CN114275773B - Method for preparing graphene by using cathode carbon block return material - Google Patents
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Abstract
The invention provides a method for preparing graphene by using cathode carbon block returns, and belongs to the technical field of solid waste treatment. According to the invention, after the acid-base leaching treatment is carried out on the cathode carbon block return material, the carbon content in the carbon powder can be increased, most of redundant impurities are removed, the particle size of the carbon powder is reduced, the quality of the carbon powder is improved, the carbon powder can be used for preparing graphene subsequently, and the utilization degree of the cathode carbon block return material is further improved; and then, under the action of an oxidant, the carbon powder is oxidized and expanded, an intercalator is inserted into gaps of the carbon powder under the ultrasonic action, the carbon powder is processed by a microwave-assisted stripping method, and under the action of the intercalator, the carbon powder is stripped into laminar graphene, so that the high-value utilization of the return material of the cathode carbon block is realized. The results of the examples show that the size of the graphene prepared by the method provided by the invention is 5-15 μm.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to a method for preparing graphene by using a cathode carbon block return material.
Background
The cathode in the aluminum industry refers to a container for containing molten aluminum liquid and electrolyte, and consists of a steel cell shell, a cathode carbon block group and a heat insulation material. The cathode carbon block is the most critical part, has double functions of conducting electricity and forming the lining of the electrolytic cell, and is mainly used for conducting current except for containing aluminum liquid and electrolyte, namely electrons are transmitted into the electrolytic cell from the cathode carbon block. In the aluminum electrolysis process, the environment in the electrolytic cell is quite severe: high temperature, strong magnetic field, strong corrosive electrolyte, cathode carbon block must bear the erosion of high temperature ice stone solution, and also must bear the electrochemical action of high temperature salt-dissolving electrolysis process, so it is easy to deform, bulge, even break, and these hazards can seriously shorten the service life of the electrolytic cell. The quality of the cathode carbon block is of great importance, and the quality of the cathode carbon block directly influences the service life of the electrolytic cell. According to different raw materials and production processes, the cathode carbon blocks for aluminum electrolysis are roughly divided into five types in the industry, namely amorphous, semi-graphitic, high graphitic, full graphitic and graphitized cathode carbon blocks. Compared with semi-graphite, high-graphite and full-graphite cathode carbon blocks, the graphitized cathode carbon block has better performance, but is soft, low in hardness, poor in mechanical wear resistance and higher in price.
However, when graphitized cathode carbon blocks are processed and assembled, a large amount of residue, also called cathode carbon block returns, is generated, which mainly comprises: 1) Sawing leftover materials; 2) Cutting graphite generated after sawing into pieces (4-0 mm); 3) Graphite (below 0.075 mm) produced after sawing. According to the productivity of 3 ten thousand tons per year, the yield is 70 percent, and the return material generates 9000 tons, wherein 900 tons of leftover materials, 5400 tons of cutting and crushing and 2700 tons of graphite powder. The cathode carbon blocks are difficult to recycle due to excessive impurities, for example, the utilization rate of sawing leftover materials only accounts for 10%; the utilization rate of the graphite cutting (the grain diameter is less than or equal to 4 mm) generated after sawing is only 60%; the availability of the graphite powder (80% below 200 mesh) produced after sawing is only 30%. Meanwhile, even if the return material of the cathode carbon block can be reused, asphalt needs to be added in the recycling process due to the small size of the residual material, so that the preparation cost of the graphitized cathode is improved, and the produced product has low strength index and cracks on the inside and the outside. Usually, the graphite residue is piled up in a large amount, which not only causes serious waste of resources, but also causes potential safety hazard and environmental problems.
Therefore, how to realize the high-value recycling of the cathode carbon block return materials becomes a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a method for preparing graphene by using cathode carbon block return materials, which can remove impurities in the cathode carbon block return materials and improve the purity of carbon powder, so that the method can be used for preparing graphene, high-value utilization of the cathode carbon block return materials is realized, and the performance of the graphene is excellent.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing graphene by using cathode carbon block returns, which comprises the following steps:
(1) Performing acid-base leaching treatment on the cathode carbon block return material to obtain carbon powder;
(2) Mixing the carbon powder obtained in the step (1), an oxidant and an intercalating agent, and then carrying out ultrasonic treatment to obtain intercalated graphite;
(3) And (3) mixing the intercalated graphite obtained in the step (2) with a solvent, and then carrying out microwave-assisted stripping to obtain graphene.
Preferably, the raw materials of the cathode carbon block return materials in the step (1) comprise petroleum coke, semi-graphite cathode carbon blocks, high-graphite cathode carbon blocks, full-graphite cathode carbon blocks or graphitized cathode carbon blocks, and the particle size of the cathode carbon block return materials is less than or equal to 75 μm.
Preferably, the acid-base leaching treatment in the step (1) comprises: mixing the cathode carbon block return material and alkali liquor for alkali extraction; then mixing the product obtained by alkali extraction with acid liquor to carry out acid extraction.
Preferably, the oxidant in step (1) includes one or more of ferric chloride, hydrogen peroxide, potassium permanganate, concentrated sulfuric acid, concentrated nitric acid and hypochlorous acid.
Preferably, the intercalation agent in step (1) includes one or more of nitromethane, ammonium persulfate and concentrated sulfuric acid.
Preferably, the molar ratio of the carbon powder, the oxidant and the intercalating agent in the step (1) is 1: (0.2-1): (4-10).
Preferably, the power of the ultrasonic treatment in the step (1) is 300-1000W, and the time of the ultrasonic treatment is 6-48 h.
Preferably, the solvent in the step (2) is water or an organic solvent.
Preferably, the organic solvent comprises one or more of N-methyl pyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide, methanol, ethanol, ethylene glycol and tetrahydrofuran.
Preferably, the frequency of the microwave-assisted stripping in the step (2) is 2450MHz, the power of the microwave-assisted stripping is 600-1800W, and the time of the microwave-assisted stripping is 3-60 s.
The invention provides a method for preparing graphene by using cathode carbon block returns, which comprises the following steps: (1) Performing acid-base leaching treatment on the cathode carbon block return material to obtain carbon powder; (2) Mixing the carbon powder obtained in the step (1), an oxidant and an intercalating agent, and then carrying out ultrasonic treatment to obtain intercalated graphite; (3) And (3) mixing the intercalated graphite obtained in the step (2) with a solvent, and then carrying out microwave-assisted stripping to obtain graphene. According to the invention, after the acid-base leaching treatment is carried out on the cathode carbon block return material, the carbon content in the carbon powder can be increased, most of redundant impurities are removed, the particle size of the carbon powder is reduced, the quality of the carbon powder is improved, the carbon powder can be used for preparing graphene subsequently, and the utilization degree of the cathode carbon block return material is further improved; then, under the action of an oxidant, carbon powder is oxidized and expanded, an intercalator is inserted into gaps of the carbon powder under the action of ultrasound, and then the carbon powder is processed by utilizing a microwave-assisted stripping method, so that the carbon powder is stripped into lamellar graphene under the action of the intercalator, residual impurities are further removed, the purity of the graphene is improved, and the high-value utilization of the cathode carbon block return material is realized; the method has simple and time-saving process and good industrial application prospect. The results of the embodiment show that the size of the graphene prepared by the method provided by the invention is 5-15 μm.
Drawings
Fig. 1 is a TEM image of graphene prepared in example 1 of the present invention.
Detailed Description
The invention provides a method for preparing graphene by using cathode carbon block returns, which comprises the following steps:
(1) Performing acid-base leaching treatment on the cathode carbon block return material to obtain carbon powder;
(2) Mixing the carbon powder obtained in the step (1), an oxidant and an intercalating agent, and then carrying out ultrasonic treatment to obtain intercalated graphite;
(3) And (3) mixing the intercalated graphite obtained in the step (2) with a solvent, and then carrying out microwave-assisted stripping to obtain graphene.
The invention carries out acid-base leaching treatment on the cathode carbon block return material to obtain carbon powder.
In the invention, the raw material of the cathode carbon block return material preferably comprises petroleum coke, semi-graphite cathode carbon block, high-graphite cathode carbon block, full-graphite cathode carbon block or graphitized cathode carbon block, and more preferably semi-graphite cathode carbon block, high-graphite cathode carbon block or full-graphite cathode carbon block. The cathode carbon blocks are selected as raw materials, the graphitization degree is high, the resource utilization efficiency of the cathode carbon block return materials can be further improved, and the yield of graphene is improved.
In the invention, the grain size of the return material of the cathode carbon block is preferably less than or equal to 75 μm, and more preferably: the mass percentage of the cathode carbon block return material is 100%, the cathode carbon block return material with the grain diameter of 48-75 mu m is 10-30%, and the cathode carbon block return material with the grain diameter less than 48 mu m is 70-90%. In the invention, when the particle size of the cathode carbon block return material does not meet the conditions, the raw material of the cathode carbon block return material is preferably crushed. The invention has no special limitation on the process of the crushing treatment, and the particle size of the return material of the cathode carbon block can meet the requirement.
In the present invention, the acid-base leaching treatment preferably includes: mixing the cathode carbon block return material and alkali liquor for alkali extraction; and then mixing the product obtained by alkali extraction with an acid solution for acid extraction.
In the present invention, the alkali solution is preferably NaOH solution, KOH solution or Ca (OH) 2 A solution; the concentration of the alkali liquor is preferably 0.01-0.1 mol/L, and more preferably 0.05-0.1 mol/L.
In the invention, the acid solution is preferably one or more of hydrochloric acid solution, nitric acid solution and sulfuric acid solution; the concentration of the acid solution is preferably 0.5 to 2mol/L, and more preferably 1 to 1.5mol/L. The invention can remove impurities in the cathode carbon block return material by carrying out acid-base leaching treatment on the cathode carbon block return material.
In the invention, the carbon content of the carbon powder is preferably 85-98 wt%, and more preferably 88-95 wt%; the particle size of the carbon powder is preferably 200 to 3000 meshes, and more preferably 500 to 1000 meshes. The invention controls the carbon powder under the conditions, which is beneficial to the subsequent intercalation treatment.
After the carbon powder is obtained, the carbon powder, the oxidant and the intercalation agent are mixed and then are subjected to ultrasonic treatment to obtain the intercalation graphite.
In the present invention, the oxidizing agent preferably includes one or more of ferric chloride, hydrogen peroxide, potassium permanganate, concentrated sulfuric acid, concentrated nitric acid, and hypochlorous acid, more preferably ferric chloride, hydrogen peroxide, potassium permanganate, concentrated sulfuric acid, concentrated nitric acid, or hypochlorous acid, and further preferably potassium permanganate, concentrated sulfuric acid, or hypochlorous acid. The invention can further promote the oxidation expansion of graphite by selecting the oxidant, thereby improving the intercalation efficiency.
In the present invention, the intercalation agent preferably includes one or more of nitromethane, ammonium persulfate and concentrated sulfuric acid, more preferably nitromethane, ammonium persulfate or concentrated sulfuric acid, and further preferably concentrated sulfuric acid. According to the invention, intercalation is carried out between graphite layers, so that subsequent microwave-assisted stripping is facilitated, and graphene is formed.
The source of the oxidizing agent and the intercalating agent is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the present invention, the molar ratio of the carbon powder, the oxidizing agent and the intercalating agent is preferably 1: (0.2-1): (4 to 10), more preferably 1: (0.4-0.8): (6 to 10), more preferably 1: (0.6-0.7): (8-10). The invention controls the molar ratio of each component in the range, and can further improve the oxidation effect and intercalation efficiency.
In the present invention, the power of the ultrasonic treatment is preferably 300 to 1000W, more preferably 400 to 900W, and further preferably 500 to 800W; the time for the ultrasonic treatment is preferably 6 to 48 hours, more preferably 12 to 40 hours, and further preferably 24 to 30 hours. The invention can further improve the intercalation efficiency by controlling the parameters of ultrasonic treatment in the range.
After the ultrasonic treatment is finished, the products of the ultrasonic treatment are preferably washed and dried in sequence to obtain the intercalated graphite. The washing method of the present invention is not particularly limited, and may be determined according to the common general knowledge in the art. The drying method is not particularly limited, and the product may be dried to a constant weight. The invention can remove impurities in the product by washing.
After the intercalated graphite is obtained, the intercalated graphite and a solvent are mixed and then subjected to microwave-assisted stripping to obtain graphene.
In the present invention, the solvent is preferably water or an organic solvent. In the present invention, the water is preferably deionized water; the organic solvent preferably comprises one or more of N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide, methanol, ethanol, glycol and tetrahydrofuran, more preferably N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethyl sulfoxide, methanol, ethanol, glycol or tetrahydrofuran, and further preferably N-methylpyrrolidone dimethyl sulfoxide, ethanol, glycol or tetrahydrofuran. The invention uses the solvent to improve the dispersion efficiency of the intercalated graphite in the solvent.
In the present invention, the frequency of the microwave-assisted stripping is preferably 2450MHz; the power of the microwave-assisted stripping is preferably 600 to 1800W, more preferably 900 to 1500W, and further preferably 1000 to 1200W; the time for the microwave-assisted stripping is preferably 3 to 60 seconds, more preferably 5 to 50 seconds, even more preferably 10 to 40 seconds, and most preferably 20 to 30 seconds. The microwave-assisted stripping instrument is not particularly limited, and the frequency and the power can meet the requirements. The invention controls the microwave-assisted stripping parameters within the range, and can improve the stripping efficiency of intercalated graphite.
After the microwave-assisted stripping is finished, the microwave-assisted stripping product is preferably washed, separated and dried in sequence to obtain the graphene.
In the present invention, the washing is preferably carried out by using a dilute acid and water in this order. In the invention, the dilute acid is preferably dilute hydrochloric acid, and the mass concentration of the dilute hydrochloric acid is preferably 1-5%; the water is preferably deionized water. In the present invention, the number of washing is not particularly limited, and the product may be made neutral. According to the present invention, impurities can be further removed by the above washing method.
In the present invention, the separation method is preferably centrifugal separation, and more preferably, the first centrifugal separation is performed first, and then the upper layer liquid is taken out and subjected to the second centrifugal separation, and the lower layer is precipitated. In the invention, the rotating speed of the first centrifugal separation is preferably 1000-1500 r/min, and the time of the first centrifugal separation is preferably 1-10 min; the rotating speed of the second centrifugal separation is preferably 3000-14000 r/min, and the time of the second centrifugal separation is preferably 10-40 min. According to the invention, impurities in graphene can be further removed through twice centrifugal separation.
In the present invention, the drying method is preferably freeze drying. In the present invention, the temperature of the freeze-drying is preferably-65 to-45 ℃, and the time of the freeze-drying is preferably 24 to 48 hours. According to the invention, the stress in the graphene can be reduced in a freeze drying manner.
According to the invention, a large amount of residual materials generated by the cathode carbon block are subjected to liquid phase stripping (microwave-assisted and ultrasonic-assisted) to prepare graphene in the presence of the intercalation agent, so that high-valued utilization of the processing return materials of the cathode carbon block of the aluminum electrolytic cell is realized, the process is simple, the environmental protection benefit is high, and the method has a good industrial application prospect. The method can also be used for high-value utilization of the same type of hydrocarbon chemical products.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
A method for preparing graphene by using a cathode carbon block return material comprises the following steps:
(1) Mixing the cathode carbon block return material with alkali liquor, then carrying out alkali extraction, mixing the product obtained by alkali extraction with acid liquor, and then carrying out acid extraction to obtain carbon powder; the raw material of the cathode carbon block return is a graphite cathode carbon block, and the particle size of the cathode carbon block return is less than or equal to 75 mu m; the alkali liquor is NaOH solution, and the concentration of the alkali liquor is 0.1mol/L; the acid solution is hydrochloric acid solution, and the concentration of the acid solution is 1.5mol/L; the carbon content of the carbon powder is 92wt%, and the granularity of the carbon powder is-300 meshes;
(2) Mixing the carbon powder obtained in the step (1), an oxidant and an intercalating agent, then carrying out ultrasonic treatment, then sequentially using 2mol/L hydrochloric acid and deionized water for washing, and finally carrying out vacuum drying at 60 ℃ to obtain intercalated graphite; the oxidant is potassium permanganate, and the intercalation agent is concentrated sulfuric acid; the molar ratio of the carbon powder to the oxidant to the intercalation agent is 1:0.6:10; the power of ultrasonic treatment is 600W, and the time of ultrasonic treatment is 8h;
(3) Mixing the intercalated graphite obtained in the step (2) with N-methyl pyrrolidone according to the mass ratio of 1:25, mixing, placing into a microwave reactor for microwave-assisted stripping, and then sequentially washing, centrifugally separating, and freeze-drying to obtain graphene; the microwave-assisted stripping frequency is 2450MHz, the microwave-assisted stripping power is 1500W, the microwave-assisted stripping time is 3s, and the microwave-assisted stripping atmosphere is nitrogen atmosphere; the washing mode is that dilute hydrochloric acid with the mass concentration of 5% and deionized water are used for washing in sequence; the centrifugal separation mode is that first centrifugal separation is carried out, then the upper layer liquid is taken for second centrifugal separation, and the lower layer sediment is taken; the rotating speed of the first centrifugal separation is 1000r/min, and the time of the first centrifugal separation is 10min; the rotating speed of the second centrifugal separation is 10000r/min, and the time of the second centrifugal separation is 10min; the temperature of the freeze drying is preferably-60 ℃, and the time of the freeze drying is 24h.
The size of the graphene prepared in example 1 is 5 to 15 μm.
A TEM image of the graphene prepared in example 1 is shown in fig. 1. As can be seen from FIG. 1, the graphene prepared by the method is stable in size and is equivalent to the existing graphene.
Example 2
A method for preparing graphene by using cathode carbon block return materials comprises the following steps:
(1) Mixing the cathode carbon block return material with alkali liquor, then carrying out alkali extraction, mixing a product obtained by the alkali extraction with acid liquor, and then carrying out acid extraction to obtain carbon powder; the raw material of the cathode carbon block return is a full-graphite cathode carbon block, and the particle size of the cathode carbon block return is less than or equal to 75 mu m; the alkali liquor is KOH solution, and the concentration of the alkali liquor is 0.05mol/L; the acid solution is hydrochloric acid solution, and the concentration of the acid solution is 1mol/L; the carbon content of the carbon powder is 95wt%, and the granularity of the carbon powder is 500 meshes;
(2) Mixing 0.2g of carbon powder obtained in the step (1), 12g of oxidant and 25mL of intercalation agent, then carrying out ultrasonic treatment, then sequentially washing by using nitromethane and deionized water, and finally carrying out vacuum drying at 60 ℃ to obtain intercalated graphite; the oxidant is ferric chloride, and the intercalation agent is nitromethane; the power of the ultrasonic treatment is 600W, and the time of the ultrasonic treatment is 48h;
(3) Mixing the intercalated graphite obtained in the step (2) with deionized water, placing the mixture into a microwave reactor for microwave-assisted stripping, and then sequentially washing, centrifugally separating and freeze-drying to obtain graphene; the microwave-assisted stripping frequency is 2450MHz, the microwave-assisted stripping power is 800W, the microwave-assisted stripping time is 60s, and the microwave-assisted stripping atmosphere is nitrogen atmosphere; the washing mode is that dilute hydrochloric acid with the mass concentration of 1% and deionized water are used for washing in sequence; the centrifugal separation mode is that first centrifugal separation is carried out, then the upper layer liquid is taken for second centrifugal separation, and the lower layer sediment is taken; the rotating speed of the first centrifugal separation is 1200r/min, and the time of the first centrifugal separation is 10min; the rotating speed of the second centrifugal separation is 15000r/min, and the time of the second centrifugal separation is 15min; the temperature of the freeze drying is preferably-60 ℃, and the time of the freeze drying is 24h.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. A method for preparing graphene by using cathode carbon block returns comprises the following steps:
(1) Performing acid-base leaching treatment on the cathode carbon block return material to obtain carbon powder;
(2) Mixing the carbon powder obtained in the step (1), an oxidant and an intercalating agent, and then carrying out ultrasonic treatment to obtain intercalated graphite;
(3) Mixing the intercalated graphite obtained in the step (2) with a solvent, and then carrying out microwave-assisted stripping to obtain graphene;
the oxidant in the step (2) comprises one or more of ferric chloride, hydrogen peroxide, potassium permanganate, concentrated nitric acid and hypochlorous acid;
the intercalation agent in the step (2) comprises one or more of nitromethane and ammonium persulfate;
the molar ratio of the carbon powder, the oxidant and the intercalation agent in the step (2) is 1: (0.2-1): (4-10);
the power of ultrasonic treatment in the step (2) is 300-1000W, and the time of ultrasonic treatment is 6-48 h;
the microwave-assisted stripping frequency in the step (3) is 2450MHz, the microwave-assisted stripping power is 600-1800W, and the microwave-assisted stripping time is 3-60 s.
2. The method as claimed in claim 1, wherein the raw material of the cathode carbon block return in step (1) comprises petroleum coke, semi-graphitic cathode carbon blocks, high graphitic cathode carbon blocks, fully graphitic cathode carbon blocks or graphitized cathode carbon blocks, and the particle size of the cathode carbon block return is less than or equal to 75 μm.
3. The method according to claim 1, wherein the acid-base leaching treatment in the step (1) comprises: mixing the cathode carbon block return material and alkali liquor for alkali extraction; then mixing the product obtained by alkali extraction with acid liquor to make acid extraction.
4. The method according to claim 1, wherein the solvent in the step (3) is water or an organic solvent.
5. The method according to claim 4, wherein the organic solvent comprises one or more of N-methylpyrrolidone, dimethylformamide, diethylformamide, dimethylsulfoxide, methanol, ethanol, ethylene glycol, and tetrahydrofuran.
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