CN115340083A - Small-particle-size asphalt-based carbon microsphere and preparation method thereof - Google Patents
Small-particle-size asphalt-based carbon microsphere and preparation method thereof Download PDFInfo
- Publication number
- CN115340083A CN115340083A CN202210993611.5A CN202210993611A CN115340083A CN 115340083 A CN115340083 A CN 115340083A CN 202210993611 A CN202210993611 A CN 202210993611A CN 115340083 A CN115340083 A CN 115340083A
- Authority
- CN
- China
- Prior art keywords
- pitch
- based carbon
- small
- asphalt
- particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 66
- 239000010426 asphalt Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011295 pitch Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000003599 detergent Substances 0.000 claims abstract description 15
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000011301 petroleum pitch Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract 2
- 239000003921 oil Substances 0.000 claims description 22
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000011300 coal pitch Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000000295 fuel oil Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000010779 crude oil Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011319 crude-oil pitch Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000011312 pitch solution Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
The invention provides a small-particle-size asphalt-based carbon microsphere and a preparation method thereof, belongs to the technical field of preparation of spherical carbon materials, and aims to solve the technical problems of complex process and high cost of the existing isotropic carbon microsphere preparation process. The preparation method comprises the following steps: uniformly mixing coal tar pitch and petroleum pitch to obtain a mixture; and stirring the mixture under the protection of inert gas for blending reaction to obtain blended asphalt after the reaction is finished, and then extracting and separating the blended asphalt by using a detergent to obtain the small-particle-size asphalt-based carbon microsphere precursor. And pre-oxidizing and carbonizing the small-particle size pitch-based carbon microsphere precursor to obtain the small-particle size pitch-based carbon microsphere. In the process of preparing the carbon microsphere precursor, only reaction raw materials are involved, no solvent or additive is needed to be additionally used, the preparation time is short, and the process is simple. In addition, the particle size of the asphalt-based carbon microsphere prepared by the method is only 0.5-3.0 mu m, the particle size is small, and the uniformity is good.
Description
Technical Field
The invention belongs to the technical field of preparation of spherical carbon materials, and particularly relates to a small-particle-size asphalt-based carbon microsphere and a preparation method thereof.
Background
In recent years, with the development of various carbon materials, the application field of the carbon materials is continuously expanded, and particularly, the isotropic pitch-based carbon microspheres can be applied to the fields of lithium ion battery cathode materials, high-performance liquid chromatographic columns, high-specific surface area activated carbon and catalyst carriers, so that the development of the pitch-based carbon microspheres with small particle size has important significance.
At present, the main preparation method of isotropic pitch carbon microspheres is as follows, in patent CN113562721a, raw material pitch is dissolved in a solvent to obtain a pitch solution, the pitch solution is put into a hydrothermal kettle, the temperature is kept at 100-250 ℃, and the pitch-based carbon microspheres are obtained by high-temperature carbonization treatment after washing. Patent CN112875700a proposes a method for preparing pitch-based carbon microspheres for supercapacitor electrodes by spray drying tetrahydrofuran soluble substances of pitch. Dissolving tetrahydrofuran soluble part of the asphalt with tetrahydrofuran to prepare different concentrations, and balling the asphalt by using a spray drying method. In patent CN110451475a, asphalt powder and a surfactant are mixed and then added into high-temperature silicone oil, and the mixture is heated and insulated in an air atmosphere to be melted into balls and surface oxidation simultaneously, so as to obtain asphalt microspheres with regular morphology and without melting, and then the asphalt microspheres are separated, washed and dried, and finally carbonized to obtain a final product, which is applied to a sodium ion battery electrode material. Patent CN111732098A proposes that crushed asphalt particles are sieved, glycerol or glycerin and a surfactant are used as an emulsifier, the mixture is stirred at the temperature of 110 ℃ to prepare small-particle-size asphalt microspheres, the sphere diameter is 20-40 microns, and the small-particle-size asphalt microspheres are finally prepared into graphitized asphalt microspheres through pre-oxidation, carbonization and graphitization and are used as negative electrode materials of lithium batteries. In patent CN105923620a, medium temperature pitch and carbon black are mixed according to a mass ratio of 100: placing the mixture in a reaction kettle in a proportion of 0.5-5 for thermal polycondensation, wherein the reaction temperature is 350-380 ℃, and an air oxidation method of blowing air into the reaction kettle is adopted to obtain the isotropic carbon microspheres. The method needs to use a solvent, a dispersing agent or a nucleating substance in the process of preparing the asphalt microspheres, needs to remove or extract at a later stage, and has complex preparation process flow and higher cost.
Disclosure of Invention
Aiming at the technical problems, the invention provides the small-particle-size asphalt-based carbon microsphere and the preparation method thereof, the preparation method only takes part in reaction raw materials, no solvent or additive is additionally used, the preparation time is short, and the process is simple.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of small-particle-size asphalt-based carbon microspheres comprises the following steps:
(1) Weighing coal pitch and petroleum pitch according to the mass ratio (90-10): (10-90) mixing to obtain a mixture;
(2) Stirring and blending the mixture in a reaction kettle under the protection of inert gas for 0.5-2h to obtain a product of blended asphalt, and extracting and separating the blended asphalt by using a detergent to obtain a small-particle-size asphalt-based carbon microsphere precursor;
(3) Pre-oxidizing the small-particle-size pitch-based carbon microsphere precursor at a certain temperature, and then carbonizing under the protection of inert gas to obtain the small-particle-size pitch-based carbon microsphere with the average particle size of 0.5-3 mu m.
The coal pitch is any one or more than two of coal tar heavy components, coal liquefaction residual oil, medium and low temperature coal tar pitch and high temperature coal tar distillate oil; the petroleum asphalt is any one or more than two of crude oil asphalt, heavy oil, secondary petroleum heavy oil, catalytic cracking slurry oil, furfural extract oil and heavy polycyclic aromatic hydrocarbon; the content of quinoline insoluble substances in the coal pitch and the petroleum pitch is less than 0.05wt%.
In the step (2), the temperature of the blending reaction of the coal pitch and the petroleum pitch mixture is 300-380 ℃, the heating rate is 5-10 ℃/min, the reaction pressure is 0-2 MPa, the reaction time is 0.5-2h, the stirring rate is 50-200rpm, and the inert gas is nitrogen and/or argon.
The detergent in the step (2) is any one or more than two of wash oil, 100# solvent oil, 200# solvent oil, toluene, benzene and chloroform, and the mass ratio of the detergent to the blended asphalt is (1-6): 1, the dissolving temperature in the extraction is 60-180 ℃.
In the step (3), the pre-oxidation temperature is 260-320 ℃, the temperature is kept for 0.5-2h, the heating rate is 0.2-2 ℃/min, the atmosphere is high-purity air, and the gas flow is 30-120 mL/min.
In the step (3), the carbonization temperature is 800-1200 ℃, the heating rate is 5-10 ℃/min, and the constant temperature is 0.5-2h; the protective atmosphere is nitrogen and/or argon, and the gas flow is 50-120mL/min.
The small-particle-size asphalt-based carbon microspheres can be applied to the fields of lithium ion battery cathode materials, high-performance liquid chromatographic columns, high-specific-surface-area activated carbon and catalyst carriers.
The invention has the beneficial effects that: coal tar pitch and petroleum pitch have large difference in structure and composition, and generally coal tar pitch has fewer aromatic rings, more short alkyl substituted side chains, more oxygen heteroatoms, smaller average relative molecular mass and higher aromaticity. The petroleum asphalt has more aromatic rings and longer alkyl branched chains, and has larger average relative molecular mass and smaller aromatic degree. The coal tar pitch and the petroleum pitch have poor compatibility and phase separation behavior in a mixed manner, and can cause flocculation and sedimentation. The invention prepares small-particle-size asphalt-based carbon microspheres rapidly by heating and blending coal pitch and petroleum pitch according to the difference of structures and compositions of the coal pitch and the petroleum pitch and by utilizing phase separation behavior caused by poor compatibility of the coal pitch and the petroleum pitch, and prepares the asphalt-based carbon microspheres with different particle sizes and yields by regulating and controlling a preparation process. In the process of preparing the carbon microsphere precursor, only reaction raw materials are involved, no solvent or additive is needed to be additionally used, the preparation time is short, and the process is simple. In addition, the particle size of the asphalt-based carbon microsphere prepared by the method is only 0.5-3.0 mu m, the particle size is small, and the uniformity is good.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM image of small particle size pitch-based carbon microspheres of example 1 of the present invention.
FIG. 2 is a partially enlarged view of small particle size pitch-based carbon microspheres of example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of small-particle-size asphalt-based carbon microspheres comprises the following steps:
selecting high-temperature coal tar distillate oil and crude oil pitch, and removing quinoline insoluble substances through pretreatment, wherein the content of the quinoline insoluble substances is less than 0.05wt%. Weighing coal pitch and crude oil pitch according to the mass ratio of 10:90, mixing; and stirring and blending the mixture in a reaction kettle under the protection of nitrogen inert gas for 0.5h at the temperature of 300 ℃ and the pressure of 0MPa (gauge pressure), wherein the heating rate is 10 ℃/min, and the stirring rate is 200rpm, so as to obtain the product, namely the blended asphalt. The blended asphalt is extracted and separated by detergent 200# solvent oil, and the mass ratio of the detergent to the blended asphalt is 1:1, drying for 2 hours at the dissolving temperature of 60 ℃ under reduced pressure at the temperature of 110 ℃ to obtain the pitch-based carbon microsphere precursor with small particle size, wherein the yield is 12wt%. Pre-oxidizing the small-particle size pitch-based carbon microsphere precursor at 260 ℃ for 0.5h at constant temperature, wherein the heating rate is 0.2 ℃/min, and the flow of high-purity air is 30mL/min; and then carbonizing at the constant temperature of 800 ℃ for 2h under the protection of nitrogen inert gas, wherein the heating rate is 5 ℃/min, and the gas flow is 120mL/min, so that the asphalt-based carbon microspheres with small particle sizes of 2 mu m are obtained, and the non-polarization characteristics of the asphalt-based carbon microspheres are isotropic carbon microspheres as shown in figures 1 and 2.
Example 2
A preparation method of small-particle-size asphalt-based carbon microspheres comprises the following steps:
selecting medium-low temperature coal tar pitch and heavy polycyclic aromatic hydrocarbon, and removing quinoline insoluble substances through pretreatment, wherein the content of the quinoline insoluble substances is less than 0.05wt%. Weighing coal pitch and petroleum pitch according to a mass ratio of 90:10, mixing; and stirring and blending the mixture in a reaction kettle for 2 hours under the protection of nitrogen inert gas at the temperature of 380 ℃ and the pressure of 2MPa (gauge pressure), wherein the heating rate is 5 ℃/min, and the stirring rate is 50rpm, so as to obtain the product, namely the blended asphalt. The blended asphalt is extracted and separated by detergent 100# solvent oil, and the mass ratio of the detergent to the blended asphalt is 6:1, drying for 2 hours at the dissolution temperature of 180 ℃ and the temperature of 110 ℃ under reduced pressure to obtain the pitch-based carbon microsphere precursor with small particle size, wherein the yield is 15wt%. Pre-oxidizing the small-particle-size pitch-based carbon microsphere precursor at the constant temperature of 320 ℃ for 1h, wherein the heating rate is 2 ℃/min, and the flow of high-purity air is 60mL/min; and then carbonizing at 1200 ℃ for 0.5h under the protection of argon inert gas at a constant temperature, wherein the heating rate is 10 ℃/min, and the gas flow is 100mL/min, so that the small-particle-size asphalt-based carbon microspheres of 3 mu m are obtained, and the non-polarization characteristics of the small-particle-size asphalt-based carbon microspheres are isotropic carbon microspheres.
Example 3
A preparation method of small-particle-size asphalt-based carbon microspheres comprises the following steps:
selecting coal liquefaction residual oil and catalytic cracking slurry oil, and removing quinoline insoluble substances through pretreatment, wherein the content of the quinoline insoluble substances is less than 0.05wt%. Weighing coal tar pitch and petroleum asphalt according to the mass ratio of 20:80, mixing; and stirring and blending the mixture in a reaction kettle for 1h under the protection of argon inert gas at the temperature of 360 ℃ and the pressure of 1MPa (gauge pressure), wherein the heating rate is 5 ℃/min, and the stirring rate is 100rpm, so as to obtain the product, namely the blended asphalt. The blended asphalt is extracted and separated by detergent wash oil, and the mass ratio of the detergent to the blended asphalt is 4:1, drying for 2 hours at the dissolution temperature of 100 ℃ under reduced pressure at the temperature of 110 ℃ to obtain the pitch-based carbon microsphere precursor with small particle size, wherein the yield is 18wt%. Pre-oxidizing the small-particle-size pitch-based carbon microsphere precursor at the constant temperature of 300 ℃ for 2h, wherein the heating rate is 1.5 ℃/min, and the flow of high-purity air is 100mL/min; and then carbonizing at the constant temperature of 1000 ℃ for 1.5h under the protection of inert gas of argon, wherein the heating rate is 6 ℃/min, and the gas flow is 80mL/min, so that the small-particle-size asphalt-based carbon microspheres of 0.5 mu m are obtained, and the non-polarization characteristics of the small-particle-size asphalt-based carbon microspheres are isotropic carbon microspheres.
Example 4
A preparation method of small-particle-size asphalt-based carbon microspheres comprises the following steps:
selecting high-temperature coal tar distillate oil and furfural extract oil, and removing quinoline insoluble substances through pretreatment, wherein the content of the quinoline insoluble substances is less than 0.05wt%. Weighing coal tar pitch and petroleum asphalt according to the mass ratio of 30:70, mixing; and stirring and blending the mixture in a reaction kettle for 1.5h under the protection of argon inert gas at the temperature of 320 ℃ and the pressure of 1.5MPa (gauge pressure), wherein the heating rate is 10 ℃/min, and the stirring rate is 150rpm, so as to obtain the product, namely the blended asphalt. Extracting and separating the blended asphalt by using a detergent toluene, wherein the mass ratio of the detergent to the blended asphalt is 2:1, drying for 2 hours at the dissolution temperature of 80 ℃ and the temperature of 110 ℃ under reduced pressure to obtain the pitch-based carbon microsphere precursor with small particle size, wherein the yield is 20wt%. Pre-oxidizing the small-particle-size pitch-based carbon microsphere precursor at the temperature of 280 ℃ for 1.5h at a heating rate of 1 ℃/min and at a high-purity air flow rate of 120mL/min; and then carbonizing at the constant temperature of 900 ℃ for 2h under the protection of nitrogen inert gas, wherein the heating rate is 8 ℃/min, and the gas flow is 50mL/min, so that the small-particle-size asphalt-based carbon microspheres of 1.5 mu m are obtained, and the non-polarization characteristics of the small-particle-size asphalt-based carbon microspheres are isotropic carbon microspheres.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the small-particle-size asphalt-based carbon microspheres is characterized by comprising the following steps of:
(1) Uniformly mixing coal tar pitch and petroleum pitch to obtain a mixture;
(2) Stirring the mixture under the protection of inert gas for blending reaction to obtain blended asphalt after the reaction is finished, and then dissolving the blended asphalt in a detergent for extraction and separation to obtain a pitch-based carbon microsphere precursor with small particle size;
(3) And pre-oxidizing and carbonizing the small-particle size pitch-based carbon microsphere precursor to obtain the small-particle size pitch-based carbon microsphere.
2. The method for preparing small-particle-size pitch-based carbon microspheres according to claim 1, wherein the method comprises the following steps: the coal pitch is any one or more than two of coal tar heavy components, coal liquefaction residual oil, medium-low temperature coal tar pitch or high-temperature coal tar distillate oil.
3. The method for preparing small-particle-size pitch-based carbon microspheres according to claim 2, wherein the method comprises the following steps: the petroleum asphalt is any one or more than two of crude oil asphalt, heavy oil, secondary petroleum heavy oil, catalytic cracking slurry oil, furfural extract oil or heavy polycyclic aromatic hydrocarbon; the content of quinoline insoluble substances in the coal pitch and the petroleum pitch is less than 0.05wt%.
4. The method for preparing small-particle-size pitch-based carbon microspheres according to claim 3, wherein the method comprises the following steps: the mass ratio of the coal pitch to the petroleum pitch in the step (1) is (90-10): (10-90).
5. The method for preparing small-particle size asphalt-based carbon microspheres according to claim 4, wherein the method comprises the following steps: the temperature of stirring and blending reaction in the step (2) is 300-380 ℃, the heating rate is 5-10 ℃/min, the reaction pressure is 0-2 MPa, the reaction time is 0.5-2h, and the stirring rate is 50-200rpm.
6. The method for preparing small-particle-size pitch-based carbon microspheres according to claim 5, wherein the method comprises the following steps: the inert gas is nitrogen and/or argon.
7. The method for preparing small-particle-size pitch-based carbon microspheres according to claim 6, wherein the method comprises the following steps: the detergent in the step (2) is any one or more than two of wash oil, 100# solvent oil, 200# solvent oil, toluene, benzene or chloroform.
8. The method for preparing small-particle-size pitch-based carbon microspheres according to claim 6, wherein the method comprises the following steps: the mass ratio of the detergent to the asphalt mixture in the step (2) (1-6) is as follows: 1, the dissolving temperature is 60-180 ℃.
9. The method for preparing small-particle-size pitch-based carbon microspheres according to claim 6, wherein the method comprises the following steps: the pre-oxidation conditions in the step (3) are as follows: the temperature is 260-320 ℃, the constant temperature is 0.5-2h, the heating rate is 0.2-2 ℃/min, the atmosphere is high-purity air, and the gas flow is 30-120 mL/min; the carbonization conditions are as follows: the temperature is 800-1200 ℃, the heating rate is 5-10 ℃/min, the constant temperature is 0.5-2h, the protective atmosphere is nitrogen and/or argon, and the gas flow is 50-120mL/min.
10. The small-particle size pitch-based carbon microspheres prepared by the method of any one of claims 1 to 9, wherein: the average grain diameter of the small-grain-diameter asphalt-based carbon microspheres is 0.5-3.0 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210993611.5A CN115340083B (en) | 2022-08-18 | 2022-08-18 | Small-particle-size asphalt-based carbon microsphere and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210993611.5A CN115340083B (en) | 2022-08-18 | 2022-08-18 | Small-particle-size asphalt-based carbon microsphere and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115340083A true CN115340083A (en) | 2022-11-15 |
| CN115340083B CN115340083B (en) | 2024-03-15 |
Family
ID=83953880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210993611.5A Active CN115340083B (en) | 2022-08-18 | 2022-08-18 | Small-particle-size asphalt-based carbon microsphere and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115340083B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4009232A (en) * | 1973-03-13 | 1977-02-22 | Kureha Kagaku Kogyo Kabushiki Kaisha | Method for the production of carbon microspheres 1-20 μ in diameter |
| CN1308113A (en) * | 2000-11-23 | 2001-08-15 | 天津大学 | Copolycondensation preparation of intermediate phase carbon microsphere |
| CN1559890A (en) * | 2004-03-03 | 2005-01-05 | 东华大学 | Preparation process of microball porous asphaltum group charring microball |
| CN101665250A (en) * | 2009-09-25 | 2010-03-10 | 福州大学 | Polymerizing-pyrolytic method for preparing mesocarbon microbead in asphaltic base |
| CN102491307A (en) * | 2011-11-25 | 2012-06-13 | 淄博矿业集团有限责任公司 | Method for preparing mesocarbon microbeads by copolycondensation |
-
2022
- 2022-08-18 CN CN202210993611.5A patent/CN115340083B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4009232A (en) * | 1973-03-13 | 1977-02-22 | Kureha Kagaku Kogyo Kabushiki Kaisha | Method for the production of carbon microspheres 1-20 μ in diameter |
| CN1308113A (en) * | 2000-11-23 | 2001-08-15 | 天津大学 | Copolycondensation preparation of intermediate phase carbon microsphere |
| CN1559890A (en) * | 2004-03-03 | 2005-01-05 | 东华大学 | Preparation process of microball porous asphaltum group charring microball |
| CN101665250A (en) * | 2009-09-25 | 2010-03-10 | 福州大学 | Polymerizing-pyrolytic method for preparing mesocarbon microbead in asphaltic base |
| CN102491307A (en) * | 2011-11-25 | 2012-06-13 | 淄博矿业集团有限责任公司 | Method for preparing mesocarbon microbeads by copolycondensation |
Non-Patent Citations (1)
| Title |
|---|
| 杨亦双: "中间相炭材料的制备及其电化学性能研究", 《中国博士学位论文全文数据库 工程科技II辑》, no. 5, pages 24 - 26 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115340083B (en) | 2024-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101294090B (en) | Fine purification method for coal tar pitch | |
| WO2015106720A1 (en) | Method for producing super activated charcoal from biomass power plant ash | |
| CN101811691A (en) | Preparation method of mesocarbon microbead | |
| CN1100093C (en) | Prepn. method of mesophase asphalt carbon microsphere | |
| CN112645304B (en) | Method for preparing high-performance mesocarbon microbeads from heavy oil | |
| CN109192524B (en) | Preparation method of activated carbon-graphene composite porous material | |
| CN113353915B (en) | Mesocarbon microbeads, preparation method thereof, spherical porous activated carbon material and application thereof | |
| CN109817915B (en) | Nano iron compound/mesocarbon microbead composite material and preparation method thereof | |
| CN111826187B (en) | Special high-performance asphalt for carbon material and preparation method thereof | |
| CN103509572B (en) | A kind of technique utilizing solvent method to prepare high-quality coal-based needle coke | |
| CN115340083B (en) | Small-particle-size asphalt-based carbon microsphere and preparation method thereof | |
| CN113830768A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN110171827B (en) | Nitrogen-doped spherical porous carbon, preparation method and application thereof | |
| CN111825086A (en) | Graphene preparation method | |
| CN115579470B (en) | Modified asphalt coated microcrystalline graphite negative electrode material and preparation method thereof | |
| CN112831335B (en) | Method for preparing mesophase pitch and mesophase carbon microspheres from heavy oil | |
| CN116081599A (en) | Preparation method and application of hard carbon anode material | |
| CN114914433A (en) | Coal-based graphite composite material and preparation method and application thereof | |
| CN112062127B (en) | Coal-based nano porous carbon and preparation method thereof | |
| CN112707380B (en) | Hard carbon precursor, soft and hard carbon composite material, and preparation method and application thereof | |
| CN105720233B (en) | Carbon material for lithium ion battery cathode, preparation method thereof, lithium ion battery cathode and lithium ion battery | |
| CN111392707B (en) | Method for preparing mesocarbon microbeads by direct coal liquefaction | |
| CN115321512B (en) | Isotropic carbon microsphere prepared from coal tar pitch and method thereof | |
| CN110803693A (en) | Anthracene oil-based mesocarbon microbeads and preparation method and application thereof | |
| CN102676196B (en) | Coal tar pitch for preparing needle coke, method for preparing same and solvent used in preparation process of coal tar pitch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |