CN111170757A - Preparation method of special fine-particle graphite material - Google Patents
Preparation method of special fine-particle graphite material Download PDFInfo
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Abstract
The invention relates to the technical field of graphite materials, in particular to a preparation method of a special fine-particle graphite material, which takes aggregate as needle petroleum coke; the powder material is graphene, pitch coke, carbon black and carbon fiber; the binder is modified medium-temperature coal pitch; the impregnant is impregnating asphalt, and fine particle graphite materials are prepared by kneading, profiling, roasting, impregnating, secondary roasting and graphitizing; the raw materials are reasonably selected, and the preparation process is scientific; the structure is uniform and fine, and the volume density is high; the physical and chemical indexes of the graphite are excellent. The volume density of the special fine-particle graphite prepared by the invention is more than or equal to 2.0g/cm3The resistivity is less than or equal to 6.0 mu omega m, the breaking strength is more than or equal to 32Mpa, the compressive strength is more than or equal to 65Mpa, the porosity is less than or equal to 10 percent, the ash content is less than or equal to 0.2 percent, and the thermal expansion coefficient is less than or equal to 2 x 10‑6/℃。
Description
Technical Field
The invention relates to the technical field of graphite materials, in particular to a preparation method of a special fine-particle graphite material.
Background
The coverage range of the special graphite is wide, and the Chinese electrical carbon product industry, the natural graphite product industry and the metallurgical carbon product industry have different understanding and classification methods for the special graphite, which are explained in terms of the custom classification of the metallurgical carbon product industry, and the special graphite mainly refers to a high-strength, high-density and high-purity graphite product (three-high graphite for short).
The three-high graphite can be divided into three types of coarse grain structure, fine grain structure and ultra-fine grain structure from the material organization structure, and the three types of special graphite mainly comprise compression molding special graphite, extrusion molding special graphite and isostatic pressing special graphite from the molding method, and in addition, the vibration molding can also be used for producing the special graphite. The high-quality special graphite-isotropic graphite is produced by isostatic pressing process.
Not all special graphite must reach the same indexes of high density, high strength and high purity, and special graphite used in different occasions has specific strength and density requirements, i.e. the strength and density indexes are different. Many specialty graphites do not need to reach high purity and ash is not a major quality indicator. Some special graphite does not need high strength and high density but needs high purity. Some special graphite such as graphite for electric spark machining needs fine-grained graphite or extra-fine-grained graphite with different physical and chemical indexes according to different machining processes and machining objects.
The application of foreign graphite products is started early, the foreign graphite products are in the leading position in the aspects of development and production of special graphite products, a complete product system is formed, the quality and the performance of the products are good, and the foreign graphite products have great advantages in international market competition. At present, the products are mainly produced by developed countries such as America, Germany, France, Japan and the like, and the demand of domestic markets for the products depends on import.
In terms of production mode, foreign enterprises mainly adopt a vibration forming mode to produce medium-thickness and thick-structure graphite products, and only a few enterprises such as SGL (Sagery) and the like can produce the graphite products with larger specifications in an extrusion forming mode.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the preparation method of the special fine-particle graphite material with reasonable raw material selection and scientific preparation process, and the method and the material are used for producing the novel fine-particle, high-density and high-purity graphite material with high physicochemical properties.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a special fine particle graphite material comprises the following steps:
s1, crushing, screening and batching, wherein the aggregate and the powder are screened according to the particle size and are batched;
s2, kneading: adding the graded ingredients into a kneading pot for stirring, wherein the kneading is divided into dry mixing and wet mixing, the dry mixing is to add aggregate and powder into the kneading pot for stirring, the kneading pot is of a double-reamer type, the temperature of the kneading pot is 220-250 ℃, the dry mixing temperature of the aggregate and the powder is 150-180 ℃, and the dry mixing time is 45-50 minutes; the temperature of the wet mixing adhesive is 140-180 ℃, and the wet mixing time is 40-45 minutes;
s3, extrusion molding and cooling: after kneading, extruding and molding the kneaded product through an electrode extruder, and then placing the molded product in water to cool the molded product to normal temperature; the bulk density of the formed green body reaches 1.80-2.0g/cm3；
S4, primary roasting: placing the molded green body into a ring-type roasting furnace, filling the furnace with coke powder, quartz sand, river sand and the like, heating gradually according to a heating curve under the condition of isolating air, wherein the heating rate is 3.0-4.0 ℃/h at 150-350 ℃, and the holding time is 55 h; at the temperature of 350-450 ℃, the heating rate is 1.5-1.8 ℃/h, and the holding time is 35 h; at the temperature of 450-550 ℃, the heating rate is 1.2-1.4 ℃/h, and the holding time is 85 h; at 550-650 ℃, the heating rate is 1.8-2.0 ℃/h, and the holding time is 55 h; at 650-750 ℃, the heating rate is 3.5-4.0 ℃/h, and the holding time is 24 h; at 750-850 ℃, the heating rate is 4.0-5.0 ℃/h, and the holding time is 24 h; at 850-1150 ℃, the heating rate is 6.5-8.5 ℃/h, and the holding time is 30 h; at 1150-1250 ℃, the heating rate is 8.0-8.5 ℃/h, and the holding time is 24 h; keeping the temperature at 1250 ℃ for 22h, then naturally cooling to room temperature and discharging;
s5, dipping: placing the roasted product into an impregnation tank, and impregnating impregnant impregnated asphalt into pores of the roasted product under certain process conditions; firstly, preheating a roasted product to 350-450 ℃, keeping the temperature for 8h, putting the roasted product into an impregnation tank, vacuumizing and pressurizing for 2.5h, then injecting an impregnant into the impregnation tank, and keeping the pressure for 2 h; the weight gain rate of impregnation is 15-17%;
s6, secondary roasting in a tunnel kiln: carrying out a rapid pitch sintering process on the impregnated product in a tunnel kiln, wherein the maximum temperature is 700 ℃ and the time is 144 h;
s7, graphitizing: putting the product after secondary roasting into an Acheson graphitizing furnace, heating the roasted product to 2800-3200 ℃ by current under the condition of air isolation, specifically heating the roasted product to 1350 ℃ from room temperature at a heating rate of 250 ℃/h, then heating the roasted product to 2200 ℃ from 1350 ℃ at a heating rate of 25 ℃/h, and freely heating the roasted product to 3200 ℃ after the temperature reaches 2200 ℃, so that the two-dimensional structure carbon product is converted into a three-dimensional graphite grid structure, and the total power transmission time is 168 h;
s8, machining: and machining the graphitized product to obtain a finished product.
Further, in the raw materials of the special fine particle graphite material, the aggregate is needle-shaped petroleum coke; the powder material is graphene, pitch coke, carbon black and carbon fiber; the binder is modified medium-temperature coal pitch; the impregnant is impregnation asphalt.
Further, the true density of the acicular petroleum coke aggregate is more than or equal to 2.13g/cm3Ash content is less than or equal to 0.20 percent, volatile matter is less than or equal to 0.25 percent, and sulfur content is less than or equal to 0.30 percent; the tensile modulus of the powder graphene is less than or equal to 1.01TPa, and the ultimate strength is less than or equal to 116 Gpa; the particle size of the powder asphalt coke is 0.05-0.10 mu m, and the true density is more than or equal to 2.13/cm3Ash content is less than or equal to 0.25 percent, sulfur content is less than or equal to 0.3 percent, and volatile matter is less than or equal to 0.5 percent; the purity of the powder carbon black is 99 percent, and the particle size is 0.04-0.08 mu m; the granularity of the powder carbon fiber is 0.03-0.07 mu m, the tensile strength is 7.0Gpa, and the density is 2.10g/cm3The resistivity is less than or equal to 35 mu omega cm; the softening point of the binder modified medium-temperature coal pitch is 83-86 ℃, the coking value is more than or equal to 48 percent, and the ash content is less than or equal to 0.30 percent; the softening point of the impregnant dipping asphalt is 83-88 ℃, the coking value is more than or equal to 48 percent, and the quinoline insoluble is less than or equal to 0.30 percent.
Further, the weight ratio of the powder graphene, the pitch coke, the carbon black and the carbon fiber is 20:30:15: 35.
Further, the weight ratio of the aggregate to the powder is 70:30-72: 28.
Further, the particle size range and the content of the crushed acicular petroleum coke are as follows according to the weight percentage:
1 μm < particle size less than or equal to 0.5 μm 15-25 wt%;
the particle size is less than or equal to 0.3 mu m and is less than or equal to 0.5 mu m, and 20-25 wt%;
0.3 mu m < 15-25 wt% with the particle size less than or equal to 0.1 mu m;
0< 45-50 wt% of particle size of 0.1 mu mm;
further, the particle size range and content of the needle petroleum coke crushed are preferably as follows:
1 μm < particle size less than or equal to 0.5 μm 20 wt%;
0.5 μm < particle size less than or equal to 0.3 μm 25 wt%;
0.3 mu m < the particle size is less than or equal to 0.1 mu m and 20 wt%;
0< particle size <0.1 μm 45 wt%.
Further, the impregnant is subjected to ultrasonic treatment before being injected into the impregnation tank.
Further, the ultrasonic treatment energy is 38J, and the ultrasonic treatment time is 30 min.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a special fine-particle graphite material, which takes aggregate as acicular petroleum coke; the powder material is graphene, pitch coke, carbon black and carbon fiber; the binder is modified medium-temperature coal pitch; the impregnant is impregnating asphalt, and fine particle graphite materials are prepared by kneading, profiling, roasting, impregnating, secondary roasting and graphitizing; the raw materials are reasonably selected, and the preparation process is scientific; the structure is uniform and fine, and the volume density is high; the physical and chemical indexes of the graphite are excellent. The volume density of the special fine-particle graphite prepared by the invention is more than or equal to 2.0g/cm3The resistivity is less than or equal to 6.0 mu omega m, the breaking strength is more than or equal to 32Mpa, the compressive strength is more than or equal to 65Mpa, the porosity is less than or equal to 10 percent, the ash content is less than or equal to 0.2 percent, and the thermal expansion coefficient is less than or equal to 2 x 10-6/℃。
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of a special fine particle graphite material comprises the following steps:
s1, crushing, screening and batching, wherein the aggregate and the powder are screened according to the particle size and are batched;
s2, kneading: adding the graded ingredients into a kneading pot for stirring, wherein the kneading is divided into dry mixing and wet mixing, the dry mixing is to add aggregate and powder into the kneading pot for stirring, the kneading pot is of a double-reamer type, the temperature of the kneading pot is 220-250 ℃, the dry mixing temperature of the aggregate and the powder is 150-180 ℃, and the dry mixing time is 45-50 minutes; the temperature of the wet mixing adhesive is 140-180 ℃, and the wet mixing time is 40-45 minutes;
s3, extrusion molding and cooling: after kneading, extruding and molding the kneaded product through an electrode extruder, and then placing the molded product in water to cool the molded product to normal temperature; the bulk density of the formed green body reaches 1.80-2.0g/cm3；
S4, primary roasting: placing the molded green body into a ring-type roasting furnace, filling the furnace with coke powder, quartz sand, river sand and the like, heating gradually according to a heating curve under the condition of isolating air, wherein the heating rate is 3.0-4.0 ℃/h at 150-350 ℃, and the holding time is 55 h; at the temperature of 350-450 ℃, the heating rate is 1.5-1.8 ℃/h, and the holding time is 35 h; at the temperature of 450-550 ℃, the heating rate is 1.2-1.4 ℃/h, and the holding time is 85 h; at 550-650 ℃, the heating rate is 1.8-2.0 ℃/h, and the holding time is 55 h; at 650-750 ℃, the heating rate is 3.5-4.0 ℃/h, and the holding time is 24 h; at 750-850 ℃, the heating rate is 4.0-5.0 ℃/h, and the holding time is 24 h; at 850-1150 ℃, the heating rate is 6.5-8.5 ℃/h, and the holding time is 30 h; at 1150-1250 ℃, the heating rate is 8.0-8.5 ℃/h, and the holding time is 24 h; keeping the temperature at 1250 ℃ for 22h, then naturally cooling to room temperature and discharging;
s5, dipping: placing the roasted product into an impregnation tank, and impregnating impregnant impregnated asphalt into pores of the roasted product under certain process conditions; firstly, preheating a roasted product to 350-450 ℃, keeping the temperature for 8h, putting the roasted product into an impregnation tank, vacuumizing and pressurizing for 2.5h, then injecting an impregnant into the impregnation tank, and keeping the pressure for 2 h; the weight gain rate of impregnation is 15-17%;
s6, secondary roasting in a tunnel kiln: carrying out a rapid pitch sintering process on the impregnated product in a tunnel kiln, wherein the maximum temperature is 700 ℃ and the time is 144 h;
s7, graphitizing: putting the product after secondary roasting into an Acheson graphitizing furnace, heating the roasted product to 2800-3200 ℃ by current under the condition of air isolation, specifically heating the roasted product to 1350 ℃ from room temperature at a heating rate of 250 ℃/h, then heating the roasted product to 2200 ℃ from 1350 ℃ at a heating rate of 25 ℃/h, and freely heating the roasted product to 3200 ℃ after the temperature reaches 2200 ℃, so that the two-dimensional structure carbon product is converted into a three-dimensional graphite grid structure, and the total power transmission time is 168 h;
s8, machining: and machining the graphitized product to obtain a finished product.
Further, in the raw materials of the special fine particle graphite material, the aggregate is needle-shaped petroleum coke; the powder material is graphene, pitch coke, carbon black and carbon fiber; the binder is modified medium-temperature coal pitch; the impregnant is impregnation asphalt.
Further, the true density of the acicular petroleum coke aggregate is more than or equal to 2.13g/cm3Ash content is less than or equal to 0.20 percent, volatile matter is less than or equal to 0.25 percent, and sulfur content is less than or equal to 0.30 percent; the tensile modulus of the powder graphene is less than or equal to 1.01TPa, and the ultimate strength is less than or equal to 116 Gpa; the particle size of the powder asphalt coke is 0.05-0.10 mu m, and the true density is more than or equal to 2.13/cm3Ash content is less than or equal to 0.25 percent, sulfur content is less than or equal to 0.3 percent, and volatile matter is less than or equal to 0.5 percent; the purity of the powder carbon black is 99 percent, and the particle size is 0.04-0.08 mu m; the granularity of the powder carbon fiber is 0.03-0.07 mu m, the tensile strength is 7.0Gpa, and the density is 2.10g/cm3The resistivity is less than or equal to 35 mu omega cm; the softening point of the binder modified medium-temperature coal pitch is 83-86 ℃, the coking value is more than or equal to 48 percent, and the ash content is less than or equal to 0.30 percent; the softening point of the impregnant dipping asphalt is 83-88 ℃, the coking value is more than or equal to 48 percent, and the quinoline insoluble is less than or equal to 0.30 percent.
Further, the weight ratio of the powder graphene, the pitch coke, the carbon black and the carbon fiber is 20:30:15: 35.
Further, the weight ratio of the aggregate to the powder is 70:30-72: 28.
Further, the particle size range and the content of the crushed acicular petroleum coke are as follows according to the weight percentage:
1 μm < particle size less than or equal to 0.5 μm 15-25 wt%;
the particle size is less than or equal to 0.3 mu m and is less than or equal to 0.5 mu m, and 20-25 wt%;
0.3 mu m < 15-25 wt% with the particle size less than or equal to 0.1 mu m;
0< 45-50 wt% of particle size of 0.1 mu mm;
further, the particle size range and content of the needle petroleum coke crushed are preferably as follows:
1 μm < particle size less than or equal to 0.5 μm 20 wt%;
0.5 μm < particle size less than or equal to 0.3 μm 25 wt%;
0.3 mu m < the particle size is less than or equal to 0.1 mu m and 20 wt%;
0< particle size <0.1 μm 45 wt%.
In this example, the impregnant was sonicated prior to injection into the impregnation tank. The aggregation of the insoluble components of the heavy oil in the dipping process of the asphalt is reduced, and the viscosity of the asphalt is reduced.
In this embodiment, the ultrasonic treatment energy is 38J, and the ultrasonic treatment time is 30 min.
Although only the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art, and all changes are encompassed in the scope of the present invention.
Claims (9)
1. A preparation method of a special fine particle graphite material is characterized by comprising the following steps:
s1, crushing, screening and batching, wherein the aggregate and the powder are screened and batched;
s2, kneading: adding the graded ingredients into a kneading pot for stirring, wherein the kneading is divided into dry mixing and wet mixing, the dry mixing is to add aggregate and powder into the kneading pot for stirring, the kneading pot is of a double-reamer type, the temperature of the kneading pot is 220-250 ℃, the dry mixing temperature of the aggregate and the powder is 150-180 ℃, and the dry mixing time is 45-50 minutes; the temperature of the wet mixing adhesive is 140-180 ℃, and the wet mixing time is 40-45 minutes;
s3, extrusion molding and cooling: after kneading, extruding and molding the kneaded product through an electrode extruder, and then placing the molded product in water to cool the molded product to normal temperature; the bulk density of the formed green body reaches 1.80-2.0g/cm3；
S4, primary roasting: placing the molded green body into a ring-type roasting furnace, filling the furnace with coke powder, quartz sand, river sand and the like, heating gradually according to a heating curve under the condition of isolating air, wherein the heating rate is 3.0-4.0 ℃/h at 150-350 ℃, and the holding time is 55 h; at the temperature of 350-450 ℃, the heating rate is 1.5-1.8 ℃/h, and the holding time is 35 h; at the temperature of 450-550 ℃, the heating rate is 1.2-1.4 ℃/h, and the holding time is 85 h; at 550-650 ℃, the heating rate is 1.8-2.0 ℃/h, and the holding time is 55 h; at 650-750 ℃, the heating rate is 3.5-4.0 ℃/h, and the holding time is 24 h; at 750-850 ℃, the heating rate is 4.0-5.0 ℃/h, and the holding time is 24 h; at 850-1150 ℃, the heating rate is 6.5-8.5 ℃/h, and the holding time is 30 h; at 1150-1250 ℃, the heating rate is 8.0-8.5 ℃/h, and the holding time is 24 h; keeping the temperature at 1250 ℃ for 22h, then naturally cooling to room temperature and discharging;
s5, dipping: placing the roasted product into an impregnation tank, and impregnating impregnant impregnated asphalt into pores of the roasted product under certain process conditions; firstly, preheating a roasted product to 350-450 ℃, keeping the temperature for 8h, putting the roasted product into an impregnation tank, vacuumizing and pressurizing for 2.5h, then injecting an impregnant into the impregnation tank, and keeping the pressure for 2 h; the weight gain rate of impregnation is 15-17%;
s6, secondary roasting in a tunnel kiln: carrying out a rapid pitch sintering process on the impregnated product in a tunnel kiln, wherein the maximum temperature is 700 ℃ and the time is 144 h;
s7, graphitizing: putting the product after secondary roasting into an Acheson graphitizing furnace, heating the roasted product to 2800-3200 ℃ by current under the condition of air isolation, specifically heating the roasted product to 1350 ℃ from room temperature at a heating rate of 250 ℃/h, then heating the roasted product to 2200 ℃ from 1350 ℃ at a heating rate of 25 ℃/h, and freely heating the roasted product to 3200 ℃ after the temperature reaches 2200 ℃, so that the two-dimensional structure carbon product is converted into a three-dimensional graphite grid structure, and the total power transmission time is 168 h;
s8, machining: and machining the graphitized product to obtain a finished product.
2. The method for preparing a special fine particle graphite material as claimed in claim 1, wherein: in the raw materials of the special fine particle graphite material, the aggregate is needle-shaped petroleum coke; the powder material is graphene, pitch coke, carbon black and carbon fiber; the binder is modified medium-temperature coal pitch; the impregnant is impregnation asphalt.
3. The method for preparing a special fine particle graphite material as claimed in claim 1, wherein: the true density of the acicular petroleum coke as the aggregate is more than or equal to 2.13g/cm3Ash content is less than or equal to 0.20 percent, volatile matter is less than or equal to 0.25 percent, and sulfur content is less than or equal to 0.30 percent; the tensile modulus of the powder graphene is less than or equal to 1.01TPa, and the ultimate strength is less than or equal to 116 Gpa; the particle size of the powder asphalt coke is 0.05-0.10 mu m, and the true density is more than or equal to 2.13/cm3Ash content is less than or equal to 0.25 percent, sulfur content is less than or equal to 0.3 percent, and volatile matter is less than or equal to 0.5 percent; what is needed isThe purity of the powder carbon black is 99 percent, and the particle size is 0.04-0.08 mu m; the granularity of the powder carbon fiber is 0.03-0.07 mu m, the tensile strength is 7.0Gpa, and the density is 2.10g/cm3The resistivity is less than or equal to 35 mu omega cm; the softening point of the binder modified medium-temperature coal pitch is 83-86 ℃, the coking value is more than or equal to 48 percent, and the ash content is less than or equal to 0.30 percent; the softening point of the impregnant dipping asphalt is 83-88 ℃, the coking value is more than or equal to 48 percent, and the quinoline insoluble is less than or equal to 0.30 percent.
4. A special fine particle graphite material production method as claimed in claim 2 or 3, characterized in that: the crushed acicular petroleum coke has the following particle size range and content in percentage by weight:
1 μm < particle size less than or equal to 0.5 μm 15-25 wt%;
the particle size is less than or equal to 0.3 mu m and is less than or equal to 0.5 mu m, and 20-25 wt%;
0.3 mu m < 15-25 wt% with the particle size less than or equal to 0.1 mu m;
0< 45-50 wt% of particle size of 0.1 mu mm.
5. A special fine particle graphite material production method as claimed in claim 2 or 3, characterized in that: the particle size range and content of the broken acicular petroleum coke are preferably as follows:
1 μm < particle size less than or equal to 0.5 μm 20 wt%;
0.5 μm < particle size less than or equal to 0.3 μm 25 wt%;
0.3 mu m < the particle size is less than or equal to 0.1 mu m and 20 wt%;
0< particle size <0.1 μm 45 wt%.
6. The method for preparing a special fine particle graphite material as claimed in claim 1, wherein: the weight ratio of the powder graphene to the pitch coke to the carbon black to the carbon fiber is 20:30:15: 35.
7. The method for preparing a special fine particle graphite material as claimed in claim 1, wherein: the weight ratio of the aggregate to the powder is 70:30-72: 28.
8. The method for preparing a special fine particle graphite material as claimed in claim 1, wherein: the impregnant is subjected to ultrasonic treatment before being injected into an impregnation tank.
9. The method for preparing a special fine particle graphite material as claimed in claim 8, wherein: the ultrasonic treatment energy is 38J, and the ultrasonic treatment time is 30 min.
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| CN112210791A (en) * | 2020-09-14 | 2021-01-12 | 中电投宁夏能源铝业青鑫炭素有限公司 | Preparation method of high-density graphitized cathode carbon block for aluminum electrolysis |
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Application publication date: 20200519 |