of the graphitized pitch-based carbon fiber obtained in example 6.
Claims (7)
1. A method of preparing spinnable pitch by combining raw materials, comprising the steps of:
(1) selecting raw materials required for preparing spinnable asphalt, and carrying out hot filtration on the raw materials to remove catalysts, other impurities and the like in the raw materials so as to obtain refined raw materials;
(2) extracting the hot filtration refining raw material obtained in the step (1) by adopting n-heptane to obtain an n-heptane solution and an n-Heptane Insoluble (HI) solution; evaporating the solvent from the n-heptane solution to obtain n-heptane soluble material (HS);
(3) extracting the n-heptane insoluble substance (HI) obtained in the step (2) with toluene to obtain a toluene solution and a toluene insoluble substance (TI); evaporating the solvent from the toluene solution to obtain toluene soluble matter (TS);
(4) extracting the toluene insoluble substance (TI) obtained in the step (3) by using pyridine to obtain a pyridine solution and a pyridine insoluble substance (PI); evaporating the solvent from the pyridine solution to obtain pyridine soluble matter (PS);
(5) extracting the pyridine insoluble substance (PI) obtained in the step (4) by using quinoline to obtain a quinoline solution and a quinoline insoluble substance (QI); evaporating the solvent of the quinoline solution to obtain quinoline soluble substance (QS);
(6) grouping the raw material family compositions obtained in the steps (1) to (5), wherein the composition of the component 1: step (2) n-Heptane Solubles (HS); and (2) component: step (3) Toluene Solubles (TS); and (3) component: step (4) Pyridine Soluble (PS); and (4) component: step (5) Quinoline Solubles (QS); and (5) component: step (6) quinoline insoluble matter (QI);
(7) mixing the grouped component 1, the component 2, the component 3, the component 4 and the component 5 obtained in the steps (1) to (6) according to a certain proportion, putting the mixture into a reaction kettle, heating the mixture to a proper temperature under the protection of nitrogen, completely melting the components, uniformly mixing the components under the stirring action, and keeping stirring, mixing and reacting for a period of time; and then cooling to obtain the spinnable asphalt.
2. A method of producing spinnable pitch by combining raw materials according to claim 1, wherein the carbon fiber is produced by the steps of:
(8) preparing the spinnable asphalt obtained in the step (7) into asphalt fibers by a melt spinning method, or further performing pre-oxidation treatment and carbonization treatment to obtain asphalt-based carbon fibers; or further, the obtained pitch-based carbon fiber is subjected to high-temperature graphitization treatment to obtain a graphitized pitch-based carbon fiber.
3. The method for preparing spinnable asphalt by combining raw materials according to claim 1, wherein the raw material required for preparing spinnable asphalt is one or a combination of more of petroleum cracking residual oil, ethylene cracking residual oil, solvent extraction oil of petroleum residual oil, coal tar pitch, biomass pitch, etc. as a starting raw material; preferably one or more of petroleum cracking residual oil, ethylene cracking residual oil, solvent extraction oil of petroleum residual oil and coal tar pitch as initial raw materials.
4. A process for the preparation of spinnable pitch by combining raw materials according to claim 1, characterised in that the raw materials are subjected to hot filtration using a filter pore size of less than 10 microns, an optimised filter pore size of less than 5 microns, and more preferably a filter pore size of less than 1 micron.
5. A process for preparing a spinnable pitch by combining the raw materials as claimed in claim 1, wherein the proportions of component 1, component 2, component 3, component 4 and component 5 are: HS 0-30%, HI-TS 5-30%, TI-PS 30-70%, PI-QS 20-60%, QI 0-40%; the optimized proportion is as follows: HS 0-10%, HI-TS 10-20%, TI-PS 35-50%, PI-QS 25-40%, QI 0-20%.
6. The method for preparing spinnable asphalt by combining raw materials as claimed in claim 1, wherein the components obtained in step (6) are placed in a reaction kettle according to a certain ratio, nitrogen is introduced, the mixture is heated and melted and stirred, the temperature is 250-450 ℃, the optimized temperature is 300-430 ℃, and the more preferable temperature is 340-420 ℃; mixing and reacting under stirring for 0.1-40h, optimally for 0.5-20h, more optimally for 2-10 h; after mixing and reacting, cooling to room temperature under the protection of nitrogen to obtain the spinnable asphalt.
7. The method for preparing spinnable asphalt by combining raw materials as claimed in claim 1, wherein the spinnable asphalt obtained in step (7) is used for preparing asphalt fiber by melt spinning, the spinning condition temperature is 280-; further, pre-oxidizing the asphalt fiber, wherein the pre-oxidizing temperature is 380 ℃ in 240-; further, carrying out carbonization treatment on the fiber at the temperature of 1000-1600 ℃ for 0.5-5h to obtain the pitch-based carbon fiber; further, graphitizing the fiber at the temperature of 2000-3000 ℃, and optimally 2600-3000 ℃, so as to obtain the graphitized asphalt-based carbon fiber.
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| CN115197732A (en) * | 2022-06-07 | 2022-10-18 | 中国矿业大学(北京) | Preparation method of high-quality synthetic spinnable asphalt and carbon fiber |
| CN115369520A (en) * | 2022-08-23 | 2022-11-22 | 易高环保能源科技(张家港)有限公司 | Mesophase pitch-based carbon fiber with mixed structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109181732A (en) * | 2018-09-30 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | A kind of method that coal tar preparation can spin pitch |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109181732A (en) * | 2018-09-30 | 2019-01-11 | 中国科学院山西煤炭化学研究所 | A kind of method that coal tar preparation can spin pitch |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115197732A (en) * | 2022-06-07 | 2022-10-18 | 中国矿业大学(北京) | Preparation method of high-quality synthetic spinnable asphalt and carbon fiber |
| CN115197732B (en) * | 2022-06-07 | 2023-12-22 | 中国矿业大学(北京) | Preparation method of high-quality synthetic spinnable asphalt and carbon fiber |
| CN115369520A (en) * | 2022-08-23 | 2022-11-22 | 易高环保能源科技(张家港)有限公司 | Mesophase pitch-based carbon fiber with mixed structure and preparation method thereof |
| CN115369520B (en) * | 2022-08-23 | 2023-09-05 | 易高碳材料控股(深圳)有限公司 | Mesophase pitch-based carbon fiber with mixed structure and preparation method thereof |
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