CN113353915A - Mesocarbon microbeads, preparation method thereof, spherical porous activated carbon material and application thereof - Google Patents
Mesocarbon microbeads, preparation method thereof, spherical porous activated carbon material and application thereof Download PDFInfo
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- CN113353915A CN113353915A CN202110811958.9A CN202110811958A CN113353915A CN 113353915 A CN113353915 A CN 113353915A CN 202110811958 A CN202110811958 A CN 202110811958A CN 113353915 A CN113353915 A CN 113353915A
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01G11/44—Raw materials therefor, e.g. resins or coal
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a mesocarbon microbead, a preparation method, a spherical porous activated carbon material and application thereof, wherein the method comprises the following steps: and pre-oxidizing the nano petroleum coke powder by using an oxidizing agent to obtain oxidized petroleum coke powder. Adding oxidized petroleum coke powder, ethylene tar and raw material asphalt into a high-pressure reaction kettle, wherein the oxidized petroleum coke is used as a nucleating agent, the ethylene tar is used as a viscosity regulator, carrying out thermal polycondensation under the atmosphere of inert gas to obtain intermediate phase asphalt, separating the prepared intermediate phase asphalt by adopting a Soxhlet extraction method to obtain intermediate phase carbon microspheres, carrying out thermal cracking treatment on the mixture of the prepared intermediate phase carbon microspheres and an alkali reagent at high temperature, and etching by using alkali to form a pore channel structure with multi-stage pore size distribution, thus obtaining the high-performance porous spherical carbon material. The preparation method can effectively control the particle size and the particle size distribution of the spherical carbon material, effectively improve the energy density of the energy storage material, easily control the preparation conditions and easily realize continuous production.
Description
Technical Field
The invention relates to the technical field of carbon material preparation, in particular to mesocarbon microbeads, a preparation method, a spherical porous activated carbon material and application thereof.
Background
Super capacitor has become an energy storage device which is concerned about and widely applied in recent years due to its advantages of short charging and discharging time, long cycle life, high power density, etc. Supercapacitors store electrical energy by forming an electric double layer at the electrode/electrolyte interface of a porous electrode material, the performance of which depends on the physical and chemical properties of the electrode material. The porous carbon material is the most common and promising super capacitor electrode material due to the advantages of higher specific surface area, excellent conductivity and cycling stability, relatively low price, environmental friendliness and the like. The petroleum asphalt contains a large amount of polycyclic aromatic hydrocarbon, and is a carbon source with high carbon content, low price and rich sources for preparing electrode materials. The petroleum asphalt can be treated to obtain mesophase asphalt, and mesophase carbon microspheres are separated from the mesophase asphalt and are good precursors for preparing porous carbon materials. The problem that the intermediate phase carbon microspheres prepared from petroleum asphalt have wider particle size distribution, poor sphericity, lower yield and the like exists, so that the development of a preparation method for obtaining the intermediate phase carbon microspheres with higher yield, narrow particle size distribution and better sphericity is particularly critical for further preparing high-performance porous spherical carbon materials. Therefore, scholars at home and abroad carry out a great deal of research and put forward a plurality of improvement methods.
The research shows that the particle size distribution of the mesocarbon microbeads is relatively uniform when the carbon black and the graphite are used as the nucleating agents, part of small particles exist in the mesocarbon microbeads by using the petroleum coke and the needle coke as the nucleating agents, and the mesocarbon microbeads prepared by the four nucleating agents have good electrochemical performance. Lin Qi-lang and the like of Fuzhou university use rosin as a nucleating agent to be added into coal tar pitch to prepare the mesophase carbon microsphere with controllable particle size and uniform particle size distribution, so that the yield of the mesophase carbon microsphere is remarkably improved, and the aromatic index of a pitch-rosin mixture is reduced. Lin Xiong-chao of the university of mining in China and the like take coal tar pitch as a raw material and biomass tar pitch as a nucleating agent to prepare the mesocarbon microbeads through a thermal polycondensation method. Manuel et al have now prepared ethylene tar into mesophase pitch by thermal polycondensation, and then activated with KOH to prepare high-performance activated carbon material, and the results show that the more mesophases in pitch after thermal polycondensation, the larger the pore volume and micropore volume of the prepared activated carbon. The Liguanke and the like treat ethylene tar by using coal tar pitch as a modifier and prepare wide-melting-domain parallel anisotropic mesophase pitch by a co-carbonization method, and the result shows that the mesophase pitch prepared from the modified ethylene tar has high order degree, good rheological property and high beta resin content, and is high-quality mesophase pitch. Chinese patent CN1116386C discloses a copolycondensation preparation method of mesophase carbon microspheres, which takes standard medium temperature coal tar pitch and secondary petroleum heavy oil with lower quinoline insoluble content as raw materials, and obtains a pitch product containing the mesophase carbon microspheres through a thermal polycondensation reaction. The carbon microsphere obtained by the method has uniform particle size, but the yield is not high. Chinese patent CN 109970038B discloses a method for producing mesocarbon microbeads by using medium-low temperature coal tar as a raw material, and the method obtains fractions with high aromatic content and a proper amount of quinoline insoluble substances by pretreatment means such as atmospheric and vacuum cutting, compounding and hydrotreating. The method has the advantages of high yield, uniform sphere diameter distribution and complex flow.
At present, mesophase carbon microspheres produced by a thermal polycondensation method often have the problems of sphere fusion, large particle size and the like while having high yield, and the development of a method which can ensure high yield and can also adjust the particle size and distribution of the carbon microspheres is very important for producing high-performance spherical porous carbon materials.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide mesophase carbon microspheres, a preparation method, a spherical porous activated carbon material and application thereof.
The invention is realized by the following steps:
the invention provides a preparation method of mesocarbon microbeads, which comprises the following steps: heating the mixture of oxidized petroleum coke powder, ethylene tar and asphalt to perform thermal polycondensation reaction to obtain an asphalt product containing mesophase carbon microspheres.
The invention also provides the mesocarbon microbeads prepared by the preparation method.
The invention also provides a preparation method of the spherical porous activated carbon material, which comprises the following steps: mixing the prepared mesocarbon microbeads with an alkali reagent, and then carrying out carbonization treatment.
The invention also provides the spherical porous activated carbon material prepared by the preparation method.
The invention also provides an application of the spherical porous activated carbon material in the aspect of supercapacitor materials.
The invention has the following beneficial effects:
the invention provides mesocarbon microbeads, a preparation method, a spherical porous activated carbon material and application thereof. Wherein, the oxidized petroleum coke powder is used as a nucleating agent, the yield of the mesophase carbon microsphere is greatly improved by stronger adsorption effect on polar short side chain aromatic hydrocarbon in the raw materials, and the ethylene tar is used as a viscosity regulator to improve the fluidity of a reaction system, so that the mesophase carbon microsphere produced by the reaction is more uniform. And carrying out thermal cracking treatment on the mixture of the prepared mesocarbon microbeads and the alkali reagent at high temperature, and etching by using alkali to form a pore channel structure with multi-stage pore diameter distribution to prepare the high-performance porous spherical carbon material. The preparation method can effectively control the particle size and the particle size distribution of the spherical carbon material, effectively improve the energy density of the energy storage material and enable the energy storage material to be applied to a super capacitor material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a graph showing the particle size distribution of example 1 of the present invention and comparative example 1;
FIG. 2 is a graph showing the charge and discharge curves at a current density of 1A/g for example 1 and comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention aims to overcome the defects of the prior art and provides mesocarbon microbeads, a preparation method, a spherical porous activated carbon material and application thereof.
The embodiment of the invention provides a method for producing activated carbon for a spherical supercapacitor by using asphalt. Asphalt is used as a raw material, oxidized petroleum coke powder is used as a nucleating agent, ethylene tar is used as a viscosity regulator, and a thermal polycondensation method is adopted to prepare the mesocarbon microbeads. By controlling the thermal polycondensation reaction conditions, such as reaction temperature, reaction time, and the addition amount of oxidized petroleum coke powder and ethylene tar, the properties of the mesophase carbon microsphere, such as particle size distribution, yield and the like, are controlled, and the mesophase carbon microsphere with small sphere diameter, smooth surface and narrow particle size distribution is further obtained by optimizing the reaction conditions and is used as a precursor for preparing the carbon material for the high-performance spherical supercapacitor. And carrying out thermal cracking treatment on the mixture of the prepared mesocarbon microbeads and the alkali reagent at high temperature, and etching by using alkali to form a pore channel structure with multi-stage pore diameter distribution to prepare the high-performance porous spherical carbon material. The preparation method can effectively control the particle size and the particle size distribution of the spherical carbon material, effectively improve the energy density of the energy storage material, and the preparation condition is easy to control and the continuous production is easy to realize.
In order to achieve the above object of the present invention, the following technical solutions are adopted:
in a first aspect, an embodiment of the present invention provides a method for preparing mesocarbon microbeads, including the following steps: heating the mixture of oxidized petroleum coke powder, ethylene tar and asphalt to perform thermal polycondensation reaction to obtain an asphalt product containing mesophase carbon microspheres.
The invention provides a method for producing activated carbon for spherical super capacitors by using asphalt, which is technically characterized by comprising the following steps of: and pre-oxidizing the nano petroleum coke powder by using an oxidizing agent to obtain oxidized petroleum coke powder. Adding oxidized petroleum coke powder, ethylene tar and raw material asphalt into a high-pressure reaction kettle, wherein the oxidized petroleum coke is used as a nucleating agent, the ethylene tar is used as a viscosity regulator, and carrying out thermal polycondensation under the atmosphere of inert gas to obtain an asphalt product containing mesophase carbon microspheres.
The petroleum coke powder with oxidized surface has higher surface activity and stronger polarity, and is easy to adsorb polar short side chain aromatic hydrocarbon in raw material asphalt, and in the heat treatment process, aromatic hydrocarbon small molecular free radicals adsorbed on the surface of the petroleum coke are combined with aromatic hydrocarbon small molecular free radicals in an asphalt phase and gradually condensed into macromolecules to form the core of the mesophase carbon microsphere. Along with the reaction, micromolecules in the raw materials are condensed into macromolecules to form an intermediate phase construction unit, and the intermediate phase construction unit is continuously accumulated on the core, so that the intermediate phase carbon microsphere is formed. The oxidized petroleum coke as the nucleating agent increases the opportunity of the raw material for polycondensation into balls, thereby increasing the yield of the mesophase carbon microspheres. The ethylene tar mainly contains dicyclic and tricyclic aromatic hydrocarbon molecules, the aromatic hydrocarbon molecules have more aliphatic side chains, and compared with asphalt, the ethylene tar has better melt flowability, can be used as a viscosity regulator to improve the flowability of a reaction system, further adjust the polycondensation reactivity, and the mesophase carbon microspheres generated by the reaction are more uniform; in addition, compared with asphalt, the ethylene tar has lower quinoline insoluble content, and the quinoline insoluble content in the raw materials can be adjusted, so that the particle size of the mesocarbon microbeads is adjusted; finally, the ethylene tar has more saturated component content compared with the asphalt, small molecules formed in the cracking process of the saturated components can be dissolved in the system, the viscosity of the reaction system is reduced, and formed hydrogen free radicals can effectively inhibit excessive condensation of macromolecules.
In an alternative embodiment, the oxidized petroleum coke powder is made by the steps of: mixing nano petroleum coke powder with an oxidant, heating for pre-oxidation reaction to obtain oxidized petroleum coke powder;
preferably, the oxidizing agent for pre-oxidizing the petroleum coke may be any one of perchloric acid, hydrogen peroxide, sulfuric acid and nitric acid, preferably hydrogen peroxide; the concentration of the hydrogen peroxide solution is 10-40%, preferably 20-30%; the mass ratio of the petroleum coke to the oxidant is 1 (1-10), preferably 1 (2-5); the grain size of the petroleum coke is 200-500 nm.
In an alternative embodiment, the reaction device of the thermal polycondensation reaction is an autoclave, and the conditions of the thermal polycondensation reaction are as follows: the reaction temperature is 350-450 ℃, and preferably 380-420 ℃; the reaction pressure is 0.5-5MPa, preferably 1.0 MPa; the reaction time is 0.5-10h, preferably 1-7 h. Incidentally, when the reaction temperature is lowered, the yield of the mesophase carbon microbeads tends to be lowered. In contrast, when the reaction temperature is increased, the yield of the mesophase carbon microbeads tends to increase. It is worth mentioning that a large amount of gas is generated in the thermal polycondensation reaction process, the generated micromolecule gas can be inhibited in the reaction system by keeping a certain pressure, the fluidity of the system is enhanced, the fusion of macromolecular components is facilitated, uniform mesophase spheres are formed, and the yield of the mesophase carbon microspheres is improved. But excessive pressure is more demanding on the equipment. In addition, when the reaction time is reduced, the small spheres in the pitch mother liquor are not fused, the yield of the mesophase carbon microspheres tends to be reduced, and the particle size tends to be reduced. On the contrary, when the reaction time is prolonged, the pellets in the pitch mother liquor are fused many times, the yield of the mesophase carbon microspheres tends to be improved, and the particle size tends to be increased.
In an alternative embodiment, the amount of ethylene tar added to the feedstock is in the range of 1 wt% to 50 wt%, preferably 5 wt% to 20 wt%, based on the total mass of the oxidized petroleum coke powder, ethylene tar and pitch; the addition amount of the oxidized petroleum coke powder is 1 wt% -30 wt%, preferably 3 wt% -15 wt%. Incidentally, when the amount of ethylene tar added is decreased and the amount of oxidized petroleum coke powder added is increased, the yield of mesophase carbon microbeads tends to increase, while the particle size distribution tends to be broadened, with the particle size being larger. On the contrary, when the amount of ethylene tar added is increased and the amount of oxidized petroleum coke powder added is decreased, the yield of mesophase carbon microspheres tends to decrease, and the particle size distribution tends to become narrower and smaller. Therefore, the yield and the particle size distribution of the mesophase carbon microspheres can be regulated and controlled by controlling the addition amount of the ethylene tar and the oxidized petroleum coke. If the amount of ethylene tar is too low, the reaction system becomes viscous, which is not favorable for producing uniform mesophase carbon microspheres. When the amount is too high, the yield of the mesophase carbon microbeads is too low. The yield of the mesophase carbon microbeads is lowered by adding too little amount of the oxidized petroleum coke, and the particle size of the mesophase carbon microbeads becomes too large by adding too much amount.
In an alternative embodiment, the solvent for separating the mesophase carbon microbeads may be any one of toluene, pyridine, tetrahydrofuran, or the like, and the alkali agent may be any one of potassium hydroxide, sodium hydroxide, or the like;
more preferably, the pitch product containing the mesophase carbon microspheres is continuously extracted by a Soxhlet extraction method until the pitch product is colorless, and the mesophase carbon microspheres are obtained after the solvent is removed and dried.
In a second aspect, the embodiment of the present invention further provides mesocarbon microbeads prepared by the above preparation method.
In a third aspect, an embodiment of the present invention further provides a method for preparing a spherical porous activated carbon material, including the following steps: and mixing the prepared mesocarbon microbeads with an alkali reagent, carbonizing to obtain a crude product, and washing and drying the crude product to obtain the mesocarbon microbeads.
In an optional embodiment, after the mesocarbon microbeads are mixed with the alkali reagent, the mixture is carbonized for 1 to 3 hours at the temperature of 650-900 ℃ in an inert atmosphere;
preferably, the alkaline agent comprises at least one of potassium hydroxide and sodium hydroxide;
preferably, the crude product obtained by carbonization is washed by acid for 6-12h at the temperature of normal temperature to 80 ℃, and then extracted, washed by water to be neutral and dried to obtain the spherical porous activated carbon material.
In a fourth aspect, the embodiment of the invention also provides a spherical porous activated carbon material prepared by the preparation method.
In a fifth aspect, the embodiment of the invention also provides an application of the spherical porous activated carbon material in a supercapacitor material.
In the embodiment of the invention, the obtained mesocarbon microbeads and a certain amount of alkali reagent are milled to be fully mixed, the mesocarbon microbeads are fully etched by the alkali reagent at high temperature to generate a large number of pore channels to form a complex structure with macroporous, mesoporous and microporous multi-level pore size distribution, and the insertion of the generated alkali metal steam in the carbon layer increases the lattice spacing of the carbon layer, improves the specific surface area and pore volume of the carbon material, thereby improving the electrochemical performance of the carbon material and enabling the carbon material to be applied to a super capacitor.
The features and properties of the present invention are described in further detail below with reference to examples.
In the following examples of the present invention, the raw material sources, components, preparation and experimental methods were the same as those of the comparative examples.
In the examples and comparative examples of the present invention, a certain petroleum pitch was used as a raw material, a certain ethylene tar was used as a viscosity modifier, and the compositional properties thereof are shown in Table 1.
TABLE 1 composition of bitumen and ethylene tar
| Four components | Asphalt | Ethylene tar |
| Saturation fraction% | 1.7 | 9.8 |
| Is divided into% | 24 | 64.7 |
| Asphaltene,% of | 52.1 | 16.4 |
| Pectin, is% | 22.2 | 9.1 |
Example 1
Mixing 10g of petroleum coke powder with 100mL of 20% hydrogen peroxide solution, stirring and reacting at 80 ℃ for 8h, and performing suction filtration and washing on a product until the product is neutral and dried to obtain oxidized petroleum coke.
Adding 80g of petroleum asphalt into a reaction kettle, then adding 10g of ethylene tar and 10g of oxidized petroleum coke, heating to 150 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, stirring for 1h at the stirring speed of 300r/min, and uniformly mixing the raw materials. And then heating to 400 ℃ at the speed of 5 ℃/min, keeping the pressure at 1.0MPa and the stirring speed at 300r/min, and reacting at constant temperature for 5 hours to obtain an asphalt product containing the mesocarbon microbeads. And continuously extracting the asphalt product in a Soxhlet extractor by using pyridine until the asphalt product is colorless, removing the solvent and drying to obtain the mesocarbon microbeads.
Mixing the mesocarbon microbeads and potassium hydroxide powder in a mass ratio of 1:3, carbonizing at 800 ℃ for 2h in a nitrogen atmosphere, pickling the product obtained after the reaction at 60 ℃ for 6h, extracting, washing with water to be neutral, and drying to obtain the spherical porous activated carbon material.
Example 2
Mixing 10g of petroleum coke powder with 100mL of 20% hydrogen peroxide solution, stirring and reacting at 80 ℃ for 8h, and performing suction filtration and washing on a product until the product is neutral and dried to obtain oxidized petroleum coke.
Adding 85g of petroleum asphalt into a reaction kettle, then adding 5g of ethylene tar and 10g of oxidized petroleum coke, heating to 150 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, stirring for 1h at the stirring speed of 300r/min, and uniformly mixing the raw materials. And then heating to 400 ℃ at the speed of 5 ℃/min, keeping the pressure at 1.0MPa and the stirring speed at 300r/min, and reacting at constant temperature for 5 hours to obtain an asphalt product containing the mesocarbon microbeads. And continuously extracting the asphalt product in a Soxhlet extractor by using pyridine until the asphalt product is colorless, removing the solvent and drying to obtain the mesocarbon microbeads.
Mixing the mesocarbon microbeads and potassium hydroxide powder in a mass ratio of 1:3, carbonizing at 800 ℃ for 2h in a nitrogen atmosphere, pickling the product obtained after the reaction at 60 ℃ for 6h, extracting, washing with water to be neutral, and drying to obtain the spherical porous activated carbon material.
Example 3
Mixing 10g of petroleum coke powder with 100mL of 20% hydrogen peroxide solution, stirring and reacting at 80 ℃ for 8h, and performing suction filtration and washing on a product until the product is neutral and dried to obtain oxidized petroleum coke.
Adding 70g of petroleum asphalt into a reaction kettle, then adding 20g of ethylene tar and 10g of oxidized petroleum coke, heating to 150 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, stirring for 1h at the stirring speed of 300r/min, and uniformly mixing the raw materials. And then heating to 400 ℃ at the speed of 5 ℃/min, keeping the pressure at 1.0MPa and the stirring speed at 300r/min, and reacting at constant temperature for 5 hours to obtain an asphalt product containing the mesocarbon microbeads. And continuously extracting the asphalt product in a Soxhlet extractor by using pyridine until the asphalt product is colorless, removing the solvent and drying to obtain the mesocarbon microbeads.
Mixing the mesocarbon microbeads and potassium hydroxide powder in a mass ratio of 1:3, carbonizing at 800 ℃ for 2h in a nitrogen atmosphere, pickling the product obtained after the reaction at 60 ℃ for 6h, extracting, washing with water to be neutral, and drying to obtain the spherical porous activated carbon material.
Example 4
Mixing 10g of petroleum coke powder with 100mL of 20% hydrogen peroxide solution, stirring and reacting at 80 ℃ for 8h, and performing suction filtration and washing on a product until the product is neutral and dried to obtain oxidized petroleum coke.
87g of petroleum asphalt is added into a reaction kettle, then 10g of ethylene tar and 3g of oxidized petroleum coke are added, the temperature is raised to 150 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, the raw materials are stirred for 1h at the stirring speed of 300r/min, and the raw materials are uniformly mixed. And then heating to 400 ℃ at the speed of 5 ℃/min, keeping the pressure at 1.0MPa and the stirring speed at 300r/min, and reacting at constant temperature for 5 hours to obtain an asphalt product containing the mesocarbon microbeads. And continuously extracting the asphalt product in a Soxhlet extractor by using pyridine until the asphalt product is colorless, removing the solvent and drying to obtain the mesocarbon microbeads.
Mixing the mesocarbon microbeads and potassium hydroxide powder in a mass ratio of 1:3, carbonizing at 800 ℃ for 2h in a nitrogen atmosphere, pickling the product obtained after the reaction at 60 ℃ for 6h, extracting, washing with water to be neutral, and drying to obtain the spherical porous activated carbon material.
Example 5
Mixing 10g of petroleum coke powder with 100mL of 20% hydrogen peroxide solution, stirring and reacting at 80 ℃ for 8h, and performing suction filtration and washing on a product until the product is neutral and dried to obtain oxidized petroleum coke.
Adding 75g of petroleum asphalt into a reaction kettle, then adding 10g of ethylene tar and 15g of oxidized petroleum coke, heating to 150 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, stirring for 1h at the stirring speed of 300r/min, and uniformly mixing the raw materials. And then heating to 400 ℃ at the speed of 5 ℃/min, keeping the pressure at 1.0MPa and the stirring speed at 300r/min, and reacting at constant temperature for 5 hours to obtain an asphalt product containing the mesocarbon microbeads. And continuously extracting the asphalt product in a Soxhlet extractor by using pyridine until the asphalt product is colorless, removing the solvent and drying to obtain the mesocarbon microbeads.
Mixing the mesocarbon microbeads and potassium hydroxide powder in a mass ratio of 1:3, carbonizing at 800 ℃ for 2h in a nitrogen atmosphere, pickling the product obtained after the reaction at 60 ℃ for 6h, extracting, washing with water to be neutral, and drying to obtain the spherical porous activated carbon material.
Example 6
Mixing 10g of petroleum coke powder with 100mL of 20% hydrogen peroxide solution, stirring and reacting at 80 ℃ for 8h, and performing suction filtration and washing on a product until the product is neutral and dried to obtain oxidized petroleum coke.
Adding 80g of petroleum asphalt into a reaction kettle, then adding 10g of ethylene tar and 10g of oxidized petroleum coke, heating to 150 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, stirring for 1h at the stirring speed of 300r/min, and uniformly mixing the raw materials. And then heating to 380 ℃ at the speed of 5 ℃/min, keeping the pressure at 1.0MPa and the stirring speed at 300r/min, and reacting at constant temperature for 1h to obtain an asphalt product containing the mesocarbon microbeads. And continuously extracting the asphalt product in a Soxhlet extractor by using pyridine until the asphalt product is colorless, removing the solvent and drying to obtain the mesocarbon microbeads.
Mixing the mesocarbon microbeads and potassium hydroxide powder in a mass ratio of 1:3, carbonizing at 800 ℃ for 2h in a nitrogen atmosphere, pickling the product obtained after the reaction at 60 ℃ for 6h, extracting, washing with water to be neutral, and drying to obtain the spherical porous activated carbon material.
Example 7
Mixing 10g of petroleum coke powder with 100mL of 20% hydrogen peroxide solution, stirring and reacting at 80 ℃ for 8h, and performing suction filtration and washing on a product until the product is neutral and dried to obtain oxidized petroleum coke.
Adding 80g of petroleum asphalt into a reaction kettle, then adding 10g of ethylene tar and 10g of oxidized petroleum coke, heating to 150 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, stirring for 1h at the stirring speed of 300r/min, and uniformly mixing the raw materials. And then heating to 420 ℃ at the speed of 5 ℃/min, keeping the pressure at 1.0MPa and the stirring speed at 300r/min, and reacting at constant temperature for 7h to obtain an asphalt product containing the mesocarbon microbeads. And continuously extracting the asphalt product in a Soxhlet extractor by using pyridine until the asphalt product is colorless, removing the solvent and drying to obtain the mesocarbon microbeads.
Mixing the mesocarbon microbeads and potassium hydroxide powder in a mass ratio of 1:3, carbonizing at 800 ℃ for 2h in a nitrogen atmosphere, pickling the product obtained after the reaction at 60 ℃ for 6h, extracting, washing with water to be neutral, and drying to obtain the spherical porous activated carbon material.
Comparative example 1
The thermal polycondensation reaction conditions and the activation conditions in example 1 were the same, and only asphalt was used as the thermal polycondensation raw material, and no petroleum coke or ethylene tar was added.
Comparative example 2
The thermal polycondensation reaction conditions and the activation conditions in example 1 were the same, the thermal polycondensation raw material was pitch, oxidized petroleum coke was added as a nucleating agent, ethylene tar was not added, and the mass ratio of pitch to oxidized petroleum coke was 9: 1.
Comparative example 3
The thermal polycondensation reaction conditions and the activation conditions in example 1 were the same, the thermal polycondensation raw material was asphalt, ethylene tar was added as a viscosity modifier, no petroleum coke was added, and the mass ratio of asphalt to ethylene tar was 9: 1.
Comparative example 4
The amount of the raw materials added, the thermal polycondensation reaction conditions, and the activation conditions in example 1 were the same, and the reaction system pressure was normal pressure.
The yield, the grain diameter and the electrochemical performance of the activated carbon material of the mesocarbon microbeads are shown in table 2, and the yield of the mesocarbon microbeads is based on the quality of the raw material asphalt. When the prepared spherical carbon material is subjected to electrochemical test, polytetrafluoroethylene is used as a binder, foamed nickel is used as a current collector, and the following steps are carried out according to the carbon material: preparing a test electrode according to the mass ratio of 9:1 of polytetrafluoroethylene, and performing constant current charge and discharge test in 6mol/L KOH solution by adopting a three-electrode system, wherein the current density is 1A/g.
Table 2 below shows the analysis of the properties of the reaction products of examples 1 to 6 and comparative examples 1 to 4.
TABLE 2 analysis of the properties of the reaction products
As can be seen from table 2 above, the mesophase carbon microbeads prepared by the schemes of examples 1 to 7 of the present invention show the characteristics of smaller spherical diameter, narrower particle size distribution and high specific capacity in terms of the yield, particle size and specific capacity of the mesophase carbon microbeads of 3 aspects, while the corresponding values of the yield, particle size and specific capacity of the mesophase carbon microbeads of comparative examples 1 to 3 do not show the significant characteristics as those of examples 1 to 7 of the present invention. In comparative example 1, the yield of the mesophase carbon microspheres is low, the particle size distribution is wide, and the electrochemical performance is poor under the condition that no ethylene tar or oxidized petroleum coke is added. In the comparative example 2, the oxidized petroleum coke is used as a nucleating agent, so that the opportunity of polycondensation and balling of raw materials is increased, and the yield of the mesophase carbon microspheres is obviously improved. In comparative example 3, the mobility of the reaction system is improved by a large amount of small molecules generated by the saturated fission in the ethylene tar, and the generated hydrogen free radicals effectively inhibit the excessive condensation of the large molecules, so that the average particle size of the mesocarbon microbeads is reduced, and the specific capacity of the prepared porous spherical carbon material is improved. In comparative example 4, the reaction system is at normal pressure, and more micromolecular gas escapes, so that the viscosity of the system is increased, the polymerization of macromolecular components is not facilitated, and the yield of the mesocarbon microbeads is reduced.
To sum up, the embodiment of the invention provides a mesophase carbon microsphere, a preparation method thereof, a spherical porous activated carbon material, a preparation method and an application thereof, wherein the method comprises the following steps: and pre-oxidizing the nano petroleum coke powder by using an oxidizing agent to obtain oxidized petroleum coke powder. Adding oxidized petroleum coke powder, ethylene tar and raw material asphalt into a high-pressure reaction kettle, wherein the oxidized petroleum coke is used as a nucleating agent, the ethylene tar is used as a viscosity regulator, carrying out thermal polycondensation under the atmosphere of inert gas to obtain intermediate phase asphalt, separating the prepared intermediate phase asphalt by adopting a Soxhlet extraction method to obtain intermediate phase carbon microspheres, carrying out thermal cracking treatment on the mixture of the prepared intermediate phase carbon microspheres and an alkali reagent at high temperature, and etching by using alkali to form a pore channel structure with multi-stage pore size distribution, thus obtaining the high-performance porous spherical carbon material. The porous spherical carbon material is mainly used as a supercapacitor material. The preparation method can effectively control the particle size and the particle size distribution of the spherical carbon material, effectively improve the energy density of the energy storage material, and the preparation condition is easy to control and the continuous production is easy to realize.
Compared with the existing preparation process of the energy storage carbon material, the preparation method has the following advantages:
(1) the method takes the oxidized petroleum coke as a nucleating agent, has stronger adsorption effect on polar short side chain aromatic hydrocarbons in the raw materials, and greatly improves the yield of the mesocarbon microbeads;
(2) the viscosity of the raw materials is adjusted by adding ethylene tar, the fluidity of a reaction system is improved, and the mesocarbon microbeads produced by the reaction are more uniform;
(3) the content of quinoline insoluble substances in the raw materials is also adjusted by adding the ethylene tar, and the particle size distribution of the mesocarbon microbeads generated by the reaction are further controlled by controlling the content of the quinoline insoluble substances;
(4) the asphalt, petroleum coke and ethylene tar which are needed by the production of the carbon microsphere are cheap and easily available raw materials, so that the production cost of producing the high-quality mesophase carbon microsphere is reduced, and the high-added-value conversion of cheap products is realized.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the mesocarbon microbeads is characterized by comprising the following steps: heating the mixture of oxidized petroleum coke powder, ethylene tar and asphalt to perform thermal polycondensation reaction to obtain an asphalt product containing mesophase carbon microspheres.
2. The method for preparing mesocarbon microbeads according to claim 1, wherein said reaction device for thermal polycondensation is an autoclave, and the conditions of said thermal polycondensation are as follows: the reaction temperature is 350-450 ℃, and preferably 380-420 ℃; the reaction pressure is 0.5-5MPa, preferably 1.0 MPa; the reaction time is 0.5-10h, preferably 1-7 h.
3. The preparation method of mesocarbon microbeads according to claim 1, wherein the ethylene tar is added in a ratio of 1-50 wt%, preferably 5-20 wt%, based on the total mass of the oxidized petroleum coke powder, the ethylene tar and the asphalt; the addition ratio of the oxidized petroleum coke powder is 1 wt% -30 wt%, and preferably 3 wt% -15 wt%.
4. The method for preparing mesocarbon microbeads according to claim 1, wherein said oxidized petroleum coke powder is prepared by the following steps: mixing nano petroleum coke powder with an oxidant, heating for pre-oxidation reaction to obtain oxidized petroleum coke powder;
preferably, the mass ratio of the petroleum coke powder to the oxidizing agent is 1:1-10, more preferably 1: 2-5; the oxidizing agent comprises at least one of perchloric acid, hydrogen peroxide, sulfuric acid and nitric acid, more preferably hydrogen peroxide; the concentration of the hydrogen peroxide solution is 10-40%, and more preferably 20-30%;
more preferably, the particle size of the nano petroleum coke powder is 200-500 nm.
5. The method for preparing mesocarbon microbeads according to any one of claims 1 to 4, further comprising: separating the prepared pitch product containing the mesocarbon microbeads by a Soxhlet extraction method to obtain the mesocarbon microbeads;
preferably, the solvent for separating the mesocarbon microbeads includes at least one of toluene, pyridine and tetrahydrofuran;
more preferably, the pitch product containing the mesophase carbon microspheres is continuously extracted by a Soxhlet extraction method until the pitch product is colorless, and the mesophase carbon microspheres are obtained after the solvent is removed and dried.
6. Mesophase carbon microbeads, which are prepared by the preparation method of any one of claims 1 to 5.
7. A method for preparing a spherical porous activated carbon material is characterized by comprising the following steps: mixing mesocarbon microbeads with an alkali reagent and then carrying out carbonization treatment, wherein the mesocarbon microbeads are the mesocarbon microbeads prepared by the preparation method of any one of claims 1-5.
8. The method for preparing a spherical porous activated carbon material as claimed in claim 7, wherein after the mesophase carbon microspheres are mixed with an alkali reagent, carbonization treatment is carried out for 1-3h at 650-900 ℃ in an inert atmosphere;
preferably, the alkaline reagent comprises at least one of potassium hydroxide and sodium hydroxide;
preferably, the crude product obtained by carbonization is washed by acid for 6-12h at the temperature of normal temperature to 80 ℃, and then extracted, washed by water to be neutral and dried to obtain the spherical porous activated carbon material.
9. A spherical porous activated carbon material produced by the production method according to claim 8.
10. Use of the spherical porous activated carbon material prepared by the preparation method according to any one of claims 7 to 8 or the spherical porous activated carbon material of 9 in a supercapacitor material.
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