CN110668837A - Preparation method of low-loss graphite electrode - Google Patents

Preparation method of low-loss graphite electrode Download PDF

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CN110668837A
CN110668837A CN201911040196.6A CN201911040196A CN110668837A CN 110668837 A CN110668837 A CN 110668837A CN 201911040196 A CN201911040196 A CN 201911040196A CN 110668837 A CN110668837 A CN 110668837A
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graphite electrode
graphene
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finished product
raw materials
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刘雁伟
魏玉明
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Datong Tongyang Carbon Co Ltd
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Datong Tongyang Carbon Co Ltd
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Abstract

The invention discloses a preparation method of a low-loss graphite electrode, relating to the technical field of electrode preparation; crushing petroleum coke, needle coke, copper powder, graphene, beta-SiC and the like, performing an activation reaction in a reaction kettle by using ethanol gas, adding graphene fibers, kneading, roasting, immersing in a zinc chloride solution for ion adsorption, drying and graphitizing; the raw materials are activated before kneading and molding, so that the method is favorable for enhancing the binding force between the raw materials in the process of forming the graphite electrode, and the breakage rate of the graphite electrode in use is improved; on the basis of increasing the graphene fiber and the additive, the method combines the early activation of raw materials and the later ion adsorption of a semi-finished product, effectively improves the strength of a finished product graphite electrode, reduces the breakage rate, and has high melting point, high elastic coefficient, good electric thermal conductivity, small thermal expansion performance and good impact performance.

Description

Preparation method of low-loss graphite electrode
Technical Field
The invention relates to the technical field of electrode preparation, in particular to a preparation method of a low-loss graphite electrode.
Background
The graphite electrode is made up by using petroleum coke and needle coke as raw material and coal pitch as binding agent through the processes of calcining, proportioning, kneading, pressing, roasting, graphitizing and machining, and is a conductor which can release electric energy in the form of electric arc in electric arc furnace to heat and melt furnace charge, and can be divided into ordinary power, high power and ultrahigh power according to its low mass index.
However, the conventional graphite electrode is unstable in structure, low in strength and easy to oxidize in a high-temperature environment, so that the graphite electrode gradually becomes thinner from an oxidation part, the abrasion resistance of the electrode is reduced, the loss is high, the structure is unstable, the performance is reduced, the emission performance and the yield of the graphite electrode are reduced to a certain extent after the graphite electrode is subjected to oxidation resistance treatment, and the production period and the energy consumption are improved. How to provide a graphite electrode with stable structure, high strength, low loss, safety and reliability is a problem to be solved at present.
Disclosure of Invention
The invention overcomes the defects in the prior art, provides a preparation method of a low-loss graphite electrode, and aims to improve the anti-loss performance of the graphite electrode and prolong the service life and the performance of the graphite electrode.
The invention is realized by the following technical scheme.
A preparation method of a low-loss graphite electrode comprises the following specific steps:
1) weighing the following raw materials in parts by weight: 30-32 parts of petroleum coke, 20-25 parts of needle coke, 10-12 parts of coal tar pitch, 5-7 parts of beta-SiC, 2-3 parts of graphene, 0.5-0.7 part of fatty alcohol-polyoxyethylene ether, 0.5-0.8 part of sodium methylnaphthalene sulfonate, 0.5-0.8 part of CaO, 0.5-0.7 part of AL2O30.5-0.7 part of hafnium carbide and 1-3 parts of copper powder.
2) Raw material activation treatment: respectively crushing and screening the solid raw materials to powder with the particle size of 30-50nm, fully mixing petroleum coke, needle coke, copper powder, graphene and beta-SiC to form a mixture A, putting the mixture A into a reaction kettle, introducing ethanol gas with the mass of 5-8% of the mixture A into the reaction kettle, and stirring and reacting for 3-5h at the temperature of 350-450 ℃ to obtain a reactant B.
3) Material molding: cooling the B to 100-150 ℃, and adding fatty alcohol-polyoxyethylene ether, sodium methyl naphthalene sulfonate, CaO, hafnium carbide and AL2O3After mixing thoroughly, adding coalMixing the asphalt to prepare paste, adding the graphene fiber into the paste to continue mixing, and then kneading and molding in a molding machine.
4) Roasting a semi-finished product: and roasting the semi-finished product obtained after kneading and molding, naturally cooling after roasting, and standing for 72 hours to obtain a graphite electrode roasted product.
5) Ion adsorption: completely immersing the obtained graphite electrode roasted product into an ionic solution, standing for 48-72h, and then drying, wherein the ionic solution is 5-10mol/L zinc chloride solution.
6) Graphitization treatment: and (3) putting the dried roasted product into a graphitization furnace, carrying out graphitization treatment on the roasted product according to a power transmission curve, wherein in the process, the temperature of the graphitization furnace is heated to 3300-.
Preferably, the reaction pressure of the reaction kettle in the step 2 is 8-15 MPa.
Preferably, in the step 2, the petroleum coke, the needle coke, the copper powder, the graphene and the beta-SiC are fully mixed at a stirring speed of 1500-.
Preferably, the graphene fiber added in the step 3 accounts for 6-10% of the mass of the paste, and the diameter of the graphene fiber is 0.5-1 mm.
Preferably, the temperature for calcination in the step 4 is 1200-1500 ℃.
Preferably, the ionic solution is 8mol/L zinc chloride solution.
Compared with the prior art, the invention has the beneficial effects that.
According to the method, the raw materials are activated before kneading and molding, and the oxygen-containing groups on the surfaces of petroleum coke, needle coke and graphene are removed by the gaseous ethanol at a certain temperature and under a certain pressure, so that the method is favorable for enhancing the binding force among the raw materials in the process of forming the graphite electrode. The sodium methylnaphthalenesulfonate and the hafnium carbide are added into the raw materials, so that the oxidation resistance of the graphite electrode is improved, and the breakage rate of the graphite electrode in use is improved; after the baked semi-finished product is obtained, the step of ion adsorption is added, so that zinc ions are attached to a dendritic structure formed between graphene fibers and other raw materials in the graphite electrode, the conductivity of the graphite electrode is effectively improved, and the graphite electrode has stable current conductivity. On the basis of increasing the graphene fiber and the additive, the method effectively improves the strength of the finished graphite electrode by combining the early activation of the raw materials and the later ion adsorption of the semi-finished product, so that the finished graphite electrode has higher strength, high melting point and high elastic coefficient, good electric thermal conductivity, smaller thermal expansion performance and better impact performance.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The technical solutions of the present invention are described in detail below with reference to examples, but the scope of protection is not limited thereto.
Example 1
A preparation method of a low-loss graphite electrode comprises the following specific steps:
1) weighing the following raw materials: weighing 30kg of petroleum coke, 23kg of needle coke, 10kg of coal tar pitch, 5kg of beta-SiC, 2kg of graphene powder, 0.7kg of fatty alcohol-polyoxyethylene ether, 0.5kg of sodium methyl naphthalene sulfonate, 0.6kg of CaO and 0.5kg of AL2O30.7kg of hafnium carbide and 1kg of copper powder.
2) Raw material activation treatment: mixing petroleum coke, needle coke, graphene, beta-SiC, CaO and AL2O3And the hafnium carbide and the copper powder are respectively crushed into nanoscale powder, the nanoscale powder is sieved to powder with the particle size of 30nm by using an airflow sieving machine, then the petroleum coke, the needle coke, the copper powder, the graphene and the beta-SiC are fully mixed to form a mixture A, the stirring speed of a stirring machine for mixing is 1800r/min, and the mixing time is 30 min. And (3) putting the A into a supercritical stirring reaction kettle, introducing ethanol gas with the mass of 6% of the A into the reaction kettle, and stirring and reacting for 4 hours at the temperature of 350 ℃ under the pressure of 12MPa to obtain a reactant B.
3) Material molding: cooling the B to about 120 ℃, adding fatty alcohol-polyoxyethylene ether,Sodium methylnaphthalenesulfonate, CaO, hafnium carbide and AL2O3And after fully mixing, adding coal tar pitch, mixing to prepare paste, adding 8% of graphene fiber by weight into the paste, continuously mixing, and kneading and molding in a molding machine, wherein the diameter of the graphene fiber is 0.5-1 mm.
4) Roasting a semi-finished product: and roasting the semi-finished product obtained after the mixing and kneading molding, putting the graphite electrode semi-finished product into a ring type roasting furnace, roasting the graphite electrode semi-finished product according to a designed heating curve, keeping the temperature at the maximum temperature of 1200 ℃ for 20 hours, naturally cooling the graphite electrode semi-finished product, and cooling the graphite electrode semi-finished product for 78 hours to obtain a graphite electrode roasted product.
5) Ion adsorption: and completely immersing the obtained graphite electrode roasted product into zinc chloride solution with the concentration of 8mol/L, standing for 72h, and then drying.
6) Graphitization treatment: and (3) putting the dried roasted product into a graphitization furnace, carrying out graphitization treatment on the roasted product according to a power transmission curve, heating the graphitization furnace to 3500 ℃ in the process, and controlling the cooling maintenance time to be 320h to obtain the finished product graphite electrode.
7) And (4) detecting quality indexes, namely detecting the resistivity, the volume density, the breaking strength, the elastic modulus and the thermal expansion coefficient of the graphitized product to judge the quality of the graphite electrode. And processing the graphitized product into a finished product with a specified specification, and then pre-assembling, packaging and warehousing according to specified matching requirements.
The detection parameters of the prepared finished product graphite electrode are as follows:
the resistivity was 5.6uΩ. m, and the bulk density was 1.60g/cm3The flexural strength is 12.5MPa, the elastic modulus is 16.1 GPa, and the thermal expansion coefficient is 1.25 multiplied by 10-6m/℃。
Example 2
A preparation method of a low-loss graphite electrode comprises the following specific steps:
1) weighing the following raw materials: weighing 32kg of petroleum coke, 20kg of needle coke, 11kg of coal tar pitch, 7kg of beta-SiC, 3kg of graphene powder, 0.5kg of fatty alcohol-polyoxyethylene ether, 0.5kg of sodium methyl naphthalene sulfonate, 0.7kg of CaO and 0.6kg of AL2O30.5kg hafnium carbide, 1.5kg copper powder.
2) Raw material activation treatment: mixing petroleum coke, needle coke, beta-SiC, CaO and AL2O3And respectively crushing the graphene, the hafnium carbide and the copper powder into nanoscale powder, sieving the nanoscale powder to obtain powder with the particle size of 50nm by using an airflow sieving machine, and fully mixing the petroleum coke, the needle coke, the copper powder, the graphene and the beta-SiC to form a mixture A, wherein the stirring speed of a stirrer for mixing is 1800r/min, and the mixing time is 30 min. And (3) putting the A into a supercritical stirring reaction kettle, introducing ethanol gas with the mass of 8% of the A into the reaction kettle, and stirring and reacting for 4.5 hours at the temperature of 400 ℃ under the pressure of 10MPa to obtain a reactant B.
3) Material molding: cooling B to about 150 ℃, adding fatty alcohol-polyoxyethylene ether, sodium methyl naphthalene sulfonate, CaO, hafnium carbide and AL2O3After fully mixing, adding coal tar pitch, mixing to prepare paste, adding graphene fibers accounting for 6% of the weight of the paste, continuously mixing, and kneading and molding in a molding machine, wherein the diameter of the graphene fibers is 0.5 mm.
4) Roasting a semi-finished product: and roasting the semi-finished product obtained after kneading and molding, putting the graphite electrode semi-finished product into a ring type roasting furnace, roasting, keeping the temperature at the highest temperature of 1500 ℃ for 20 hours, naturally cooling, and cooling for 80 hours to obtain a graphite electrode roasted product.
5) Ion adsorption: and completely immersing the obtained graphite electrode roasted product into a zinc chloride solution with the concentration of 5mol/L, standing for 72h, and then drying.
6) Graphitization treatment: and (3) putting the dried roasted product into a graphitization furnace, carrying out graphitization treatment on the roasted product according to a power transmission curve, wherein the temperature of the graphitization furnace is heated to 3300 ℃, and the cooling maintenance time is controlled to be 320h, so that a finished product graphite electrode is obtained.
7) And (4) detecting quality indexes, namely detecting the resistivity, the volume density, the breaking strength, the elastic modulus and the thermal expansion coefficient of the graphitized product to judge the quality of the graphite electrode. And processing the graphitized product into a finished product with a specified specification, and then pre-assembling, packaging and warehousing according to specified matching requirements.
The detection parameters of the prepared finished product graphite electrode are as follows:
the resistivity was 5.5uΩ. m, and the bulk density was 1.65g/cm3Flexural strength of 13.1MPa, elastic modulus of 15.8GPa, and thermal expansion coefficient of 1.29X 10-6m/℃。
Example 3
A preparation method of a low-loss graphite electrode comprises the following specific steps:
1) weighing the following raw materials: weighing 31kg of petroleum coke, 25kg of needle coke, 12kg of coal tar pitch, 6kg of beta-SiC, 2.5kg of graphene powder, 0.6kg of fatty alcohol-polyoxyethylene ether, 0.5kg of sodium methyl naphthalene sulfonate, 0.6kg of hafnium carbide, 0.6kg of CaO and 0.7kg of AL2O32kg of copper powder.
2) Raw material activation treatment: mixing petroleum coke, needle coke, beta-SiC, CaO, graphene powder, hafnium carbide and AL2O3And respectively crushing the copper powder into nanoscale powder, sieving the nanoscale powder by using a gas flow sieving machine to obtain powder with the particle size of 30-50nm, and fully mixing petroleum coke, needle coke, copper powder, graphene and beta-SiC to form a mixture A, wherein the stirring speed of a stirrer for mixing is 1500r/min, and the mixing time is 20 min. And (3) putting the A into a supercritical stirring reaction kettle, introducing ethanol gas with the mass of 5% of the A into the reaction kettle, and stirring and reacting for 4 hours at the temperature of 350 ℃ under the pressure of 15MPa to obtain a reactant B.
3) Material molding: cooling the B to about 130 ℃, adding fatty alcohol-polyoxyethylene ether, sodium methyl naphthalene sulfonate, graphene, CaO and AL2O3After fully mixing, adding coal tar pitch, mixing to prepare paste, adding graphene fibers accounting for 6% of the weight of the paste, continuously mixing, and kneading and molding in a molding machine, wherein the diameter of the graphene fibers is 1 mm.
4) Roasting a semi-finished product: and roasting the semi-finished product obtained after the mixing and kneading molding, putting the graphite electrode semi-finished product into a ring type roasting furnace, roasting the graphite electrode semi-finished product according to a designed heating curve, keeping the temperature at the maximum temperature of 1400 ℃ for 20 hours, naturally cooling, and cooling for 72 hours to obtain a graphite electrode roasted product.
5) Ion adsorption: and completely immersing the obtained graphite electrode roasted product into a zinc chloride solution with the concentration of 10mol/L, standing for 72 hours, and then drying.
6) Graphitization treatment: and (3) putting the dried roasted product into a graphitization furnace, carrying out graphitization treatment on the roasted product according to a power transmission curve, wherein the temperature of the graphitization furnace is heated to 3200 ℃, and the cooling maintenance time is controlled to be 320h, so that a finished product graphite electrode is obtained.
7) And (4) detecting quality indexes, namely detecting the resistivity, the volume density, the breaking strength, the elastic modulus and the thermal expansion coefficient of the graphitized product to judge the quality of the graphite electrode. And processing the graphitized product into a finished product with a specified specification, and then pre-assembling, packaging and warehousing according to specified matching requirements.
The detection parameters of the prepared finished product graphite electrode are as follows:
the resistivity was 5.5uΩ. m, and the bulk density was 1.62g/cm3The flexural strength is 12.2MPa, the elastic modulus is 14.7GPa, and the thermal expansion coefficient is 1.2 multiplied by 10-6m/℃。
The above examples prove that the raw materials are activated before kneading and molding, and the oxygen-containing groups on the surfaces of petroleum coke, needle coke and graphene are removed by gaseous ethanol at a certain temperature and pressure, so that the method is favorable for enhancing the bonding force among the raw materials in the process of forming the graphite electrode. The sodium methylnaphthalenesulfonate and the hafnium carbide are added into the raw materials, so that the oxidation resistance of the graphite electrode is improved, and the breakage rate of the graphite electrode in use is improved; after the baked semi-finished product is obtained, the step of ion adsorption is added, so that zinc ions are attached to a dendritic structure formed between graphene fibers and other raw materials in the graphite electrode, the conductivity of the graphite electrode is effectively improved, and the graphite electrode has stable current conductivity. On the basis of increasing the graphene fiber and the additive, the method effectively improves the strength of the finished graphite electrode by combining the early activation of the raw materials and the later ion adsorption of the semi-finished product, so that the finished graphite electrode has higher strength, high melting point and high elastic coefficient, good electric thermal conductivity, smaller thermal expansion performance and better impact performance.
While the invention has been described in further detail with reference to specific preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (6)

1. A preparation method of a low-loss graphite electrode is characterized by comprising the following specific steps:
1) weighing the following raw materials in parts by weight: 30-32 parts of petroleum coke, 20-25 parts of needle coke, 10-12 parts of coal tar pitch, 5-7 parts of beta-SiC, 2-3 parts of graphene, 0.5-0.7 part of fatty alcohol-polyoxyethylene ether, 0.5-0.8 part of sodium methylnaphthalene sulfonate, 0.5-0.8 part of CaO, 0.5-0.7 part of AL2O30.5-0.7 part of hafnium carbide and 1-3 parts of copper powder;
2) raw material activation treatment: respectively crushing and screening various solid raw materials to powder with the particle size of 30-50nm, fully mixing petroleum coke, needle coke, copper powder, graphene and beta-SiC to form a mixture A, putting the mixture A into a reaction kettle, introducing ethanol gas with the mass of 5-8% of the mixture A into the reaction kettle, and stirring and reacting for 3-5 hours at the temperature of 350-450 ℃ to obtain a reactant B;
3) material molding: cooling the B to 100-150 ℃, and adding fatty alcohol-polyoxyethylene ether, sodium methyl naphthalene sulfonate, CaO, hafnium carbide and AL2O3After fully mixing, adding coal tar pitch, mixing to prepare paste, adding graphene fibers into the paste, continuously mixing, and then kneading and molding in a molding machine;
4) roasting a semi-finished product: roasting the semi-finished product obtained after kneading and molding, naturally cooling after roasting, and standing for 72 hours to obtain a graphite electrode roasted product;
5) ion adsorption: completely immersing the obtained graphite electrode roasted product into an ionic solution, standing for 48-72h, and then drying, wherein the ionic solution is 5-10mol/L zinc chloride solution;
6) graphitization treatment: and (3) putting the dried roasted product into a graphitization furnace, carrying out graphitization treatment on the roasted product according to a power transmission curve, wherein in the process, the temperature of the graphitization furnace is heated to 3300-.
2. The method for preparing the graphite electrode with low loss according to claim 1, wherein the reaction pressure of the reaction kettle in the step 2 is 8-15 MPa.
3. The method for preparing the graphite electrode with low loss as claimed in claim 1, wherein the stirring speed for fully mixing the petroleum coke, the needle coke, the copper powder, the graphene and the β -SiC in the step 2 is 1500-1800r/min, and the mixing time is 20-30 min.
4. The method for preparing a low-loss graphite electrode as claimed in claim 1, wherein the graphene fiber added in step 3 is 6-10% by mass of the paste, and the diameter of the graphene fiber is 0.5-1 mm.
5. The method as claimed in claim 1, wherein the calcination temperature in step 4 is 1200-1500 ℃.
6. The method of claim 1, wherein the ionic solution is a zinc chloride solution with a concentration of 8 mol/L.
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