Method for efficiently preparing petroleum asphalt-based mesocarbon microbeads

Abstract

The invention discloses a method for efficiently preparing petroleum asphalt-based mesocarbon microbeads. The method comprises the following steps: firstly, carrying out full mixing and preheating treatment on petroleum asphalt and an additive under a certain temperature, a certain N2 flow and a certain stirring speed, thus removing a small molecule compound which is difficult to polymerize; secondly, carrying out thermal polymerization reaction by keeping constant temperature for 2 to 6 hours under N2 protection and under the conditions that the pressure is 0.5 to 2.0 MPa and the temperatureis 380 to 420 DEG C, thus obtaining polymerized asphalt containing mesocarbon microbeads; finally, carrying out hot melting and filtration on the polymerized asphalt by using wash oil of which the boiling range is 245 to 290 DEG C, and carrying out vacuum drying after extracting filter cake by organic solvents of pyridine, methylbenzene and the like, thus obtaining the petroleum asphalt-based mesocarbon microbeads. According to the method disclosed by the invention, the petroleum asphalt and the additive which are used in the invention are rich in sources and lower in cost; by controlling themass percentage of the additive, the mesocarbon microbeads which are uniform in particle size distribution, controllable in size and relatively higher in yield can be prepared, and the mesocarbon microbeads can be used as lithium ion battery cathode materials after the mesocarbon microbeads are carbonized and graphitized.

Description

technical field

[0001] The invention belongs to the field of carbon materials, and in particular relates to a method for preparing mesophase carbon microspheres by using petroleum pitch as a raw material. Background technique

[0002] As a new type of carbon material, mesophase carbon microspheres (MCMB) were first separated from mesophase pitch by Japanese scholar Yamada et al. in 1973. Due to its unique sheet structure and good physical and chemical properties, it has become the first choice for the preparation of lithium One of the preferred raw materials for ion battery negative electrode materials, catalyst supports, high specific surface area activated carbon materials, high performance liquid chromatography column packing, etc.

[0003] At present, the methods for preparing mesophase carbon microspheres include thermal polycondensation method, suspension method, emulsification method, chemical vapor deposition method and so on. Among them, the mesophase carbon micros...

Examples

Embodiment 1

[0022] Mix petroleum pitch and carbon black N110 with a mass fraction of 2% and place it in a reactor, then raise the temperature to 300°C at a rate of 4°C / min, 2 Under the conditions of flow rate 60mL / min, mechanical stirring speed 150r / min, and constant temperature 2h preheating treatment, a sufficient mixture of petroleum pitch and carbon black N110 from which small molecules have been removed can be obtained. after N 2 Under protection, the temperature was raised to 400°C at a rate of 5°C / min, and under the conditions of a pressure of 1MPa and a mechanical stirring speed of 200r / min, the polymerization was carried out at a constant temperature for 4h to obtain polymerized petroleum pitch containing mesophase carbon microspheres. Use 2 times the mass of washing oil to stir, dissolve and filter the above-mentioned polymerized petroleum asphalt at 190°C, and extract the filtered filter cake with pyridine until the reflux liquid is colorless. Afterwards, the extracted filter ...

Embodiment 2

[0024] Mix petroleum pitch and rosin with a mass fraction of 2%, and then raise the temperature to 300°C at a rate of 4°C / min. 2 Under the conditions of flow rate 40mL / min, mechanical stirring speed 200r / min, constant temperature 2h preheating treatment, that is to obtain a sufficient mixture of petroleum pitch and rosin from which small molecules have been removed. after N 2 Under protection, the temperature was raised to 410°C at a rate of 5°C / min, under the conditions of a pressure of 1MPa and a mechanical stirring speed of 200r / min, the polymerization was carried out at a constant temperature for 5h to obtain polymerized petroleum pitch containing mesophase carbon microspheres. Use 3 times the mass of washing oil to mechanically dissolve and filter the above-mentioned polymerized petroleum asphalt at 180°C, and extract the filtered filter cake with toluene until the reflux liquid is colorless. Afterwards, the extracted filter cake was vacuum-dried at 60° C. and a vacuum d...

Embodiment 3

[0026] Mix petroleum pitch and rosin with a mass fraction of 5%, and then raise the temperature to 280°C at a heating rate of 5°C / min. 2 Under the conditions of flow rate 80mL / min, mechanical stirring speed 200r / min, constant temperature 2h preheating treatment, that is to obtain a sufficient mixture of petroleum pitch and rosin from which small molecules have been removed. after N 2 Under protection, the temperature was raised to 410°C at a rate of 6°C / min, and under the conditions of pressure 1MPa and mechanical stirring speed 200r / min, polymerization was carried out at a constant temperature for 4 hours to obtain polymerized petroleum pitch containing mesophase carbon microspheres. Then use 2 times the mass of washing oil to stir, dissolve and filter the above-mentioned polymerized petroleum asphalt at 170°C, and extract the filtered filter cake with tetrahydrofuran until the reflux liquid is colorless. Afterwards, the extracted filter cake was vacuum-dried at 90° C. and a...

technical field

[0001] The invention belongs to the field of carbon materials, and in particular relates to a method for preparing mesophase carbon microspheres by using petroleum pitch as a raw material. Background technique

[0002] As a new type of carbon material, mesophase carbon microspheres (MCMB) were first separated from mesophase pitch by Japanese scholar Yamada et al. in 1973. Due to its unique sheet structure and good physical and chemical properties, it has become the first choice for the preparation of lithium One of the preferred raw materials for ion battery negative electrode materials, catalyst supports, high specific surface area activated carbon materials, high performance liquid chromatography column packing, etc.

[0003] At present, the methods for preparing mesophase carbon microspheres include thermal polycondensation method, suspension method, emulsification method, chemical vapor deposition method and so on. Among them, the mesophase carbon micros...

Examples

Embodiment 1

[0022] Mix petroleum pitch and carbon black N110 with a mass fraction of 2% and place it in a reactor, then raise the temperature to 300°C at a rate of 4°C / min, 2 Under the conditions of flow rate 60mL / min, mechanical stirring speed 150r / min, and constant temperature 2h preheating treatment, a sufficient mixture of petroleum pitch and carbon black N110 from which small molecules have been removed can be obtained. after N 2 Under protection, the temperature was raised to 400°C at a rate of 5°C / min, and under the conditions of a pressure of 1MPa and a mechanical stirring speed of 200r / min, the polymerization was carried out at a constant temperature for 4h to obtain polymerized petroleum pitch containing mesophase carbon microspheres. Use 2 times the mass of washing oil to stir, dissolve and filter the above-mentioned polymerized petroleum asphalt at 190°C, and extract the filtered filter cake with pyridine until the reflux liquid is colorless. Afterwards, the extracted filter ...

Embodiment 2

[0024] Mix petroleum pitch and rosin with a mass fraction of 2%, and then raise the temperature to 300°C at a rate of 4°C / min. 2 Under the conditions of flow rate 40mL / min, mechanical stirring speed 200r / min, constant temperature 2h preheating treatment, that is to obtain a sufficient mixture of petroleum pitch and rosin from which small molecules have been removed. after N 2 Under protection, the temperature was raised to 410°C at a rate of 5°C / min, under the conditions of a pressure of 1MPa and a mechanical stirring speed of 200r / min, the polymerization was carried out at a constant temperature for 5h to obtain polymerized petroleum pitch containing mesophase carbon microspheres. Use 3 times the mass of washing oil to mechanically dissolve and filter the above-mentioned polymerized petroleum asphalt at 180°C, and extract the filtered filter cake with toluene until the reflux liquid is colorless. Afterwards, the extracted filter cake was vacuum-dried at 60° C. and a vacuum d...

Embodiment 3

[0026] Mix petroleum pitch and rosin with a mass fraction of 5%, and then raise the temperature to 280°C at a heating rate of 5°C / min. 2 Under the conditions of flow rate 80mL / min, mechanical stirring speed 200r / min, constant temperature 2h preheating treatment, that is to obtain a sufficient mixture of petroleum pitch and rosin from which small molecules have been removed. after N 2 Under protection, the temperature was raised to 410°C at a rate of 6°C / min, and under the conditions of pressure 1MPa and mechanical stirring speed 200r / min, polymerization was carried out at a constant temperature for 4 hours to obtain polymerized petroleum pitch containing mesophase carbon microspheres. Then use 2 times the mass of washing oil to stir, dissolve and filter the above-mentioned polymerized petroleum asphalt at 170°C, and extract the filtered filter cake with tetrahydrofuran until the reflux liquid is colorless. Afterwards, the extracted filter cake was vacuum-dried at 90° C. and a...