CN110683845A - Preparation method of carbon graphite product with superfine structure - Google Patents
Preparation method of carbon graphite product with superfine structure Download PDFInfo
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Abstract
The invention provides a preparation method of a carbon graphite product with an extremely fine structure, which comprises the following steps: carbonizing, pulverizing and processing the agriculture and forestry waste biomass to obtain a spheroidal ultramicro powder material with the particle size less than or equal to 3 mu m; and mixing the powder material with an adhesive, an additive and a graphitization promoter in a liquid phase, drying, molding, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the carbon graphite product with the ultrafine structure. The method takes the agricultural and forestry waste biomass as the raw material, avoids the use of energy materials, is energy-saving and environment-friendly, and is easy to prepare the spheroidal ultramicro powder after the material is carbonized; the method adopts superfine agricultural and forestry waste biomass as the raw material, ensures the integral consistency of the carbon graphite product with a fine structure, improves the isotropy, avoids the problems of internal cracking and the like, reduces the production cost and the process control cost of the carbon graphite product with the superfine structure, improves the density and the strength of the carbon graphite product with the superfine structure, and has good comprehensive performance.
Description
Technical Field
The invention relates to the technical field of carbon graphite, in particular to a preparation method of a carbon graphite product with an ultra-fine structure.
Background
The carbon graphite product is a high-temperature-resistant and oxidation-resistant conductive material which is manufactured by using cokes such as petroleum coke, pitch coke and the like as raw materials and coal pitch as an adhesive through processes such as crushing, batching, kneading, molding, sintering, dipping, graphitizing, machining and the like, and is widely applied to different fields such as metallurgy, chemical engineering, aerospace, electronics, machinery, building materials, nuclear energy and the like, for example, the carbon graphite product is used as a wear-resistant bearing and a sealing ring; an electrode for electric discharge machining, an electrode for electrolytic machining; a crystallizer for continuous casting; a heater, a crucible and a furnace lining for semiconductor production; sintering mould and aerospace craft gas vane and engine protective sheath etc..
At present, petroleum coke, pitch coke and the like are mostly adopted as raw materials for carbon graphite products produced in China, and due to the problems of shortage of energy, environmental pollution and the like, and shortage of energy materials such as the petroleum coke, the pitch coke and the like, the development of the industry is severely limited along with the increase of cost, the shortage of raw materials and the like caused by the stop of production, the limitation of production and the like for domestic environmental pollution treatment. Secondly, the coke products such as petroleum coke and the like have the problems of cracking, breakage and the like caused by the removal of volatile matters in the carbonization and graphitization processes due to the special structure, and the performance of the fine structure graphite is seriously influenced. Thirdly, the coke products such as petroleum coke and the like are easy to cause complex appearance in the crushing process and are difficult to be processed into spherical-like ultra-micro powder materials with the particle size less than or equal to 3 mu m, so that the anisotropy of the carbon graphite products with fine structures is caused, and the performance of the carbon graphite products with fine structures is further influenced. Fourth, the carbon graphite product mostly adopts a kneading method to mix the master batch, the adhesive and other additive components, and the particle size of primary particles is large, so that the isotropy of the graphite electrode is poor, and finally the difference of the graphite electrode performance is caused. The mixing kneading belongs to dry mixing, the adhesive has certain viscosity, the mixing kneading mode easily causes uneven distribution of material components, and the graphite electrode is easy to crack in the production process due to different shrinkage ratios and shrinkage speeds of various components which are not uniformly mixed under the condition of temperature change, so that the graphite electrode is finally scrapped, and the production cost of the graphite electrode is greatly improved.
The inventor considers that a series of problems of raw material shortage, cost rise, environmental pollution and the like caused by energy materials are solved by adopting plant products and the like as raw materials. And moreover, various performances of the carbon graphite product with the superfine structure are further improved.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon graphite product with an extremely fine structure, which is energy-saving and environment-friendly and has higher density and strength.
In view of the above, the present invention provides a method for preparing a carbon graphite product with an extremely fine structure, comprising the following steps: carbonizing, pulverizing and processing the agriculture and forestry waste biomass to obtain spheroidal ultramicro powder less than or equal to 3 mu m; and mixing the ultrafine powder with an adhesive, an additive and a graphitization promoter in a liquid phase, drying, molding, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the carbon graphite product with the ultrafine structure.
Preferably, the agricultural and forestry waste biomass is one or more of rice straw, wheat straw, bamboo straw and coconut shell.
Preferably, the temperature of the carbonization is 500-1100 ℃.
Preferably, the particle size of the milled powder is 3 μm or less.
Preferably, the graphitization promoter is one or more of silicon, silicon oxide, silicon carbide, boron, manganese oxide, rare earth elements, iron oxide and calcium carbonate.
Preferably, the additive is one or more of polyethylene glycol, polyvinyl alcohol, polypropylene alcohol, polyethylene oxide, polyacrylic acid and sodium carboxymethyl cellulose.
Preferably, the bulk density of the dried powder is 0.3-1.6g/cm3The granularity of the powder is 0.1-50um, and the moisture content of the powder is less than 1%.
Preferably, the molding control specific gravity is 1.2-1.75g/cm3。
Preferably, the roasting temperature of the primary roasting is lower than that of the primary roastingThe temperature is 300 ℃ and 1200 ℃, and the specific gravity range is 1.1-1.75 g/cm3The roasting time is 50-360 hours.
Preferably, the temperature of the graphitization treatment is 2300-3500 ℃, and the time of the graphitization treatment is 1-30 days.
The invention provides a preparation method of a carbon graphite product with an extremely fine structure, which comprises the following steps: carbonizing, pulverizing and processing the agriculture and forestry waste biomass to obtain spheroidal ultramicro powder less than or equal to 3 mu m; and mixing the ultrafine powder with an adhesive, an additive and a graphitization promoter in a liquid phase, drying, molding, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the carbon graphite product with the ultrafine structure. Compared with the prior art, the invention takes the agricultural and forestry waste biomass as the raw material, avoids the use of energy materials, and the carbonized material is easy to be prepared into spheroidal ultramicro powder, thereby laying a foundation for reducing the anisotropy of the fine-structure graphite; the method adopts superfine agricultural and forestry waste biomass as a raw material, adopts a liquid phase method to mix a main material, an adhesive, an additive and other materials, ensures the overall consistency of the carbon graphite product with a fine structure, further improves the isotropy, avoids the problems of internal cracking and the like, reduces the production cost and the process control cost of the carbon graphite product with the superfine structure, is energy-saving and environment-friendly, improves the density and the strength of the carbon graphite product with the superfine structure, and has good comprehensive performance.
Drawings
FIG. 1 is an SEM image of carbonized raw material and processed morphology in example 1 of the present invention;
fig. 2 is an external view of fine-structured graphite prepared in example 1 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The embodiment of the invention discloses a preparation method of a carbon graphite product with an extremely fine structure, which comprises the following steps: carbonizing, pulverizing and processing the agriculture and forestry waste biomass to obtain spheroidal ultramicro powder less than or equal to 3 mu m; and mixing the ultrafine powder with an adhesive, an additive and a graphitization promoter in a liquid phase, drying, molding, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the carbon graphite product with the ultrafine structure.
As a preferred scheme, the agricultural and forestry waste biomass is one or more of rice straw, wheat straw, bamboo straw and coconut shell. The temperature of the carbonization is preferably 500-1100 ℃, and more preferably 500-900 ℃. The invention preferably adjusts different carbonization temperatures according to different raw materials, and ensures the sufficient discharge of impurities and volatile matters.
Preferably, the carbonized material is pulverized, and the particle size of the pulverized material is preferably less than 3 μm. The shape of the pulverized material is processed, and the sphere-like shape of the material is ensured, so that the isotropy of the raw material is ensured.
In the step of liquid phase mixing, a solvent, a binder, a graphitization promoter and an additive are uniformly mixed, the main material after morphology treatment is finally added and mixed, solid contents and viscosities of different parts are tested at intervals, and when the difference between the solid contents and the viscosities of the different parts is less than +/-2%, the uniformity of mixing can be ensured. The adhesive is preferably low-temperature asphalt, tar, resin or high-temperature modified asphalt. The additive is one or more of polyethylene glycol, polyvinyl alcohol, polypropylene alcohol, polyethylene oxide, polyacrylic acid and sodium carboxymethyl cellulose, and the addition amount of the additive is 0.1-5 wt% of the superfine powder. The graphitization promoter is one or more of silicon, silicon oxide, silicon carbide, boron, manganese oxide, rare earth elements, iron oxide and calcium carbonate, and the addition amount of the graphitization promoter is 2-8 wt% of the ultrafine powder. The solvent adopted by the liquid phase mixing is water or alcohol. The main function of the additive is to ensure that the liquid phase can be uniformly dispersed during mixing, and the isotropy and the comprehensive performance of the final product can be improved only if various components are uniformly dispersed.
After the drying step, the invention forms mixed powder with evenly distributed components. The bulk density of the dried powder is preferably 0.3-1.6g/cm3The particle size of the powder is excellentIs selected to be 0.1-50um, and the water content of the powder is preferably less than 1%.
Preferably, the forming is performed by press forming using an isostatic press or a die press. The molding specific gravity is preferably 1.2 to 1.75g/cm3。
Preferably, the roasting temperature of the primary roasting is 300-1200 ℃, and the specific gravity range is 1.1-1.75 g/cm3The roasting time is 50-360 hours. The roasting temperature of the secondary roasting is below 850 ℃. The number of repetition of the firing and impregnation in the present invention is selected according to the selected raw material and the desired product, and preferably 3 to 8 times.
Preferably, the calcination and graphitization process according to the present invention must be carried out under a submerged condition or under a protective gas atmosphere, preferably argon, helium or neon. The temperature of the graphitization treatment is preferably 2300-3000 ℃, and more preferably 2300-2900 ℃; the time for the graphitization treatment is preferably 1 to 30 days, more preferably 15 to 30 days.
According to the scheme, the agricultural and forestry waste biomass such as rice straws, wheat straws, bamboo rods, coconut shells and the like is used as the raw material, a series of problems such as shortage of raw materials, cost rise, environmental pollution and the like caused by energy materials are solved, meanwhile, the carbonized material is easy to be made into powder, the particle size is less than 3 mu m, the spherical-like ultrafine powder material less than or equal to 3 mu m can be obtained through shape treatment, and a foundation is laid for reducing the anisotropy of the subsequent fine-structure graphite. The invention adopts superfine raw materials and adopts a liquid phase method to mix the main materials, the adhesive, the additive and other materials, thereby ensuring the integral consistency of the carbon graphite product with the fine structure, further improving the isotropy, avoiding the problems of internal cracking and the like caused by elastic deformation caused by temperature change, reducing the production cost and the process control cost of the carbon graphite product with the fine structure and improving various performances of the carbon graphite product with the fine structure.
The invention has the following advantages:
1. the raw materials are green and environment-friendly: the plant product is adopted as the raw material, the raw material source is green and environment-friendly, the source is wide, and the problems of raw material shortage, high cost and the like caused by energy materials are solved.
2. The isotropy is good: the carbonized material of the plant product is easy to crush and can be processed into a spheroidal ultra-micro powder material with the particle size less than or equal to 3 mu m after shape treatment, the spheroidal structure and the ultra-fine (less than 3 mu m) particle size ensure the isotropy of the final ultra-fine structure carbon graphite product and improve the performance of the product.
3. High performance: excellent performance of the carbon graphite product with the extremely fine structure is ensured by raw materials with excellent isotropy and a special processing technology.
For further understanding of the present invention, the following embodiments are provided to illustrate the technical solutions of the present invention in detail, and the scope of the present invention is not limited by the following embodiments.
The raw materials adopted in the embodiment of the invention are all commercially available.
Example 1
Weighing 1000kg of coconut shell, carbonizing by using a rotary furnace at 900 ℃, and preserving heat for 30 hours;
grinding the carbonized material by a grinder, wherein the grain size of the ground powder is less than or equal to 1 mu m;
grinding, and performing sphericization treatment to obtain main material with spherical shape as shown in FIG. 1;
weighing 400kg of alcohol, adding 2kg of PVA, stirring for 30min, then adding 40kg of asphalt with a softening point of 280 ℃ and 10kg of ferric oxide, stirring, uniformly dispersing, adding 200kg of the shape-treated main material, grinding while stirring, and stopping stirring when the difference between the solid content and the viscosity of different parts is less than +/-2%;
drying the liquid to ensure that the particle size range is controlled to be 0.1-50um and the bulk density range of the powder is controlled to be 0.3-1.6g/cm3The particle size distribution of the powder is ensured to be 0.1-50um, the moisture of the powder is controlled to be less than 1%, and the shape is spherical;
isostatic pressing is carried out by using an isostatic pressing machine, and the specific gravity range is controlled as follows: 1.2-1.75g/cm3；
Impregnating by using low-temperature asphalt (the softening point is less than 70);
roasting at 800 ℃, wherein the roasting time is as follows: 300 hours;
after the baking is finished, the impregnation and the baking are carried out again and repeatedly for three times, so as to ensure the density of the carbon graphite product semi-finished product with the superfine structure>1.9g/cm3；
Graphitizing the calcined superfine carbon graphite product semi-finished product at 2900 ℃, wherein the graphitizing time is 10 days;
and after the graphitization is finished, cooling along with the furnace temperature to obtain the carbon graphite product with the superfine structure. The calcination and graphitization of the invention are carried out under the condition of embedding and isolating air.
FIG. 1 is an SEM image of carbonized raw material and processed morphology in example 1 of the present invention. As seen from the SEM image, most particles belong to the nanometer level, the maximum particle size of the powder preparation is less than 1 μm, the small particle size of the primary particles is ensured, and the isotropy of the product is further improved.
FIG. 2 is an appearance diagram of a carbon graphite product with an extremely fine structure prepared by the embodiment of the present invention, that is, a carbon graphite product with a fine structure finally prepared by using bio-based carbon, which has a primary particle size of not more than 3 μm, has a finer and smoother surface than a conventional product.
Comparative example 1
Weighing 1000kg of petroleum coke, and grinding the petroleum coke into powder with the granularity D50=18-22 μm;
500kg of petroleum coke powder was weighed and kneaded with 125kg of asphalt having a softening point of 92 ℃ and 10kg of iron oxide.
Isostatic pressing is carried out by using an isostatic pressing machine, and the specific gravity range is controlled as follows: 1.2-1.75g/cm3；
Impregnating by using low-temperature asphalt (the softening point is less than 70);
roasting at 800 ℃, wherein the roasting time is as follows: 300 hours;
after the baking is finished, the impregnation and the baking are carried out again and repeatedly for three times, so as to ensure the density of the semi-finished product of the fine-structure carbon graphite product>1.9g/cm3；
Graphitizing the semi-finished product of the carbon graphite product with the fine structure after roasting at 2900 ℃, wherein the graphitizing time is 10 days;
and after the graphitization is finished, cooling along with the furnace temperature to obtain the conventional fine-structure carbon graphite product.
The performances of the carbon graphite product with an extremely fine structure prepared in this example and the carbon graphite product with a fine structure prepared in comparative example 1 were measured, respectively, and the results are shown in table 1.
TABLE 1 Performance results for fine structure carbon graphite articles prepared in inventive example 1 and comparative example 1
| Inspection parameters | Purity of | Primary particle size | Bulk density | Compressive strength | Flexural strength |
| Unit of | % | μm | g/cm3 | Mpa | Mpa |
| Example 1 carbon graphite product having very Fine Structure | 99 | ≤1μm | 1.98 | 42 | 25 |
| Conventional fine structure graphite article prepared in comparative example 1 | 99 | 20 | 1.95 | 41 | 25 |
Example 2
Weighing 1000kg of rice straw, carbonizing by using a rotary furnace at 900 ℃, and preserving heat for 30 hours;
grinding the carbonized material by a grinder, wherein the grain size of the ground powder is less than or equal to 1 mu m;
grinding the powder and then carrying out spheroidization treatment, wherein the shape is required to be similar to a sphere;
weighing 400kg of alcohol, adding 2kg of PVA, stirring for 30min, then adding 40kg of asphalt with a softening point of 280 ℃ and 10kg of ferric oxide, stirring, uniformly dispersing, adding 200kg of the shape-treated main material, grinding while stirring, and stopping stirring when the difference between the solid content and the viscosity of different parts is less than +/-2%;
drying the liquid to ensure that the particle size range is controlled to be 0.1-50 μm and the bulk density range of the powder is controlled to be 0.3-1.6g/cm3The particle size distribution of the powder is ensured to be 0.1-50um, the moisture of the powder is controlled to be less than 1%, and the shape is spherical;
isostatic pressing is carried out by using an isostatic pressing machine, and the specific gravity range is controlled as follows: 1.2-1.75g/cm3；
Impregnating by using low-temperature asphalt (the softening point is less than 70);
roasting at 900 ℃, wherein the roasting time is as follows: 400 hours;
after the baking is finished, the impregnation and the baking are carried out again and repeatedly for three times, so as to ensure the density of the carbon graphite product semi-finished product with the superfine structure>1.9 g/cm3；
Graphitizing the calcined superfine carbon graphite product semi-finished product at 2900 ℃, wherein the graphitizing time is 15 days;
and after the graphitization is finished, cooling along with the furnace temperature to obtain the carbon graphite product with the superfine structure. The calcination and graphitization of the invention are carried out under the condition of embedding and isolating air.
The performances of the carbon graphite product with an extremely fine structure prepared in this example and the conventional carbon graphite product with a fine structure prepared in comparative example 1 were measured, respectively, and the results are shown in table 2.
Table 2 performance results for fine structure carbon graphite articles prepared in inventive example 2 and comparative example 1
| Inspection parameters | Purity of | Primary particle size | Bulk density | Compressive strength | Flexural strength |
| Unit of | % | μm | g/cm3 | Mpa | Mpa |
| Example 2 carbon graphite product having very Fine Structure | 99 | ≤1 | 1.96 | 42 | 25 |
| Conventional fine structure graphite article prepared in comparative example 1 | 99 | 20 | 1.95 | 41 | 25 |
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a carbon graphite product with an extremely fine structure is characterized by comprising the following steps:
carbonizing, pulverizing and processing the agriculture and forestry waste biomass to obtain spheroidal ultramicro powder less than or equal to 3 mu m;
and mixing the ultrafine powder with an adhesive, an additive and a graphitization promoter in a liquid phase, drying, molding, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the carbon graphite product with the ultrafine structure.
2. The preparation method of claim 1, wherein the agricultural and forestry waste biomass is one or more of rice straw, wheat straw, bamboo and coconut shell.
3. The method as claimed in claim 1, wherein the carbonization temperature is 500-1100 ℃.
4. The method of claim 1, wherein the milled powder has a particle size of 3 μm or less.
5. The preparation method according to claim 1, wherein the graphitization promoter is one or more of silicon, silicon oxide, silicon carbide, boron, manganese oxide, rare earth elements, iron oxide, and calcium carbonate.
6. The preparation method according to claim 1, wherein the additive is one or more of polyethylene glycol, polyvinyl alcohol, polypropylene alcohol, polyethylene oxide, polyacrylic acid, and sodium carboxymethylcellulose.
7. The method according to claim 1, wherein the bulk density of the dried powder is 0.3 to 1.6g/cm3The granularity of the powder is 0.1-50um, and the moisture content of the powder is less than 1%.
8. The production method according to claim 1, wherein the molding control specific gravity is 1.2 to 1.75g/cm3。
9. The method as claimed in claim 1, wherein the primary calcination is carried out at a calcination temperature of 300-1200 ℃ and a specific gravity in the range of 1.1-1.75 g/cm3The roasting time is 50-360 hours.
10. The method according to any one of claims 1 to 8, wherein the graphitization temperature is 2300-3500 ℃ and the graphitization time is 1-30 days.
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