CN110668820A - Preparation method of high-performance carbon graphite product with superfine structure - Google Patents
Preparation method of high-performance carbon graphite product with superfine structure Download PDFInfo
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Abstract
The invention provides a preparation method of a high-performance carbon graphite product with an extremely fine structure, which comprises the following steps: compounding the graphite micro powder and the first adhesive in a granulation mode, and carbonizing to obtain a composite particle material; and (3) mixing the composite particle material with a second adhesive, an additive and a graphitization promoter in a liquid phase, drying, forming, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the high-performance carbon graphite product with the ultrafine structure. Compared with the prior art, the invention takes the graphite micro powder as the raw material, thereby saving energy and protecting environment; after granulation, an isotropic composite granular material is obtained, so that the anisotropy of a subsequent carbon graphite product with an ultrafine structure is greatly reduced; thirdly, the problems of internal cracking and the like caused by elastic deformation caused by temperature change are avoided, the density and the strength of the carbon graphite product with the ultrafine structure are improved, and the comprehensive performance is good.
Description
Technical Field
The invention relates to the technical field of carbon graphite, in particular to a preparation method of a high-performance carbon graphite product with an extremely 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 sphere-like powder materials, so that the anisotropy of the fine-structure carbon graphite product is caused, and the performance of the fine-structure carbon graphite product is further influenced. Fourthly, the master batch, the adhesive and other additive components are mostly mixed in a kneading mode in the existing carbon graphite product, and the isotropy of the fine-structure carbon graphite product is poor due to the large particle size of primary particles, so that the performance difference of the fine-structure carbon graphite product is finally 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 shrinkage ratio and the shrinkage speed of various components which are not uniformly mixed under the condition of temperature change cause the carbon graphite product with the superfine structure to be easy to crack in the production process, finally cause the rejection of the carbon graphite product with the superfine structure, and greatly improve the production cost of the carbon graphite product with the superfine structure.
The inventor considers that the graphite micropowder is used as the raw material, so that the problems of shortage of raw materials, cost rise, environmental pollution and the like caused by energy materials are solved, the anisotropy of the subsequent carbon graphite product with the superfine structure is greatly reduced, and the strength of the carbon graphite product with the superfine structure is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a high-performance carbon graphite product with an extremely fine structure, which has high density and strength and good comprehensive performance.
In view of the above, the invention provides a preparation method of a high-performance carbon graphite product with an extremely fine structure, which comprises the following steps: compounding the graphite micro powder and the first adhesive in a granulation mode, and carbonizing to obtain a composite particle material; and (3) mixing the composite particle material with a second adhesive, an additive and a graphitization promoter in a liquid phase, drying, forming, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the high-performance carbon graphite product with the ultrafine structure.
Preferably, the steps of obtaining the composite particulate material are: adding a first adhesive into a solvent, uniformly stirring, adding graphite micropowder, granulating, drying, carbonizing and sizing to obtain the composite granular material.
Preferably, the temperature of the carbonization is 500-1100 ℃.
Preferably, the particle size of the composite particulate material is from 5 to 70 μm.
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 first binder and the second binder are respectively and independently one or more of asphalt, tar and resin.
Preferably, the molding control specific gravity is 1.5-1.9 g/cm3。
Preferably, the roasting temperature of the primary roasting is300 ℃ and 1200 ℃, and the specific gravity range is 1.4-1.9 g/cm3The roasting time is 50-360 hours.
Preferably, the roasting temperature of the secondary roasting is below 850 ℃.
Preferably, the temperature of the graphitization treatment is 2300-3000 ℃, and the time of the graphitization treatment is 1-30 days.
The invention provides a preparation method of a high-performance carbon graphite product with an extremely fine structure, which comprises the following steps: compounding the graphite micro powder and the first adhesive in a granulation mode, and carbonizing to obtain a composite particle material; and (3) mixing the composite particle material with a second adhesive, an additive and a graphitization promoter in a liquid phase, drying, forming, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the high-performance carbon graphite product with the ultrafine structure. Compared with the prior art, the invention takes the graphite micro powder as the raw material, thereby saving energy and protecting environment; the composite particle material obtained after granulation greatly reduces the anisotropy of the subsequent fine-structure graphite; thirdly, the problems of internal cracking and the like caused by elastic deformation caused by temperature change are avoided, the density and the strength of the carbon graphite product with the ultrafine structure are improved, and the comprehensive performance is good.
Drawings
FIG. 1 is an SEM photograph of the starting material used in example 1 of the present invention;
FIG. 2 is an SEM image of graphite after secondary granulation 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 high-performance carbon graphite product with an extremely fine structure, which comprises the following steps: compounding the graphite micro powder and the first adhesive in a granulation mode, and carbonizing to obtain a composite particle material; and (3) mixing the composite particle material with a second adhesive, an additive and a graphitization promoter in a liquid phase, drying, forming, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the high-performance carbon graphite product with the ultrafine structure.
As a preferred scheme, the granularity of the graphite micro powder adopted by the invention is less than or equal to 3 microns. The raw material solves a series of problems of raw material shortage, cost rise, environmental pollution and the like brought by energy materials, and simultaneously the material forms isotropic aggregate after composite carbonization, thereby laying a foundation for reducing the anisotropy of subsequent carbon graphite products with superfine structures.
Preferably, the step of obtaining the composite particle material comprises: adding a first adhesive into a solvent, uniformly stirring, adding graphite micropowder, granulating, drying, carbonizing, and shaping to obtain the composite granular material, wherein the solvent comprises but is not limited to water or alcohol and other liquid which does not pollute the environment. The temperature of the carbonization is 500-1100 ℃. The particle size of the composite particle material is 5-70 μm. Wherein, in the step of preparing the composite particulate material, the drying is preferably spray drying or freeze drying.
Because graphite has polarity, the finer the particles, the stronger the polarity, the graphite with extremely fine structure is difficult to be prepared, and the graphite has anisotropy, if the graphite single particles are directly used as raw materials, the isotropy of the prepared graphite with fine structure is poor. The invention adopts secondary granulation to prepare the small single-particle graphite micro powder into isotropic graphite secondary particles, thereby not only reducing the polarity of graphite and improving the anisotropy of graphite, but also finally improving the comprehensive performance of carbon graphite products with superfine structures.
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 first binder and the second binder are respectively and independently one or more of asphalt, tar and resin. The additive is a material for preventing sedimentation, and is preferably CMC, PEO or PVA. The graphitization promoter is one or more of silicon, silicon oxide, silicon carbide, boron, manganese oxide, rare earth elements, iron oxide and calcium carbonate. The solvent adopted by the liquid phase mixing is water or alcohol or other liquid which does not pollute the environment.
Preferably, the mass ratio of the graphite micro powder to the first binder is preferably 3-10:1, more preferably 5: 1; the mass ratio of the composite particle material to the second binder is preferably 3-10:1, more preferably 5: 1; the mass ratio of the composite particulate material to the additive is preferably 50-200:1, more preferably 100: 1; the mass ratio of the composite particulate material to the graphitization promoter is preferably 10-50:1, more preferably 20: 1.
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 overall consistency of the carbon product with the superfine 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 superfine structure, and improving various performances of the carbon graphite product with the superfine structure.
In the step of preparing the high-performance carbon graphite product with the superfine structure, the moisture of the powder is controlled to be as follows after drying: 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 1.5 to 1.9 g/cm3。
Preferably, the roasting temperature of the primary roasting is 300-1200 ℃, and the specific gravity range is 1.4-1.9 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 firing and graphitization process of the present invention must be carried out under an immersion condition or a protective gas atmosphere. Wherein, the first protective gas atmosphere for roasting is preferably nitrogen, argon, helium or neon; the second protective gas atmosphere for the graphitization treatment is 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 graphite micropowder with the particle size of less than or equal to 3 microns is used as the raw material, a series of problems of raw material shortage, cost increase, environmental pollution and the like caused by energy materials are solved, and the anisotropy of the subsequent carbon graphite product with the ultrafine structure is greatly reduced after the material is subjected to composite carbonization in isotropic granulation modes such as spray drying and the like.
In addition, the invention adopts the superfine graphite micropowder and adopts a liquid phase method to mix the main material, the adhesive, the additive and other materials, thereby ensuring the overall consistency of the carbon graphite product with the superfine structure, further improving the isotropy through composite granulation, and avoiding the problems of internal cracking and the like caused by elastic deformation caused by temperature change. The invention reduces the production cost and the process control cost of the carbon graphite product with the superfine structure, improves various performances of the carbon graphite product with the superfine structure, enables the carbon graphite product with the superfine structure to be applied to high-end fields such as aerospace, nuclear graphite and the like, and fills the domestic blank in the market.
The invention has the following advantages:
1. the raw material source is wide: the graphite micropowder with the particle size of less than or equal to 3 mu m is used as a raw material, the raw material 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: after the graphite micropowder is mixed with the adhesive and the additive, the isotropy of the final carbon graphite product with the superfine structure is ensured and the performance of the product is improved through isotropic granulation modes such as spray drying, freeze drying and the like.
3. High performance: the excellent performance of the carbon graphite product with the superfine structure is ensured by the graphite secondary particles with excellent isotropy and the 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
1. And (3) granulation:
adding 40kg of asphalt with the softening point of 90 ℃ into 400kg of alcohol, uniformly stirring, and adding 200kg of graphite micro powder with the particle size of less than 3 microns;
granulating and drying in a spray drying mode;
drying, carbonizing at 500 deg.C, and shaping to obtain granules with particle size of about 30 μm and maximum particle size of less than 70 μm.
Fig. 1 is an SEM image of the raw graphite fine powder used in this example. As can be seen from the figure, the single particle size of the graphite micropowder is less than or equal to 3 μm, and most of the graphite particles are flaky, so that the graphite micropowder is difficult to be made into fine-structure graphite by direct use and has poor isotropy.
FIG. 2 is an SEM photograph of graphite after secondary granulation in this example, in which the particle size of the granulated secondary particles is about 30 μm and the maximum particle size is less than 70 μm.
2. Preparing a carbon graphite product with an extremely fine structure:
weighing 400kg of alcohol, adding 2kg of PEO, stirring for 30min, adding 40kg of asphalt with a softening point of 280 ℃ and 10kg of ferric oxide, and stirring;
after being dispersed uniformly, 200kg of granulated main material is added and mixed uniformly;
drying the liquid;
carrying out isostatic pressing by using an isostatic pressing machine;
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 carbon product with the superfine structure>1.95g/cm3；
Graphitizing the calcined superfine carbon product semi-finished product at 2900 ℃, wherein the graphitizing time is 10 days;
after the graphitization is finished, the graphite is cooled along with the furnace temperature to obtain the carbon graphite product with the superfine structure and high performance and density.
Comparative example 1
Weighing 1000kg of petroleum coke, and grinding the petroleum coke into powder with the granularity D50=8-15 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/cm 3;
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 example 1 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 1.
Table 1 performance results for carbon graphite articles prepared in example 1 and comparative example 1
| Inspection parameters | Purity of | Primary particlesDegree of rotation | Bulk density | Compressive strength | Flexural strength |
| Unit of | % | μm | g/cm3 | Mpa | Mpa |
| Example 1 | 99 | ≤3 | 2.02 | 42 | 25 |
| Comparative example 1 | 99 | ≤10 | 1.98 | 41 | 25 |
Example 2
1. And (3) granulation:
adding 40kg of asphalt with the softening point of 90 ℃ into 40kg of 400kg of alcohol, uniformly stirring, and adding 200kg of graphite micro powder with the particle size of less than 2 mu m;
drying by freeze drying, granulating by kneading, carbonizing at 800 deg.C, and shaping to obtain granules with particle size of about 30 μm and maximum particle size of less than 70 μm.
2. Preparing a carbon graphite product with an extremely fine structure:
weighing 400kg of alcohol, adding 2kg of PVA, stirring for 30min, adding 40kg of asphalt with the softening point of 280 ℃ and 10kg of ferric oxide, and stirring;
after being dispersed uniformly, 200kg of granulated main material is added and mixed uniformly;
drying the liquid;
carrying out isostatic pressing by using an isostatic pressing machine;
impregnating by using low-temperature asphalt (the softening point is less than 70);
roasting at 900 ℃, wherein the roasting time is as follows: 360 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 semi-finished product with the superfine structure>1.95 g/cm3；
Graphitizing the roasted carbon graphite semi-finished product with the superfine structure at 2900 ℃, wherein the graphitizing time is 10 days;
after the graphitization is finished, the graphite is cooled along with the furnace temperature to obtain the carbon graphite product with the superfine structure and high performance and density.
The performances of the carbon graphite product with an extremely fine structure prepared in example 2 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 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 | 99 | ≤2 | 2.01 | 41 | 25 |
| Comparative example 1 | 99 | 10 | 1.98 | 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 high-performance carbon graphite product with an extremely fine structure is characterized by comprising the following steps:
compounding the graphite micro powder and the first adhesive in a granulation mode, and carbonizing to obtain a composite particle material;
and (3) mixing the composite particle material with a second adhesive, an additive and a graphitization promoter in a liquid phase, drying, forming, repeatedly dipping and roasting for 3-8 times, and performing graphitization treatment to obtain the high-performance carbon graphite product with the ultrafine structure.
2. The method of claim 1, wherein the step of obtaining the composite particulate material is:
adding a first adhesive into a solvent, uniformly stirring, adding graphite micropowder, granulating, drying, carbonizing and sizing to obtain the composite granular material.
3. The method as claimed in claim 1, wherein the carbonization temperature is 500-1100 ℃.
4. The method of claim 1, wherein the particle size of the composite particulate material is 5 to 70 μm.
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 method according to claim 1, wherein the first binder and the second binder are each independently one or more of asphalt, tar and resin.
7. The production method according to claim 1, wherein the molding control specific gravity is 1.5 to 1.9 g/cm3。
8. 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 1.4-1.9 g/cm3The roasting time is 50-360 hours.
9. The method according to any one of claims 1 to 8, wherein the roasting temperature of the secondary roasting is 850 ℃ or lower.
10. The method according to any one of claims 1 to 8, wherein the graphitization temperature is 2300-3000 ℃ and the graphitization time is 1-30 days.
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