CN115215656A - Preparation method of binder-free high-density graphite material and prepared graphite material - Google Patents
Preparation method of binder-free high-density graphite material and prepared graphite material Download PDFInfo
- Publication number
- CN115215656A CN115215656A CN202210958179.6A CN202210958179A CN115215656A CN 115215656 A CN115215656 A CN 115215656A CN 202210958179 A CN202210958179 A CN 202210958179A CN 115215656 A CN115215656 A CN 115215656A
- Authority
- CN
- China
- Prior art keywords
- roasting
- impregnation
- graphite material
- green coke
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/522—Graphite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses a preparation method of a binderless high-density graphite material and the prepared graphite material, which relate to the technical field of graphite preparation and aim to solve the problem that the comprehensive performance of a binderless graphite product needs to be improved; the method comprises the steps of crushing, grinding, uniformly mixing, profiling and primary roasting the green coke, carrying out primary impregnation and pre-roasting on a primary roasted product, and then sequentially carrying out secondary roasting, secondary impregnation and pre-roasting, wherein impregnants used for the primary impregnation and the secondary impregnation are suspension containing the green coke; finally, roasting and graphitizing for three times in sequence to obtain the binder-free high-density graphite material; the invention takes the green coke as the raw material, does not use a binder, and prepares a suspension liquid by using the green coke as the impregnant, and the final product has a single homogeneous structure, has various performances such as lower porosity, higher volume density, good resistivity and the like, and can meet the application requirements of more occasions.
Description
Technical Field
The invention relates to the technical field of graphite preparation, in particular to a preparation method of a binder-free high-density graphite material and the prepared graphite material.
Background
The binder is an important raw material in graphite production, usually asphalt, and mainly has the functions of binding coke powder to enable the coke powder to be pressed and formed, forming binding coke in the roasting process, and firmly binding the coke powder into a whole, thereby ensuring that the material has stronger mechanical properties and other properties. It can be said that the production of graphite materials is almost always possible using binders.
However, although the binder has a great effect, the improvement of the performance of the graphite material is also greatly restricted by the characteristics of the binder. Because the binder and the coke powder are different substances, the prepared graphite material is a heterogeneous structure of aggregate carbon-binder carbon-impregnant carbon, and the aggregate carbon has great difference with other carbon in performance, so that the uniformity of the material is poor. In addition, there are distinct interfacial layers between different carbons, which are often defective portions of the material. These causes lead to undesirable mechanical, thermoelectric and isotropic properties of graphite materials.
The graphite material without adhesive is prepared by using the raw materials without adhesive, adhering powder together by utilizing the self-adhesive property of the raw materials and roasting the powder into a whole, wherein the whole material has a homogeneous structure and does not have an obvious interface layer. The existing unbonded graphite material mostly takes raw coke, MCMB and the like as raw materials, adopts a process route of grinding, forming, roasting and graphitizing, and has the advantages of short process flow and uniform product structure. However, the binder-free process generally does not adopt an impregnation process (heterogeneous phase is avoided, and pitch coke is used as a raw material for impregnation but has generally poor performance), and pores left by escape of volatile components after roasting of the material are not filled, so that the final product has high porosity, low volume density, low mechanical performance and low thermoelectric performance and is difficult to meet the use requirements, and therefore, the binder-free graphite material is not effectively popularized and applied in reality.
The invention discloses a method for preparing a binderless graphite product by using raw petroleum coke powder and coal tar pitch mesophase spherulite powder as mixed raw materials and performing compression molding, roasting and graphitization, wherein the improved particle size fraction and the improved pressing process can improve the volume density and the breaking strength of the product to a certain extent, but the problems of high porosity and high electrical resistivity cannot be solved. Therefore, a method for preparing a binder-free high-density graphite material and a prepared graphite material are needed to solve the problem.
Disclosure of Invention
The invention aims to provide a preparation method of a binder-free high-density graphite material and the prepared graphite material, so as to solve the problem that the comprehensive performance of a binder-free graphite product needs to be improved.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a binderless high-density graphite material comprises the following steps of: crushing and grinding raw coke, uniformly mixing, profiling and roasting for the first time, then carrying out primary impregnation and pre-roasting on a primary roasted product, and then sequentially carrying out secondary roasting, secondary impregnation and pre-roasting, wherein impregnants used for the primary impregnation and the secondary impregnation are suspension liquid containing the raw coke; and finally, sequentially roasting and graphitizing for three times to obtain the binder-free high-density graphite material.
Preferably, the impregnant is a suspension prepared from green coke, the solid matter of the impregnant is green coke, and the liquid matter of the impregnant is one of oleic acid, diesel oil, kerosene or gasoline.
Preferably, the average particle size of the green coke in the impregnant used for one-time impregnation is 0.5-2 μm, and the mass percentage of the green coke in the impregnant is 30-60%.
Preferably, the average particle size of the green coke in the impregnant used for the secondary impregnation is 0.1 to 0.5 μm, and the mass percentage of the green coke in the impregnant is 40 to 80%.
Preferably, the first impregnation and pre-baking and the second impregnation and pre-baking specifically include: vacuumizing and preheating before dipping at 80-200 deg.c, the first dipping pressure of 2-4 MPa and the second dipping pressure of 3-5 MPa higher than the first one, introducing nitrogen gas while maintaining the dipping pressure, and heating to 500 deg.c at 5-10 deg.c/hr.
Preferably, the raw coke is delayed coking petroleum coke, and the volatile content of the delayed coking petroleum coke is 7-15%; drying the green coke moisture before crushing and grinding the green coke, wherein the drying temperature is 100-150 ℃; crushing and grinding the raw coke to an average particle size of 20-100 mu m; the compression molding adopts mould pressing or isostatic pressing, the molding pressure is 100-240 MPa, and the pressure maintaining time is 0-20 min; the maximum temperature of the primary roasting is 700-900 ℃, and the heating rate is 2-10 ℃/h.
Preferably, the maximum temperature of the secondary roasting is 700-900 ℃, and the heating rate is 2-10 ℃/h.
Preferably, the three times of roasting adopt high-pressure roasting, the roasting pressure is 2-4 MPa, the highest temperature is 1100 ℃, and the heating rate is 2-10 ℃/h.
Preferably, the graphitization temperature curve is sequentially from 30 ℃/h to 900 ℃, from 10 ℃/h to 1200 ℃, from 30 ℃/h to 2000 ℃, from 40 ℃/h to 3000 ℃ of the graphitization maximum temperature, and then the heat is preserved for 10h, and then the product is cooled to room temperature at 60 ℃/h.
The isotropy of the binderless high-density graphite material prepared by the method is less than or equal to 1.05, and the porosity is<16% and a volume density of not less than 1.72g/cm 3 Strength against breaking>22MPa, resistivity<13μΩ·m。
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the binder-free high-density graphite material and the prepared graphite material, raw coke is used as a raw material, a binder is not used, and the raw coke is prepared into a suspension liquid which is used as an impregnant, so that a final product is of a single homogeneous structure, has various performances such as low porosity, high volume density and good resistivity, and can meet the application requirements of many occasions.
2. The preparation method of the binderless high-density graphite material adopts twice impregnation, wherein the green coke obtained by the twice impregnation has finer granularity, larger concentration and larger impregnation pressure, and the twice impregnation effect is ensured.
3. According to the preparation method of the binder-free high-density graphite material, after two times of impregnation, pressure is maintained and temperature is raised for pre-roasting, so that the impregnant in the green body is coked partially and is solidified in the green body, and the back overflow effect after the impregnation is finished is avoided.
4. The preparation method of the binder-free high-density graphite material has the advantages that the one-time roasting temperature is low, the roasted blank still has certain volatile components, the suspension in the impregnant can be favorably bonded with the blank and solidified into a whole, and the generation of heterogeneous phase is avoided.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
Referring to fig. 1, the method for preparing a binderless high density graphite material of the present invention comprises:
crushing and grinding the raw coke, uniformly mixing, profiling and roasting for one time, wherein optionally, the moisture of the raw coke is dried before crushing and grinding the raw coke, and the drying temperature can be 100-150 ℃; the raw coke is crushed and ground into powder with the average particle size of 20-100 mu m; the compression molding can adopt mould pressing or isostatic pressing, the molding pressure is preferably 100-240 MPa, and the pressure maintaining time is 0-20 min; the maximum temperature of the primary roasting is preferably 700-900 ℃, and the heating rate can be 2-10 ℃/h;
carrying out primary impregnation and pre-roasting on a primary roasted product, and then sequentially carrying out secondary roasting, secondary impregnation and pre-roasting, wherein impregnants used for the primary impregnation and the secondary impregnation are both suspension liquid containing green coke, specifically, a solid substance in the impregnant is the green coke, a liquid substance in the impregnant can be one of oleic acid, diesel oil, kerosene or gasoline, in a preferred embodiment, the average particle size of the green coke in the impregnant used for the primary impregnation is 0.5-2 mu m, the mass percentage of the green coke in the impregnant is 30-60%, the average particle size of the green coke in the impregnant used for the secondary impregnation is 0.1-0.5 mu m, and the mass percentage of the green coke in the impregnant is 40-80%; and finally, sequentially roasting and graphitizing for three times to obtain the binder-free high-density graphite material.
In a preferred embodiment, the first impregnation and pre-baking and the second impregnation and pre-baking specifically comprise: before dipping, vacuumizing and preheating, wherein the dipping temperature is 80-200 ℃, the primary dipping pressure is 2-4 MPa, the secondary dipping pressure is 3-5 MPa, and the secondary dipping pressure is higher than the primary dipping pressure, nitrogen is respectively introduced after the two dipping steps are finished, the dipping pressure is kept, the temperature is increased to 500 ℃ under the pressure, and the temperature rising rate is 5-10 ℃/h.
The secondary roasting can be the same as the primary roasting, namely the highest temperature is 700-900 ℃, and the heating rate is 2-10 ℃/h.
The third roasting preferably adopts high-pressure roasting, the roasting pressure is 2-4 MPa, the highest temperature is 1100 ℃, and the heating rate is 2-10 ℃/h.
In a preferred embodiment, the graphitization temperature curve is sequentially raised to 900 ℃ at 30 ℃/h, raised to 1200 ℃ at 10 ℃/h, raised to 2000 ℃ at 30 ℃/h, raised to 3000 ℃ at 40 ℃/h, held for 10h, and cooled to room temperature at 60 ℃/h.
The following tests were carried out using the same batch of delayed coking petroleum coke with a volatile content of 7-15% as the feedstock:
example 1
Drying petroleum green coke at 120 deg.C, grinding to average particle size of 50 μm, and mixing. And (3) filling the powder into a mold, carrying out isostatic pressing for molding, wherein the molding pressure is 220MPa, and the pressure maintaining time is 10min. And after the molding is finished, performing a primary roasting process, wherein the roasting maximum temperature is 800 ℃, and the heating rate is 3 ℃/h.
And after the primary baking and sintering, performing primary impregnation, wherein the used impregnant is a prepared green coke suspension, the liquid is oleic acid, the solid is green coke, the average particle size of the green coke is 1 mu m, and the mass percent is 50%. The dipping process is firstly vacuumized to 300Pa, then the product is preheated to 250 ℃, and the product is dipped for 6h under the pressure of 2MPa and the temperature of 220 ℃. After the impregnation is finished, discharging the impregnation liquid, simultaneously filling nitrogen, maintaining the pressure, and raising the temperature to 500 ℃ at 5 ℃/h for pre-roasting. Taking out the product after the product is cooled and carrying out secondary roasting.
And after the secondary roasting and sintering, carrying out secondary impregnation, wherein an impregnant is a prepared green coke suspension, a liquid substance is oleic acid, a solid substance is green coke, the particle size of the green coke is 0.3 mu m, the mass percent is 60%, the impregnation pressure is 3MPa, and other conditions are the same as those of primary impregnation and pre-roasting. And taking out the product after cooling, and roasting for three times, wherein the highest temperature is 1100 ℃, the heating rate is 3 ℃/h, and nitrogen is introduced in the roasting process to maintain the pressure at 2MPa.
After the third baking and sintering, graphitizing the product, wherein the graphitization temperature curve is that 30 ℃/h is increased to 900 ℃,10 ℃/h is increased to 1200 ℃,30 ℃/h is increased to 2000 ℃,40 ℃/h is increased to 3000 ℃ of graphitization maximum temperature, preserving the heat for 10h, and then cooling to room temperature at 60 ℃/h. The final product was a binderless high density graphite material having a porosity of 14.4% and a bulk density of 1.75g/cm 3 Flexural strength 25.0MPa, resistivity 11.9 μ Ω. M, and isotropy 1.04.
Example 2
Drying petroleum green coke at 150 deg.C, grinding to average particle size of 100 μm, and mixing. And (3) putting the powder into a die, and carrying out isostatic pressing at the forming pressure of 200MPa for 15min. And after the molding is finished, performing a primary roasting process, wherein the roasting maximum temperature is 900 ℃, and the heating rate is 5 ℃/h.
And after primary roasting and sintering, performing primary impregnation by using an impregnating agent which is prepared green coke suspension, wherein the liquid is kerosene, the solid is green coke, the average particle size of the green coke is 2 mu m, and the mass percentage of the green coke is 40%. The dipping process is firstly vacuumized to 300Pa, then the product is preheated to 220 ℃ and dipped for 6h under the pressure of 3MPa and the temperature of 200 ℃. After the impregnation is finished, discharging the impregnation liquid, filling nitrogen gas, maintaining the pressure, and raising the temperature to 500 ℃ at the speed of 10 ℃/h for pre-roasting. Taking out the product after the product is cooled and carrying out secondary roasting.
After the secondary roasting and sintering, secondary impregnation is carried out, the impregnant is prepared green coke suspension, wherein the liquid is kerosene, the solid is green coke, the green coke granularity is 0.5 mu m, the mass percent is 50%, the impregnation pressure is 4MPa, and other conditions are the same as the primary impregnation and the pre-roasting. And taking out the product after cooling, and roasting for three times, wherein the highest temperature is 1100 ℃, the heating rate is 5 ℃/h, and nitrogen is introduced in the roasting process to maintain the pressure at 3MPa.
After the three times of baking and sintering, graphitizing the product, wherein the graphitization temperature curve is 30 ℃/h to 900 ℃,10 ℃/h to 1200 ℃,30 ℃/h to 2000 ℃,40 ℃ based on the blood vesselh, heating to the maximum graphitization temperature of 3000 ℃, preserving the heat for 10h, and then cooling to the room temperature at the speed of 60 ℃/h. The final product was a binderless high density graphite material having a porosity of 15.8% and a bulk density of 1.72g/cm 3 Flexural strength 22.4MPa, resistivity 12.6 mu omega m and isotropy 1.05.
Example 3
Drying petroleum green coke at 100 deg.C, grinding to average particle size of 30 μm, and mixing. And (3) putting the powder into a die, carrying out isostatic pressing at the forming pressure of 240MPa for 5min. And after the molding is finished, performing a primary roasting process, wherein the roasting maximum temperature is 700 ℃, and the heating rate is 8 ℃/h.
And after the primary baking and sintering, performing primary impregnation, wherein the used impregnant is a prepared green coke suspension, the liquid is diesel oil, the solid is green coke, the average particle size of the green coke is 0.5 mu m, and the mass percent is 40%. The dipping process is firstly vacuumized to 300Pa, then the product is preheated to 200 ℃, and the product is dipped for 6h under the pressure of 4MPa and the temperature of 160 ℃. After the impregnation is finished, discharging the impregnation liquid, filling nitrogen gas, maintaining the pressure, and raising the temperature to 500 ℃ at the speed of 10 ℃/h for pre-roasting. Taking out the product after the product is cooled and carrying out secondary roasting.
After the secondary roasting and sintering, secondary impregnation is carried out, the impregnant is prepared green coke suspension, wherein the liquid is diesel oil, the solid is green coke, the particle size of the green coke is 0.1 mu m, the mass percent is 50 percent, the impregnation pressure is 5MPa, and other conditions are the same as the primary impregnation and the pre-roasting. And taking out the product after cooling, and roasting for three times, wherein the highest temperature is 1100 ℃, the heating rate is 2 ℃/h, and nitrogen is introduced in the roasting process to maintain the pressure at 4MPa.
After the three-time baking and sintering, graphitizing the product, wherein the graphitization temperature curve is 30 ℃/h to 900 ℃,10 ℃/h to 1200 ℃,30 ℃/h to 2000 ℃,40 ℃/h to 3000 ℃ of the graphitization maximum temperature, preserving the heat for 10h, and cooling to room temperature at 60 ℃/h. The final product was a binderless high density graphite material having a porosity of 14.2% and a bulk density of 1.80g/cm 3 Flexural strength 25.5MPa, resistivity 11.2 mu omega m and isotropy 1.02.
Comparative example 1
Drying petroleum green coke at 120 deg.C, grinding to average particle size of 50 μm, and mixing. And (3) filling the powder into a mold, carrying out isostatic pressing for molding, wherein the molding pressure is 220MPa, and the pressure maintaining time is 10min. And after the molding is finished, entering a primary roasting process, wherein the highest roasting temperature is 800 ℃, and the heating rate is 3 ℃/h.
Directly graphitizing the product after cooling, wherein the graphitization temperature curve is 30 ℃/h to 900 ℃,10 ℃/h to 1200 ℃,30 ℃/h to 2000 ℃,40 ℃/h to 3000 ℃ of the graphitization maximum temperature, preserving the heat for 10h, and cooling to room temperature at 60 ℃/h. The final product has a porosity of 18.3% and a bulk density of 1.62g/cm 3 Flexural strength of 17.8MPa, resistivity of 16.3 mu omega m and isotropy of 1.10.
Comparative example 2
Drying petroleum coke at 120 deg.C, crushing, grinding to average particle size of 50 μm, and mixing. And (3) putting the powder into a die, carrying out isostatic pressing at 220MPa, and keeping the pressure for 10min. And after the molding is finished, performing a primary roasting process, wherein the roasting maximum temperature is 800 ℃, and the heating rate is 3 ℃/h.
And after primary roasting and sintering, performing primary impregnation by using an impregnating agent which is prepared green coke suspension, wherein the liquid is oleic acid, the solid is green coke, the average particle size of the green coke is 1 mu m, and the mass percentage of the green coke is 50%. The dipping process is firstly vacuumized to 300Pa, then the product is preheated to 250 ℃, and the product is dipped for 6h under the pressure of 2MPa and the temperature of 220 ℃. After the impregnation is finished, discharging the impregnation liquid, simultaneously filling nitrogen, maintaining the pressure, and raising the temperature to 500 ℃ at 5 ℃/h for pre-roasting. Taking out the product after the product is cooled and carrying out secondary roasting.
After the secondary roasting product is cooled, graphitizing the product, wherein the graphitization temperature curve is 30 ℃/h to 900 ℃,10 ℃/h to 1200 ℃,30 ℃/h to 2000 ℃,40 ℃/h to 3000 ℃ of the graphitization maximum temperature, preserving the heat for 10h, and cooling to room temperature at 60 ℃/h. The porosity of the final product is 16.1 percent, and the volume density is 1.70g/cm 3 Flexural strength 21.3MPa, resistivity 13.6 mu omega m and isotropy 1.07.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
The present invention is not described in detail, but is known to those skilled in the art.
Claims (10)
1. A preparation method of a binderless high-density graphite material is characterized by comprising the following steps of: crushing and grinding raw coke, uniformly mixing, profiling and roasting for the first time, then carrying out primary impregnation and pre-roasting on a primary roasted product, and then sequentially carrying out secondary roasting, secondary impregnation and pre-roasting, wherein impregnants used for the primary impregnation and the secondary impregnation are suspension liquid containing the raw coke; and finally, sequentially roasting and graphitizing for three times to obtain the binder-free high-density graphite material.
2. The method for preparing the binderless high density graphite material of claim 1 wherein: the impregnant is suspension prepared from green coke, the solid matter is the green coke, and the liquid matter is one of oleic acid, diesel oil, kerosene or gasoline.
3. The method for preparing the binderless high density graphite material of claim 1 or 2, wherein: the average particle size of the green coke in the impregnant used for the primary impregnation is 0.5-2 mu m, and the mass percentage of the green coke in the impregnant is 30-60%.
4. The method for preparing a binderless high density graphite material according to claim 1 or 2, wherein: the average particle size of the green coke in the impregnant used for the secondary impregnation is 0.1-0.5 mu m, and the mass percentage of the green coke in the impregnant is 40-80%.
5. The method for preparing the binderless high density graphite material of claim 1, wherein the first impregnation and pre-baking and the second impregnation and pre-baking specifically comprise: before impregnation, vacuumizing and preheating, wherein the impregnation temperature is 80-200 ℃, the primary impregnation pressure is 2-4 MPa, the secondary impregnation pressure is 3-5 MPa, the secondary impregnation pressure is higher than the primary impregnation pressure, nitrogen is respectively introduced after the two impregnations are finished, the impregnation pressure is kept, the temperature is increased to 500 ℃ under the pressure, and the temperature increase rate is 5-10 ℃/h.
6. The method of preparing a binderless high density graphite material of claim 1 wherein:
the raw coke is delayed coking petroleum coke, and the volatile component content is 7-15%;
drying the green coke moisture before crushing and grinding the green coke, wherein the drying temperature is 100-150 ℃;
crushing and grinding the green coke to an average particle size of 20-100 mu m;
the compression molding adopts mould pressing or isostatic pressing, the molding pressure is 100-240 MPa, and the pressure maintaining time is 0-20 min;
the maximum temperature of the primary roasting is 700-900 ℃, and the heating rate is 2-10 ℃/h.
7. The method of preparing a binderless high density graphite material of claim 1 wherein: the maximum temperature of the secondary roasting is 700-900 ℃, and the heating rate is 2-10 ℃/h.
8. The method of preparing a binderless high density graphite material of claim 1 wherein: the third roasting adopts high-pressure roasting, the roasting pressure is 2-4 MPa, the highest temperature is 1100 ℃, and the heating rate is 2-10 ℃/h.
9. The method of preparing a binderless high density graphite material of claim 1 wherein: the graphitization temperature curve is sequentially from 30 ℃/h to 900 ℃, from 10 ℃/h to 1200 ℃, from 30 ℃/h to 2000 ℃, from 40 ℃/h to 3000 ℃ of graphitization maximum temperature, preserving heat for 10h, and then cooling to room temperature at 60 ℃/h.
10. A binderless high density graphite material prepared by the process of any one of claims 1 to 9, wherein: the isotropy degree of the graphite material is less than or equal to 1.05, and the porosity is<16 percent and volume density ≧ 1.72g/cm 3 Strength against breaking>22MPa, resistivity<13μΩ·m。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210958179.6A CN115215656B (en) | 2022-08-11 | 2022-08-11 | Preparation method of binder-free high-density graphite material and prepared graphite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210958179.6A CN115215656B (en) | 2022-08-11 | 2022-08-11 | Preparation method of binder-free high-density graphite material and prepared graphite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115215656A true CN115215656A (en) | 2022-10-21 |
| CN115215656B CN115215656B (en) | 2023-05-05 |
Family
ID=83615483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210958179.6A Active CN115215656B (en) | 2022-08-11 | 2022-08-11 | Preparation method of binder-free high-density graphite material and prepared graphite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115215656B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4071604A (en) * | 1974-12-03 | 1978-01-31 | Advanced Technology Center, Inc. | Method of producing homogeneous carbon and graphite bodies |
| US4202868A (en) * | 1976-07-01 | 1980-05-13 | Maruzen Petrochemical Co., Ltd. | Production of high-density carbon materials |
| CN101033064A (en) * | 2006-03-07 | 2007-09-12 | 宁波杉杉新材料科技有限公司 | Method of preparing isotropic carbon material and prepared carbon material |
| CN102910912A (en) * | 2012-07-25 | 2013-02-06 | 天津市贝特瑞新能源科技有限公司 | High-hardness isostatic graphite and preparation method thereof |
| CN104446646A (en) * | 2014-12-04 | 2015-03-25 | 大同新成新材料股份有限公司 | Impregnating method of preparing isostatic pressing graphite product |
| CN107032792A (en) * | 2017-05-16 | 2017-08-11 | 江西宁新新材料股份有限公司 | A kind of high-strength high-density graphite material and preparation method thereof |
| CN107986788A (en) * | 2017-12-22 | 2018-05-04 | 天津市贝特瑞新能源科技有限公司 | A kind of preparation method of isostatic pressing formed graphite |
| CN114573371A (en) * | 2022-04-18 | 2022-06-03 | 中钢天源股份有限公司 | Deep impregnation method of isostatic pressing graphite |
-
2022
- 2022-08-11 CN CN202210958179.6A patent/CN115215656B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4071604A (en) * | 1974-12-03 | 1978-01-31 | Advanced Technology Center, Inc. | Method of producing homogeneous carbon and graphite bodies |
| US4202868A (en) * | 1976-07-01 | 1980-05-13 | Maruzen Petrochemical Co., Ltd. | Production of high-density carbon materials |
| CN101033064A (en) * | 2006-03-07 | 2007-09-12 | 宁波杉杉新材料科技有限公司 | Method of preparing isotropic carbon material and prepared carbon material |
| CN102910912A (en) * | 2012-07-25 | 2013-02-06 | 天津市贝特瑞新能源科技有限公司 | High-hardness isostatic graphite and preparation method thereof |
| CN104446646A (en) * | 2014-12-04 | 2015-03-25 | 大同新成新材料股份有限公司 | Impregnating method of preparing isostatic pressing graphite product |
| CN107032792A (en) * | 2017-05-16 | 2017-08-11 | 江西宁新新材料股份有限公司 | A kind of high-strength high-density graphite material and preparation method thereof |
| CN107986788A (en) * | 2017-12-22 | 2018-05-04 | 天津市贝特瑞新能源科技有限公司 | A kind of preparation method of isostatic pressing formed graphite |
| CN114573371A (en) * | 2022-04-18 | 2022-06-03 | 中钢天源股份有限公司 | Deep impregnation method of isostatic pressing graphite |
Non-Patent Citations (1)
| Title |
|---|
| 卞正华: "用生石油焦粉制造高密度细结构石墨制品", 《炭素技术》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115215656B (en) | 2023-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102530933B (en) | Artificial graphite product taking emulsified asphalt as binder and preparation method thereof | |
| US4190637A (en) | Graphite having improved thermal stress resistance and method of preparation | |
| CN115583835B (en) | Low-porosity high-mechanical-strength carbon graphite material and preparation method thereof | |
| CN102502594A (en) | Method for preparing isotropic graphite containing coal-based needle coke as aggregate | |
| CN108610049B (en) | Isotropic graphite material, method for the production thereof and use thereof | |
| CN115872744B (en) | Method for preparing high-performance binder-free carbon graphite material by solid-phase densification | |
| CN111018554A (en) | Method for preparing ultrahigh-power graphite electrode by using graphene | |
| KR101618736B1 (en) | Isotropic graphite article and and method of manufacturing the same | |
| CN108218430B (en) | Isostatic pressing graphite product and preparation method thereof | |
| CN115215656B (en) | Preparation method of binder-free high-density graphite material and prepared graphite material | |
| JPS589879A (en) | Manufacture of anisotropic carbon formed body | |
| US2502183A (en) | Production of carbon bodies | |
| CN109867522B (en) | Preparation method of collector shoe carbon sliding plate and collector shoe carbon sliding plate | |
| CN117088689A (en) | Short-process preparation method of graphite and graphite product | |
| JPH08508001A (en) | Structural carbon heat insulating material and manufacturing method thereof | |
| CN109133926B (en) | Sealing graphite and preparation method thereof | |
| US10377672B2 (en) | Methods for producing polygranular graphite bodies | |
| US3393085A (en) | Thermally stable carbon articles | |
| JPS61122110A (en) | Production of high-density carbon material | |
| US3993738A (en) | High strength graphite and method for preparing same | |
| CN114634361A (en) | Preparation method of isotropic isostatic pressing graphite with fine structure | |
| RU2377223C1 (en) | Method to produce composite carbon materials | |
| CN111269021B (en) | Copper-iron-carbon composite sliding plate and preparation method and application thereof | |
| KR102202219B1 (en) | Method for densifying carbon block | |
| EP4317358A1 (en) | Coal-based heat storage carbon material and preparation method therefor and application thereof, and composition for preparing coal-based heat storage carbon material and application of composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |