CN115893372A - Method for preparing carbon microspheres from pitch depolymerized by supercritical methanol and application of carbon microspheres - Google Patents
Method for preparing carbon microspheres from pitch depolymerized by supercritical methanol and application of carbon microspheres Download PDFInfo
- Publication number
- CN115893372A CN115893372A CN202310000982.3A CN202310000982A CN115893372A CN 115893372 A CN115893372 A CN 115893372A CN 202310000982 A CN202310000982 A CN 202310000982A CN 115893372 A CN115893372 A CN 115893372A
- Authority
- CN
- China
- Prior art keywords
- carbon microspheres
- asphalt
- depolymerized
- washing
- carbon
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 112
- 239000004005 microsphere Substances 0.000 title claims abstract description 112
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000010426 asphalt Substances 0.000 claims abstract description 65
- 238000005406 washing Methods 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 24
- 229920002545 silicone oil Polymers 0.000 claims abstract description 24
- 239000007772 electrode material Substances 0.000 claims abstract description 22
- 239000003990 capacitor Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000003208 petroleum Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 238000006068 polycondensation reaction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011295 pitch Substances 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011301 petroleum pitch Substances 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011294 coal tar pitch Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000011302 mesophase pitch Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000011318 synthetic pitch Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Images
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention relates to a method for preparing carbon microspheres by utilizing pitch depolymerized by supercritical methanol and application thereof. Then mixing the depolymerized asphalt and the dimethyl silicone oil according to a certain proportion, preparing a crude product of the carbon microsphere by an emulsification-thermal polycondensation method, and obtaining the pure carbon microsphere after centrifugal separation, washing and drying. The asphalt raw material used in the invention is cheap and easy to obtain, and the cost is lower; the reaction process is simple to operate, and complex equipment is not needed; the prepared carbon microsphere has smooth surface, narrow particle size distribution range and excellent electrochemical performance, and has good application prospect in capacitor electrode material.
Description
Technical Field
The invention belongs to the field of high-efficiency processing and utilization of heavy oil, and particularly relates to a method for preparing carbon microspheres by utilizing pitch depolymerized by supercritical methanol, wherein the carbon microspheres are applied to the field of electrochemical materials.
Background
In recent years, carbon materials such as carbon microspheres, carbon fibers, mesophase pitch, electrode materials and the like produced from petroleum pitch have been hot research points for high value-added utilization of heavy oil.
The carbon microsphere is a novel functional material, has good chemical and thermal stability, is easy to graphitize, is an excellent electric conduction and thermal conduction material, and has wide application and development prospects in the aspects of lithium ion batteries, electrode materials, catalyst carriers and the like. The focus of the technical research and development in the field at present is the preparation method of the mesocarbon microbeads, which mainly comprises a solvothermal method, a chemical vapor deposition method, a thermal polycondensation method, an emulsification method and a suspension method.
In the preparation process of the carbon microsphere, besides the preparation mode has important influence on the formation of the microsphere, the raw material composition and the nucleating agent play a key role in the nucleation, growth and fusion process of the mesophase and influence the coalescence, crystallization and particle size distribution of the carbon microsphere. The raw materials adopted in the prior art mainly comprise coal pitch, coal tar, petroleum pitch, synthetic resin, synthetic pitch and the like, for example, patent 201810173414.2 discloses that medium-temperature coal tar pitch and an aromatic active copolycondensation agent are mixed according to a certain mass proportion, and the mesophase carbon microspheres with high yield and uniform particle size are prepared through copolycondensation, so that the requirements of high-quality and high-value-added carbon materials on the raw materials are met. Patent 201610470744.9 discloses that coal tar pitch and petroleum asphalt are mixed according to the mass ratio of 10:90 to 90: mixing in 10 range, adding catalyst FeBr 3 Then, the intermediate phase carbon microsphere with controllable grain diameter can be prepared by thermal polycondensation.
The petroleum asphalt has rich resources, and is mainly prepared by passing residual oil obtained by atmospheric and vacuum distillation of crude oil through a C 3 -C 5 Extracting with alkane solvent. Although there are many reports on the preparation of carbon materials directly from petroleum pitch, petroleum pitch is the heaviest component in petroleum, has strong aromaticity and polarity, and is usually highly aggregated under normal conditions and exists as supramolecular aggregates. In the high-temperature processing process, the pitch is easy to further condense to cause coking, so that in the process of preparing a carbon material by using petroleum pitch as a raw material, the pitch is prepared byThe asphaltene grows in a primary compact aggregation state, and high-performance materials such as carbon microspheres and carbon fibers are difficult to prepare. If the primary aggregation state of the depolymerized asphalt is broken, the grade of the prepared carbon material can be greatly improved. Until now, no technical report for preparing carbon microspheres by utilizing pitch depolymerized by supercritical methanol is available.
Disclosure of Invention
The invention aims to solve the problem of developing an efficient processing and utilizing way of inferior heavy oil, and aims to provide a preparation method and application of carbon microspheres. The method for depolymerizing the asphalt aggregate by using the supercritical methanol is used for efficiently depolymerizing the asphalt aggregate to a substructure level or even a monomolecular state so as to prepare the carbon microsphere with excellent performance by using an emulsification-thermal polycondensation method in the subsequent process, and is applied to the field of electrode materials.
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing carbon microspheres by utilizing pitch depolymerized by supercritical methanol.
In order to achieve the purpose, the invention is realized by the following technical scheme:
(1) Asphalt depolymerization
The asphalt used in the invention is residual oil obtained from naphthenic base crude oil to mix C 4 The alkane serves as the bitumen after solvent extraction. Mixing methanol and asphalt according to the mass ratio of 10 to 1;
(2) Preparation of carbon microspheres
Separating the depolymerized asphalt in the step (1), mixing the depolymerized asphalt with dimethyl silicon oil according to a mass ratio of 1 to 1;
(3) Separating and purifying carbon microballoon
And (3) cooling the reaction kettle after the preparation process of the carbon microspheres in the step (2) to room temperature, taking out a product, carrying out centrifugal separation on the product in a centrifugal machine at the rotating speed of 4800rpm, wherein the liquid with the gray upper layer obtained by the centrifugation is emulsified dimethyl silicone oil, and the sediment at the bottom is the crude carbon microspheres prepared by the emulsion polycondensation method. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and continuing washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres.
(4) Carbon microsphere application
In order to use the prepared carbon microspheres as capacitor electrode materials, the carbon microspheres are loaded on foamed nickel and used as working electrodes.
The evaluation method of the carbon microsphere used as the electrochemical electrode material comprises the following steps: and (4) carrying out electrochemical performance test on the working electrode at room temperature by adopting an electrochemical workstation. The test system uses silver-silver chloride as a reference electrode, a platinum electrode as a counter electrode and foam nickel loaded with carbon microspheres as a working electrode to form a three-electrode system, constant current charge/discharge test and cyclic voltammetry performance test are carried out in 1mol/L KOH electrolyte with the current density of 0.1A/g, and the specific capacitance of the carbon microsphere electrode material is calculated according to the formula (1).
Description of the symbols: c in the formula (1) is specific capacitance (F/g); i is a charge/discharge current (A); m is 1cm 2 Mass (g) of the carbon microspheres loaded on the foamed nickel; Δ t is the discharge time(s); and delta V is a charge-discharge voltage interval.
Compared with the prior art, the invention mainly has the following advantages:
(1) The asphalt raw material used in the invention is cheap and easy to obtain, and the cost is lower.
(2) Methanol is used as a supercritical solvent and a reactant, and raw materials are easy to obtain; the asphalt depolymerization process is simple to operate and does not need complex equipment;
(3) The asphalt is depolymerized by adopting supercritical methanol, the aromatic lamellar stacking degree of the asphalt is weakened, and the prepared carbon microsphere has good sphericity and controllable particle size.
(4) The invention adopts the emulsification-thermal polycondensation method to prepare the carbon microspheres without adding other auxiliary agents, has simple product separation and is beneficial to large-scale production.
(5) The carbon microspheres prepared from the pitch depolymerized by the supercritical methanol are applied to electrochemical electrode materials, and show good electron transport performance.
Drawings
Fig. 1 is a constant current charge and discharge curve of examples 2, 4 and comparative example 1.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. Other embodiments that are within the scope of the invention will be apparent to those of ordinary skill in the art from the embodiments disclosed herein.
The asphalt mixed by methanol and a certain mass ratio refers to residual oil obtained from naphthenic base crude oil and mixed C 4 And (3) extracting the obtained asphalt by using alkane as a solvent.
Example 1
Mixing methanol and asphalt according to a mass ratio of 10 to 1, transferring the mixture to a high-temperature high-pressure magnetic stirring reaction kettle, replacing air in the kettle with nitrogen, screwing all valves, heating to 300 ℃ at a heating rate of 4 ℃/min, wherein the pressure reaches 8MPa, depolymerizing the asphalt with supercritical methanol for 2h, and then filtering and separating the depolymerized asphalt; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and continuing washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microspheres have smooth surfaces, good sphericity and a particle size of 1-6 μm. The electrochemical performance of the carbon microsphere prepared in this example as a working electrode of a capacitor was measured, and the discharge time and specific capacitance of the electrode material are shown in table 1.
Example 2
Mixing methanol and asphalt according to a mass ratio of 30; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and continuing washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microspheres have smooth surfaces, good sphericity and a particle size of 1-6 μm. The electrochemical performance of the carbon microsphere prepared in this example as a working electrode of a capacitor was measured, and the discharge time and specific capacitance of the electrode material are shown in table 1.
Example 3
Mixing methanol and asphalt according to a mass ratio of 50 to 1, transferring the mixture to a high-temperature high-pressure magnetic stirring reaction kettle, replacing air in the kettle with nitrogen, screwing all valves, heating to 350 ℃ at a heating rate of 4 ℃/min, depolymerizing the asphalt with supercritical methanol for 4 hours when the pressure reaches 10MPa, and then filtering and separating the depolymerized asphalt; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and continuing washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microspheres have smooth surfaces, good sphericity and a particle size of 1-6 μm. The carbon microspheres prepared in this example were used as capacitor working electrodes to measure their electrochemical properties, and the discharge time and specific capacitance values of the electrode materials are shown in table 1.
Example 4
Mixing methanol and asphalt according to a mass ratio of 70 to 1, transferring the mixture to a high-temperature high-pressure magnetic stirring reaction kettle, replacing air in the kettle with nitrogen, screwing all valves, heating the mixture to 380 ℃ at a heating rate of 4 ℃/min, wherein the pressure reaches 11MPa, depolymerizing the asphalt with supercritical methanol for 5 hours, and then filtering and separating the depolymerized asphalt; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and then continuously washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microsphere has smooth surface, good sphericity and 1-6 μm particle size. The carbon microspheres prepared in this example were used as capacitor working electrodes to measure their electrochemical properties, and the discharge time and specific capacitance values of the electrode materials are shown in table 1.
Example 5
Mixing methanol and asphalt according to a mass ratio of 100 to 1, transferring the mixture to a high-temperature high-pressure magnetic stirring reaction kettle, replacing air in the kettle with nitrogen, screwing all valves, heating to 400 ℃ at a heating rate of 4 ℃/min, wherein the pressure reaches 12MPa, depolymerizing the asphalt with supercritical methanol for 2h, and then filtering and separating the depolymerized asphalt; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and continuing washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microspheres have smooth surfaces, good sphericity and a particle size of 1-6 μm. The carbon microspheres prepared in this example were used as capacitor working electrodes to measure their electrochemical properties, and the discharge time and specific capacitance values of the electrode materials are shown in table 1.
Example 6
Mixing methanol and asphalt according to a mass ratio of 20 to 1, transferring the mixture to a high-temperature high-pressure magnetic stirring reaction kettle, replacing air in the kettle with nitrogen, screwing all valves, heating to 320 ℃ at a heating rate of 4 ℃/min, wherein the pressure reaches 8MPa, depolymerizing the asphalt with supercritical methanol for 3 hours, and then filtering and separating the depolymerized asphalt; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and continuing washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microspheres have smooth surfaces, good sphericity and a particle size of 1-6 μm. The carbon microspheres prepared in this example were used as capacitor working electrodes to measure their electrochemical properties, and the discharge time and specific capacitance values of the electrode materials are shown in table 1.
Example 7
Mixing methanol and asphalt according to a mass ratio of 40:1, transferring the mixture into a high-temperature high-pressure magnetic stirring reaction kettle, replacing air in the kettle with nitrogen, screwing all valves, heating to 340 ℃ at a heating rate of 4 ℃/min, depolymerizing the asphalt with supercritical methanol for 4 hours when the pressure reaches 9MPa, and then filtering and separating the depolymerized asphalt; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and continuing washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microspheres have smooth surfaces, good sphericity and a particle size of 1-6 μm. The carbon microspheres prepared in this example were used as capacitor working electrodes to measure their electrochemical properties, and the discharge time and specific capacitance values of the electrode materials are shown in table 1.
Example 8
Mixing methanol and asphalt according to a mass ratio of 60 to 1, transferring the mixture to a high-temperature high-pressure magnetic stirring reaction kettle, replacing air in the kettle with nitrogen, screwing all valves, heating to 360 ℃ at a heating rate of 4 ℃/min, wherein the pressure reaches 11MPa, depolymerizing the asphalt with supercritical methanol for 5 hours, and then filtering and separating the depolymerized asphalt; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and then continuously washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microsphere has smooth surface, good sphericity and 1-6 μm particle size. The carbon microspheres prepared in this example were used as capacitor working electrodes to measure their electrochemical properties, and the discharge time and specific capacitance values of the electrode materials are shown in table 1.
Example 9
Mixing methanol and asphalt according to a mass ratio of 80 to 1, transferring the mixture to a high-temperature high-pressure magnetic stirring reaction kettle, replacing air in the kettle with nitrogen, screwing all valves, heating to 380 ℃ at a heating rate of 4 ℃/min, allowing the pressure to reach 12MPa, depolymerizing the asphalt with supercritical methanol for 2 hours, and filtering to separate depolymerized asphalt; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and then continuously washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microsphere has smooth surface, good sphericity and 1-6 μm particle size. The electrochemical performance of the carbon microsphere prepared in this example as a working electrode of a capacitor was measured, and the discharge time and specific capacitance of the electrode material are shown in table 1.
Example 10
Mixing methanol and asphalt according to a mass ratio of 90 to 1, transferring the mixture to a high-temperature high-pressure magnetic stirring reaction kettle, replacing air in the kettle with nitrogen, screwing all valves, heating to 320 ℃ at a heating rate of 4 ℃/min, wherein the pressure reaches 8MPa, depolymerizing the asphalt with supercritical methanol for 5 hours, and then filtering and separating the depolymerized asphalt; mixing depolymerized asphalt and dimethyl silicone oil according to a mass ratio of 1. And taking out the crude carbon microspheres, washing with petroleum ether to remove light components and dimethyl silicone oil on the surfaces of the crude carbon microspheres until the washing liquid becomes colorless, and then continuously washing with absolute ethyl alcohol. And (5) after washing, placing the carbon microspheres in a vacuum drying oven for drying for 5 hours to obtain the carbon microspheres. The carbon microsphere has smooth surface, good sphericity and 1-6 μm particle size. The carbon microspheres prepared in this example were used as capacitor working electrodes to measure their electrochemical properties, and the discharge time and specific capacitance values of the electrode materials are shown in table 1.
Comparative example 1
In this example, the asphalt without being depolymerized by supercritical methanol was directly prepared into carbon microspheres by the emulsion-thermal polycondensation method, and the reaction conditions and the operation steps were the same as those of example 2. The carbon microsphere prepared by the comparative example has unsmooth surface, flocculent particles are attached to the surface of the carbon microsphere, the sphericity is general, and the particle size is 0.5-22 mu m. The carbon microspheres prepared in this example were used as capacitor working electrodes to measure their electrochemical properties, and the discharge time and specific capacitance values of the electrode materials are shown in table 1. The discharge time is only 3.6s, and the specific capacitance is very small, which indicates that the electron transport rate of the carbon microsphere prepared by the comparative example as an electrode material is poor.
TABLE 1 discharge time and specific capacitance of carbon microsphere electrode materials
| Item | Discharge time(s) | Specific capacitance (F/g) |
| Comparative example 1 | 3.6 | 0.45 |
| Example 1 | 225.1 | 28.14 |
| Example 2 | 169.9 | 21.23 |
| Example 3 | 215.7 | 26.96 |
| Example 4 | 128.5 | 16.07 |
| Example 5 | 223.6 | 27.95 |
| Example 6 | 241.7 | 30.21 |
| Example 7 | 210.9 | 26.36 |
| Example 8 | 237.0 | 29.63 |
| Example 9 | 241.4 | 30.18 |
| Example 10 | 255.6 | 31.95 |
Claims (3)
1. A method for preparing carbon microspheres by utilizing pitch depolymerized by supercritical methanol is characterized by comprising the following steps:
(1) Mixing methanol and asphalt according to a mass ratio of 10 to 1;
(2) Separating out the depolymerized asphalt in the step (1) by filtering, mixing the depolymerized asphalt with dimethyl silicone oil according to a mass ratio of 1;
(3) And (3) cooling to room temperature after the heating in the step (2) is finished, taking out a product, and performing centrifugal separation at the rotating speed of 4800rpm to obtain bottom sediment, namely the prepared crude carbon microspheres. And (3) washing the crude carbon microspheres with petroleum ether until the eluate is colorless, then continuing washing with absolute ethyl alcohol, and drying in a vacuum drying oven for 5 hours after washing to obtain the carbon microspheres.
2. The method for preparing carbon microspheres by using asphalt depolymerized by supercritical methanol according to claim 1, wherein the asphalt used in the step (1) is residual oil obtained from naphthenic crude oil to mix C 4 The alkane serves as the bitumen after solvent extraction.
3. The method for preparing carbon microspheres from pitch depolymerized with supercritical methanol according to claim 1, wherein the prepared carbon microspheres are used as capacitor electrode materials, and the specific capacitance can reach 15-32F/g at a current density of 0.1A/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310000982.3A CN115893372A (en) | 2023-01-03 | 2023-01-03 | Method for preparing carbon microspheres from pitch depolymerized by supercritical methanol and application of carbon microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310000982.3A CN115893372A (en) | 2023-01-03 | 2023-01-03 | Method for preparing carbon microspheres from pitch depolymerized by supercritical methanol and application of carbon microspheres |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115893372A true CN115893372A (en) | 2023-04-04 |
Family
ID=86471254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310000982.3A Pending CN115893372A (en) | 2023-01-03 | 2023-01-03 | Method for preparing carbon microspheres from pitch depolymerized by supercritical methanol and application of carbon microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115893372A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19935447A1 (en) * | 1999-07-28 | 2001-02-01 | Thorsten Kraft | Carbon microspheres, useful as anode material for lithium battery or starting materials for wear-resistant sintered carbon part, e.g. petrol engine piston or tubular furnace, are prepared by pyrolysis of amine producing ammonia |
| CN102942172A (en) * | 2012-11-22 | 2013-02-27 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
| US20130241094A1 (en) * | 2011-04-28 | 2013-09-19 | Yizhou KONG | Preparation method for asphalt-based spherical activated carbon which requires no infusibilization process |
| CN109609183A (en) * | 2018-12-11 | 2019-04-12 | 西安交通大学 | Coal tar Method for treatment of oil based on supercritical methanol |
| CN110697676A (en) * | 2018-07-10 | 2020-01-17 | 中国石油大学(北京) | Hollow carbon microsphere and preparation method thereof |
| CN110697677A (en) * | 2018-07-10 | 2020-01-17 | 中国石油大学(北京) | Hollow carbon microsphere and preparation method thereof |
| CN112755578A (en) * | 2020-12-22 | 2021-05-07 | 同济大学 | Asphalt cement separation method based on supercritical fluid extraction |
| CN114522634A (en) * | 2022-02-18 | 2022-05-24 | 四川轻化工大学 | Method for separating mesocarbon microbeads through supercritical extraction |
-
2023
- 2023-01-03 CN CN202310000982.3A patent/CN115893372A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19935447A1 (en) * | 1999-07-28 | 2001-02-01 | Thorsten Kraft | Carbon microspheres, useful as anode material for lithium battery or starting materials for wear-resistant sintered carbon part, e.g. petrol engine piston or tubular furnace, are prepared by pyrolysis of amine producing ammonia |
| US20130241094A1 (en) * | 2011-04-28 | 2013-09-19 | Yizhou KONG | Preparation method for asphalt-based spherical activated carbon which requires no infusibilization process |
| CN102942172A (en) * | 2012-11-22 | 2013-02-27 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
| CN110697676A (en) * | 2018-07-10 | 2020-01-17 | 中国石油大学(北京) | Hollow carbon microsphere and preparation method thereof |
| CN110697677A (en) * | 2018-07-10 | 2020-01-17 | 中国石油大学(北京) | Hollow carbon microsphere and preparation method thereof |
| CN109609183A (en) * | 2018-12-11 | 2019-04-12 | 西安交通大学 | Coal tar Method for treatment of oil based on supercritical methanol |
| CN112755578A (en) * | 2020-12-22 | 2021-05-07 | 同济大学 | Asphalt cement separation method based on supercritical fluid extraction |
| CN114522634A (en) * | 2022-02-18 | 2022-05-24 | 四川轻化工大学 | Method for separating mesocarbon microbeads through supercritical extraction |
Non-Patent Citations (1)
| Title |
|---|
| 陈康等: "超临界流体改质煤焦油研究进展", 化工进展, vol. 38, no. 4, 30 April 2019 (2019-04-30), pages 1702 - 1713 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107720721B (en) | Mesocarbon microspheres and preparation method thereof | |
| CN110437862B (en) | Preparation method of intermediate phase pitch coke, negative electrode material and lithium battery | |
| CN102653397A (en) | Preparation method of coal tar-based mesocarbon microbead | |
| CN112552946B (en) | Preparation method of mesophase pitch | |
| CN107474866B (en) | A kind of preparation method of high-quality mesophase pitch | |
| CN103359702A (en) | Preparation method of mesophase carbon microspheres with different particle sizes | |
| CN102491307A (en) | Method for preparing mesocarbon microbeads by copolycondensation | |
| CN108584904A (en) | A kind of method that by-product pitch cycle thermal polycondensation prepares mesocarbon microspheres | |
| CN1100093C (en) | Prepn. method of mesophase asphalt carbon microsphere | |
| CN112645304B (en) | Method for preparing high-performance mesocarbon microbeads from heavy oil | |
| CN113955756A (en) | Carbonized amino acid modified lignin and preparation method thereof | |
| CN110357069B (en) | Method for preparing mesocarbon microbeads by using emulsification-hydrogenation-thermal polymerization ternary coupling system | |
| CN115093874A (en) | Preparation method and system of low-quinoline insoluble matter high-softening-point petroleum-based coated asphalt | |
| CN113582159B (en) | High-capacitance porous carbon material and preparation method thereof | |
| CN113353915B (en) | Mesocarbon microbeads, preparation method thereof, spherical porous activated carbon material and application thereof | |
| CN115893372A (en) | Method for preparing carbon microspheres from pitch depolymerized by supercritical methanol and application of carbon microspheres | |
| CN112831335B (en) | Method for preparing mesophase pitch and mesophase carbon microspheres from heavy oil | |
| CN104425821A (en) | Lithium ion battery graphite anode material and preparation method thereof | |
| CN111573748A (en) | N, P-codoped porous carbon-NiS2Electrode material of super capacitor and preparation method thereof | |
| CN111826187A (en) | Novel high-performance asphalt special for carbon material and preparation method thereof | |
| CN110993363A (en) | Super-capacitor electrode carbon material and preparation method thereof | |
| CN107601492B (en) | Preparation method of two-dimensional graphite-like structure material | |
| CN111377428B (en) | Method for preparing needle coke by using medium-low temperature coal tar | |
| CN113562721A (en) | Preparation method and application of asphalt-based carbon microspheres | |
| CN110803693A (en) | Anthracene oil-based mesocarbon microbeads and preparation method and application thereof |
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 |