CN117139322B - High-value treatment method for waste cathode carbon blocks - Google Patents

High-value treatment method for waste cathode carbon blocks Download PDF

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CN117139322B
CN117139322B CN202310910806.3A CN202310910806A CN117139322B CN 117139322 B CN117139322 B CN 117139322B CN 202310910806 A CN202310910806 A CN 202310910806A CN 117139322 B CN117139322 B CN 117139322B
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CN117139322A (en
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杨文杰
刘长春
霍强
吴广鑫
王伟杰
陈浩
乔云泽
原紫渲
华宇
詹明哲
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Zhengzhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation

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Abstract

The application relates to the technical field of waste solid treatment of waste cathode carbon blocks, and particularly discloses a high-value treatment method of waste cathode carbon blocks, which comprises the following steps of: s1, placing a waste cathode carbon block into an electrolyte solution, taking the waste cathode carbon block as an anode, and pulverizing the waste cathode carbon block by adopting an electrolytic method to obtain a solid-liquid mixture; s2, carrying out solid-liquid separation, washing and drying on the solid-liquid mixture to obtain solid powder; s3, carrying out flotation on the solid powder to obtain carbon powder ore pulp and electrolyte ore pulp; s4, carrying out solid-liquid separation and drying on the carbon powder ore pulp to obtain a carbon powder product; s5, evaporating and calcining the electrolyte pulp to obtain an electrolyte product. According to the application, the waste cathode carbon blocks are electrolyzed and pulverized by an electrolysis method, the electrolyte products after separation and purification in the waste cathode carbon blocks can be recycled in aluminum electrolysis production, the pulverized carbon powder has a particle size reaching a micron level and uniform particle size distribution, and the high-purity high-value carbon powder is conveniently obtained by flotation.

Description

High-value treatment method for waste cathode carbon blocks
Technical Field
The application relates to the technical field of waste solid treatment of waste cathode carbon blocks, in particular to a high-value treatment method of waste cathode carbon blocks.
Background
In the production process of electrolytic aluminum, cathode carbon blocks in the aluminum electrolysis cell are subjected to penetration corrosion and deformation and cracking due to long-term contact with high-temperature aluminum liquid and strong-corrosiveness electrolyte, and are required to be replaced irregularly, so that a large number of waste cathode carbon blocks are generated, and the method is dangerous solid waste. The main components of the waste cathode carbon block are carbonaceous, the content of which is 30-70wt%, and the rest is mainly Na 3AlF6、Al2O3、NaF、CaF2, cyanide and other electrolytes. When the waste cathode carbon blocks are stacked in open air, cyanide and soluble fluoride in the waste cathode carbon blocks can permeate into the nature along with rainwater, water vapor and the like, pollute water and soil, cause serious fluorine-cyanide pollution, not only harm natural water resources, but also cause a large number of death or variation of plants. In addition, the waste cathode carbon blocks reacted with water can generate toxic gas, so that the personal safety is endangered.
At present, the method for treating the waste cathode carbon blocks comprises the following steps: landfill, fire, pyrolysis, oxidation, acid-base, and flotation. Wherein, the floatation method is a method for separating carbon and electrolyte in the waste cathode carbon block particles by utilizing the hydrophilic and hydrophobic principles of substances and adopting a physical and chemical combination method.
The process of treating the waste cathode carbon blocks by adopting a flotation method can be divided into four working sections of crushing and grinding, flotation, evaporation and calcination. Wherein, the grinding is to grind the waste cathode carbon blocks to the granularity required by the flotation process; adding a foaming agent, a collector, an inhibitor, a dispersing agent, a pH regulator and other flotation agents during flotation, and obtaining carbon powder products and ore pulp through roughing, selecting and scavenging; evaporating the ore pulp to obtain an electrolyte; the electrolyte is calcined to obtain high-purity electrolyte, which is reused in the electrolytic aluminum process.
The flotation method has higher requirements on classification management of solid wastes of aluminum electrolysis enterprises, and waste cathode carbon blocks are required to be piled up and treated in a classified manner according to the use time. The longer the service time of the aluminum electrolysis cell, the more electrolyte permeates into the cathode carbon blocks, the higher the graphitization degree of carbon and the lower the carbon content, and the greater the treatment difficulty of the waste cathode carbon blocks; and, the mixing treatment of the waste cathode carbon blocks with different service times can increase the treatment cost and the technical difficulty.
Wherein, in the crushing and grinding process, the waste cathode carbon blocks increase the difficulty of crushing due to the lubricating effect of graphite and high-hardness electrolyte. In the flotation process, toxic flammable gases such as HCN, H 2、NH3、CH4 and the like can be released, and potential safety hazards exist; meanwhile, the aluminum content in the carbon powder is still about 2wt%, high-value utilization can be realized only after deep impurity removal, and secondary pollution can be caused by cyanide and fluoride in the fluorine-containing wastewater.
Disclosure of Invention
In view of the above, the application provides a high-value treatment method for waste cathode carbon blocks, which is characterized in that the waste cathode carbon blocks are electrolyzed and pulverized by an electrolytic method, electrolyte products after separation and purification in the waste cathode carbon blocks can be recycled in aluminum electrolysis production, and pulverized carbon powder has a particle size reaching a micron level and uniform particle size distribution, so that high-purity high-value carbon powder can be obtained by flotation conveniently.
The application provides a high-value treatment method of waste cathode carbon blocks, which adopts the following technical scheme:
The high-value treatment method of the waste cathode carbon blocks comprises the following steps:
S1, placing the waste cathode carbon blocks in an electrolyte solution, and pulverizing the waste cathode carbon blocks by an electrolytic method by taking the waste cathode carbon blocks as anodes to obtain a solid-liquid mixture;
S2, sequentially carrying out solid-liquid separation, washing and drying on the solid-liquid mixture to obtain solid powder;
S3, carrying out flotation on the solid powder to obtain carbon powder ore pulp and electrolyte ore pulp;
S4, sequentially carrying out solid-liquid separation and drying on the carbon powder ore pulp to obtain a carbon powder product;
S5, evaporating and calcining the electrolyte pulp in sequence to obtain an electrolyte product.
In some alternative embodiments of the present application, in step S1, the electrolyte in the electrolyte solution is dissolved in a solvent in the form of ions, and during electrolysis, anions in the electrolyte solution move toward the anode and cations move toward the cathode; therefore, the electrolyte and the solvent for preparing the electrolyte solution can realize the purpose of electrolyzing and pulverizing the waste cathode carbon blocks by adopting an electrolytic method as long as the conditions are met.
In some alternative embodiments of the application, the electrolyte is selected from the group consisting of an inorganic acid, an inorganic base, a strong acid strong base salt, a strong base weak acid salt, a strong acid weak base salt, and a weak acid weak base salt, and the inorganic acid and the inorganic base cannot be present in the same electrolyte solution at the same time.
In some alternative embodiments of the present application, the mineral acid is selected from the group consisting of sulfuric acid (H 2SO4), nitric acid (HNO 3), perchloric acid (HClO 4), ferrate (H 2FeO4), and hydrochloric acid (HCl).
In some alternative embodiments of the present application, the inorganic base is selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), lithium hydroxide (LiOH), calcium hydroxide (Ca (OH) 2), aluminum hydroxide (Al (OH) 3), and magnesium hydroxide (Mg (OH) 2).
In some alternative embodiments of the present application, the strong acid strong base salt is selected from the group consisting of sodium chloride (NaCl), sodium fluoride (NaF), sodium sulfate (Na 2SO4), sodium nitrate (NaNO 3), potassium chloride (KCl), potassium fluoride (KF), potassium sulfate (K 2SO4), potassium nitrate (KNO 3), potassium hydrogen sulfate (KHSO 4), and sodium hydrogen sulfate (NaHSO 4).
In some alternative embodiments of the application, the strong base weak acid salt is selected from potassium ferrate (K 2FeO4), potassium carbonate (K 2CO3).
In some alternative embodiments of the application, the strong acid weak base salt is selected from the group consisting of ammonium chloride (NH 4 Cl), ammonium sulfate ((NH 4)2SO4), and ammonium nitrate (NH 4NO3).
In some alternative embodiments of the application, the weak acid weak base salt is selected from ammonium bicarbonate (NH 4HCO3).
In some alternative embodiments of the application, the electrolyte is selected from the group consisting of inorganic acids, inorganic bases, and strong acid strong base salts, and the inorganic acids and the inorganic bases cannot be present in the same electrolyte solution at the same time.
In some embodiments of the application, the electrolyte is selected from inorganic acids. Further, in some embodiments of the application, the mineral acid is selected from sulfuric acid, e.g., 98wt% concentrated sulfuric acid, and the like.
In some embodiments of the application, the electrolyte is selected from strong acid and strong base salts. Further, in some embodiments of the application, the strong acid strong base salt is selected from the group consisting of sodium chloride (NaCl), sodium fluoride (NaF), sodium sulfate (Na 2SO4), and potassium sulfate (K 2SO4).
In some embodiments of the application, the electrolyte is selected from inorganic bases. Further, in some alternative embodiments of the application, the inorganic base is selected from NaOH.
In some alternative embodiments of the application, the electrolyte comprises an inorganic base selected from NaOH and KOH and a strong acid strong base salt selected from NaF, KF, naCl and KCl.
In some alternative embodiments of the application, the molar concentration of OH - in the electrolyte solution is 0.1-20mol/L, X - and the molar concentration is 0.5-1.5mol/L; x - is selected from F - and Cl -. Wherein X - is used for assisting the anion OH - to play a role in electrolytic pulverization of the waste cathode carbon blocks so as to further obtain a high-purity high-quality carbon powder product through flotation.
In some alternative embodiments of the application, X - is selected from F -.
In some alternative embodiments of the application, X - comprises F - and Cl -, and the molar ratio of F - to Cl - is 1 or more; for example: 1:1, 2:1, 2.33:1, 7:3, 2.5:1, 3:1, 4:1, 5.25:1, 6.14:1, 6.2:1, 9:1, etc.
In some alternative embodiments of the application, the molar ratio of F - to Cl - is (4-6.2): 1.
In some alternative embodiments of the present application, in step S1, the electrolysis temperature of the electrolysis process is selected from 20-200 ℃; for example: 25 ℃,30 ℃,35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 95 ℃,100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, etc. If the electrolyte solution is water as solvent, the electrolysis process can be carried out under normal pressure when the electrolysis temperature is lower than 100 ℃; when the electrolysis temperature is equal to or higher than 100 ℃, the electrolysis process may be performed by selecting conventional techniques for preventing the electrolyte solution from boiling, such as a high-pressure environment.
In some alternative embodiments of the application, the electrolytic process controls the current density to between 0.1 and 100A/cm 2.
In some alternative embodiments of the present application, in step S1, the power source used in the electrolysis method is selected from a direct current power source or an alternating current power source.
In some embodiments of the application, in step S1, the power source used for the electrolysis is selected from a direct current power source.
In some alternative embodiments of the application, the direct current is selected from a constant current direct current power supply or a constant voltage direct current power supply.
In some alternative embodiments of the application, the constant current dc power source has a current of 4-20A; for example: 5A, 6A, 7A, 8A, 9A, 10A, 11A, 12A, 13A, 14A, 15A, 16A, 17A, 18A, 19A, etc.
In some alternative embodiments of the application, the constant voltage dc power supply has a voltage of 0.1 to 100V; for example: 1V, 2V, 3V, 4V, 5V, 6V, 7V, 8V, 9V, 10V, 15V, 20V, 25V, 30V, 35V, 40V, 45V, 50V, 55V, 60V, 65V, 70V, 75V, 80V, 85V, 90V, 95V, etc.
In some alternative embodiments of the present application, in step S1, the cathode material used in the electrolytic process is selected from metals and conductive ceramics.
In some alternative embodiments of the present application, the metal is selected from the group consisting of iron (Fe), tungsten (W), copper (Cu), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), titanium (Ti), zirconium (Zr), lead (Pd), cadmium (Cd), niobium (Nb), yttrium (Y), rhodium (Rh), tantalum (Ta), platinum (Pt), and germanium (Ge).
In some alternative embodiments of the application, the conductive ceramic is selected from WC、TiC、NbC、Cr3C2、Mo2C、VC、ZrC、SiC、V2O5、Ag2S、TiO2、Nb2O5、CdO、CsO、MoO3、CdS、WO3、BaO、SnO2、Ta2O5、BaTiO3、PbCrO4、ZnO、ZnF2、Fe2O3、 and Cr2O3、MnO、CoO、NiO、Cu2O、SnO、Pr2O3、Sb2S3、MoO2、SiC、Co3O4、TiS2、Mn3O4、WC、TiC、NbC、Cr3C2、Mo2C、VC、ZrC、SiC、CuAl2O4、NiAl2O4、CuCr2O4、NiCr2O4、ZnCr2O4、FeAl2O4、CrB2、TaB2、ZrB2、TiB2、ReB2、Mo2FeB2、Mo2NiB2、WCoB、CaB6、NiFe2O4 and CuFe 2O4.
In some embodiments of the application, in step S1, the cathode material used in the electrolytic process is selected from metals.
In some embodiments of the application, the metal is selected from tungsten (W).
In some alternative embodiments of the application, in step S2, the means of solid-liquid separation is selected from filtration (e.g., suction filtration), centrifugation, sedimentation and decantation.
In some alternative embodiments of the present application, in step S2, the liquid obtained after the solid-liquid separation of the solid-liquid mixture is subjected to oxidation treatment and then can be recycled as the electrolyte solution in step S1. Wherein, the oxidation treatment can be to introduce or add an oxidant into the electrolyte in the electrolytic process, or can be to introduce or add the oxidant into the electrolyte after the electrolysis is finished so as to eliminate CN -. The oxidant is selected from Cl2、ClO2、H2SO4、Na2O2、H2O2、O2、HNO3、 chlorite, perchlorate, permanganate, ferrate, and perchlorate, etc.
In some alternative embodiments of the application, in step S3, the concentration of the flotation is selected from 5-50wt%, e.g. 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, etc.
In some embodiments of the application, in step S3, the concentration of the flotation is selected from 30wt%.
In some alternative embodiments of the application, in step S3, the flotation process includes rougher, cleaner and scavenger. Wherein the number of roughings, the carefully chosen and the number of sweeps are each independently selected from 1, 2, 3,4 or 5. For example, roughing 1 time, refining 1 time, scavenging 1 time; roughing for 1 time, selecting for 2 times and scavenging for 1 time; roughing for 2 times, selecting for 2 times and scavenging for 2 times; roughing for 3 times, selecting for 2 times and scavenging for 2 times; roughing 2 times, selecting 1 time, scavenging 1 time, etc.
In some alternative embodiments of the application, in step S3, the agent for flotation comprises a collector and a frother. The collector is selected from the group consisting of carbon float based agents such as coal and graphite, including but not limited to hydrocarbon oil collectors such as diesel oil and kerosene, and combination collectors comprising hydrocarbon oil, emulsifiers, fusel, oleic acid, and the like. The foaming agent is selected from the foaming agents such as coal, graphite, and other common hydroxy compounds, ether and ether alcohols, pyridine and ketone, such as terpineol oil, fatty alcohol, sodium dodecyl benzene sulfonate, and heavy pyridine.
In some embodiments of the application, the collector is selected from diesel.
In some embodiments of the application, the foaming agent is selected from the group consisting of pinitol oils.
In some alternative embodiments of the application, in step S3, the pH of the flotation is selected from 5-11, e.g. 5.5、6、6.5、7、7.1、7.2、7.3、7.4、7.5、7.6、7.7、7.8、7.9、8.0、8.1、8.2、8.3、8.4、8.5、8.6、8.7、8.8、8.9、9、9.5、10、10.5, etc.
In some alternative embodiments of the application, in step S3, the stirring speed of the flotation is between 1000 and 3000r/min; for example: 1500r/min, 2000r/min, 2500r/min, etc.
In some alternative embodiments of the application, in step S4, the means of solid-liquid separation is selected from sedimentation, filtration, centrifugation, sedimentation or decantation.
In some alternative embodiments of the present application, in step S4, the drying means is selected from drying, air drying, natural drying, and the like.
In some alternative embodiments of the application, in step S5, the temperature of the calcination is 350-650 ℃; for example: 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, etc.
In summary, the application has the following beneficial effects:
According to the application, the waste cathode carbon blocks are electrolyzed and pulverized by an electrolysis method, the electrolyte products after separation and purification in the waste cathode carbon blocks can be recycled in aluminum electrolysis production, the pulverized carbon powder has a particle size reaching a micron level and uniform particle size distribution, and the high-purity high-value carbon powder is conveniently obtained by flotation.
Drawings
FIG. 1 is a graph showing the particle size distribution of the solid powder obtained in step S2 in example 1 of the present application;
FIG. 2 is an SEM image of the solid powder obtained in step S2 of example 1 of the application;
FIG. 3 is a graph showing the particle size distribution of the solid powder obtained in step S2 in example 16 of the present application;
Fig. 4 is an SEM image of the solid powder obtained in step S2 in example 16 of the present application.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples
The waste cathode carbon blocks of the aluminum electrolysis cell used in the following examples are from a manufacturer in Henan.
Cutting the waste cathode carbon blocks into a plurality of waste cathode carbon block samples with the size of 9cm multiplied by 6cm multiplied by 3 cm. Randomly selecting three waste cathode carbon block samples, mechanically crushing the three waste cathode carbon block samples, and further grinding the three waste cathode carbon block samples until the fineness is less than or equal to 100 meshes. The waste cathode material mainly contains phases such as carbon (C), cryolite (Na 3AlF6), alumina (Al 2O3), sodium fluoride (NaF), calcium fluoride (CaF 2) and the like through XRD detection. The chemical components and the content of the waste cathode carbon blocks are detected by elemental analysis, and the detection results are shown in table 1.
TABLE 1 chemical composition and content of waste cathode carbon blocks
Element(s) C Na Al Ca F Others
Content by weight percent 46.5 15.3 6.5 0.8 12.1 18.8
Example 1
In this embodiment, a method for treating a waste cathode carbon block with high value specifically includes the following steps:
S1, taking a waste cathode carbon block sample as an anode, taking a tungsten plate with the size of 10cm multiplied by 5cm multiplied by 1cm as a cathode, respectively placing the anode and the cathode in an electrolytic tank with the length of 30cm multiplied by 20cm multiplied by the height of 20cm, and placing 3000ml of electrolyte solution in the electrolytic tank, and electrifying by a constant-current direct-current power supply to pulverize the waste cathode carbon block to obtain a solid-liquid mixture; wherein the electrolyte aqueous solution is selected from concentrated sulfuric acid, the direct current is 10A, and the electrolysis temperature is 50 ℃;
S2, standing the solid-liquid mixture obtained in the step S1 for 24 hours at 20 ℃, then carrying out solid-liquid separation in a suction filtration mode to obtain a filter cake, washing the filter cake once with 20ml of water, and drying the filter cake for 24 hours in an anaerobic environment at a drying temperature of 100 ℃ to obtain solid powder; wherein, the liquid obtained after the solid-liquid mixture is subjected to solid-liquid separation can be used as the electrolyte solution in the step S1 for recycling;
S3, floating the solid powder obtained in the step S2 to obtain carbon powder ore pulp and electrolyte ore pulp; the flotation process comprises the following steps: roughing for 2 times, selecting for 2 times and scavenging for 2 times, wherein the collector for flotation is selected from diesel oil, the foaming agent for flotation is selected from pine oil, the flotation concentration is 30wt%, the pH value for flotation is 8, and the stirring rotation speed is 2000r/min.
S4, sequentially carrying out solid-liquid separation and drying on the carbon powder ore pulp obtained in the step S3 to obtain a carbon powder product;
S5, evaporating and calcining the ore pulp at 500 ℃ in sequence to obtain an electrolyte product.
The solid powder obtained in step S2 of example 1 was subjected to particle size distribution and scanning electron microscope detection, wherein the particle size distribution detection result is shown in fig. 1, and the scanning electron microscope detection result is shown in fig. 2.
As can be seen from fig. 1 and fig. 2, the present application adopts an electrolytic process to electrolytically pulverize the waste cathode carbon blocks, and the solid powder obtained in step S2 has a particle size up to micron level and uniform particle size distribution, so as to facilitate flotation in the subsequent step to obtain high purity carbon powder.
Examples 2 to 6
Examples 2-6 differ from example 1 only in that: the aqueous electrolyte solution used in step S1 is different. Among them, the results of the detection of the aqueous electrolyte solutions and the solid powder, carbon powder products and electrolyte products used in examples 1 to 6 are shown in Table 2.
TABLE 2
As can be seen from Table 2, the fluorine element in the waste cathode carbon blocks can be separated more thoroughly by pulverizing the waste cathode carbon blocks by adopting an electrolytic method. Wherein, the fluorine content in the solid powder obtained after the electrolysis in the step S2 in the example 1 is as low as 0.037wt%, the ash content is as low as 1.29wt%, and the fixed carbon content is as high as 91.59wt%.
And when the electrolyte aqueous solution is inorganic acid, strong acid and strong alkali salt or inorganic alkali, the carbon powder product with high carbon content and the electrolyte product with high electrolyte content are obtained. Among them, the results of the test of example 1 using an inorganic acid and example 2 using an inorganic base were comparable and superior to those of examples 3 to 6 using a strong acid and strong base salt.
Examples 7 to 15
Examples 7-14 differ from example 1 only in that: the aqueous electrolyte solution used in step S1 is different. Wherein the electrolyte in the aqueous electrolyte solution used in example 7 was NaOH, the electrolyte in the aqueous electrolyte solution used in example 8 was composed of NaOH and NaF, the electrolyte in the aqueous electrolyte solution used in example 9 was composed of NaOH and NaCl, and the electrolytes in the aqueous electrolyte solutions used in examples 10 to 15 were composed of NaOH, naF and NaCl. Among them, the results of the detection of the aqueous electrolyte solutions and the solid powder, carbon powder products and electrolyte products used in examples 7 to 15 are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, the use of electrolytes composed of NaOH and NaF and/or NaCl also completely separated the fluorine element from the waste cathode carbon blocks and resulted in carbon powder products with high carbon content and electrolyte products with high electrolyte content.
As is evident from a comparison of examples 7-9, the concentration of anions in the electrolyte solutions in examples 7-9 are the same, but the anions in example 7 are OH -, the anions in example 8 are OH - and F -, and the anions in example 9 are OH - and Cl -. The electrolyte products obtained in examples 7-9 were comparable in electrolyte content. The carbon powder products obtained in examples 7 and 9 had comparable carbon content. However, the carbon content of the carbon powder product obtained in example 8 was significantly improved (93.25 wt% in example 7, 93.24wt% in example 9, 96.80wt% in example 8) compared to examples 7 and 9.
As is evident from a comparison of examples 10-15, the molar ratios of OH - and X - were the same in examples 10-15, but the molar ratios of F - and Cl - included in X - were different. The electrolyte products obtained in examples 10-15 were comparable in electrolyte content. For the carbon powder product, as the molar ratio of F - to Cl - decreases, the carbon content in the carbon powder product increases and then decreases.
Wherein the carbon content in the carbon powder product (92.55 wt% in example 15) is slightly lower than the case where X - is Cl - (93.24 wt% in example 9) at a molar ratio of F - to Cl - of 1:1; the carbon content in the carbon powder product (example 11 was 97.33wt%, example 12 was 99.35wt%, example 13 was 98.51 wt%) was significantly higher than in the case of X - being Cl - (example 9 was 93.24 wt%) and X - being F - (example 8 was 96.80 wt%) when the molar ratio of F - to Cl - was in the range of the interval 6:1 to 4:1.
Example 16
Example 16 differs from example 1 only in that the power supply used was a constant voltage dc power supply with a voltage of 5V.
The solid powder obtained in step S2 of example 16 was subjected to particle size distribution and scanning electron microscope detection, wherein the particle size distribution detection result is shown in fig. 3 and the scanning electron microscope detection result is shown in fig. 4.
As can be seen from fig. 3 and fig. 4, the present application uses a constant voltage dc power supply to electrolyze and pulverize the waste cathode carbon blocks, and the solid powder obtained in step S2 has a particle size up to micron level and uniform particle size distribution, so that the high purity carbon powder is obtained by flotation in the subsequent step.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present application, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the application, and are also considered to be within the scope of the application.

Claims (32)

1. The high-value treatment method for the waste cathode carbon blocks is characterized by comprising the following steps of:
S1, placing the waste cathode carbon blocks in an electrolyte solution, and pulverizing the waste cathode carbon blocks by an electrolytic method by taking the waste cathode carbon blocks as anodes to obtain a solid-liquid mixture;
The electrolyte in the electrolyte solution is selected from inorganic acid, inorganic base, strong acid strong base salt, strong base weak acid salt, strong acid weak base salt and weak acid weak base salt, and the inorganic acid and the inorganic base cannot exist in the same electrolyte solution at the same time;
S2, sequentially carrying out solid-liquid separation, washing and drying on the solid-liquid mixture to obtain solid powder;
S3, carrying out flotation on the solid powder to obtain carbon powder ore pulp and electrolyte ore pulp;
S4, sequentially carrying out solid-liquid separation and drying on the carbon powder ore pulp to obtain a carbon powder product;
S5, evaporating and calcining the electrolyte pulp in sequence to obtain an electrolyte product.
2. The method for the high-value treatment according to claim 1, wherein the inorganic acid is selected from the group consisting of sulfuric acid, nitric acid, perchloric acid, ferric acid and hydrochloric acid.
3. The method for high-value treatment according to claim 1, wherein the inorganic base is selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, aluminum hydroxide and magnesium hydroxide.
4. The method for high-value treatment according to claim 1, wherein the strong acid and strong base salt is selected from the group consisting of sodium chloride, sodium fluoride, sodium sulfate, sodium nitrate, potassium chloride, potassium fluoride, potassium sulfate, potassium nitrate, potassium hydrogen sulfate and sodium hydrogen sulfate.
5. The method for high-value treatment according to claim 1, wherein the strong alkali weak acid salt is selected from the group consisting of potassium ferrate, potassium carbonate and potassium bicarbonate.
6. The method for high-value treatment according to claim 1, wherein the strong acid weak base salt is selected from the group consisting of ammonium chloride, ammonium sulfate and ammonium nitrate.
7. The method of claim 1, wherein the weak acid weak base salt is selected from ammonium bicarbonate.
8. The method of claim 1, wherein the electrolyte is selected from the group consisting of inorganic acids.
9. The method for high-value processing according to claim 8, wherein the inorganic acid is selected from the group consisting of sulfuric acid, nitric acid and hydrochloric acid.
10. The method for high value processing according to claim 8, wherein the inorganic acid is selected from sulfuric acid.
11. The method of claim 1, wherein the electrolyte is selected from the group consisting of inorganic bases.
12. The method for high value processing according to claim 11, wherein the inorganic base is selected from the group consisting of sodium hydroxide and potassium hydroxide.
13. The method for high value processing according to claim 11, wherein the inorganic base is selected from sodium hydroxide.
14. The method according to claim 1, wherein in step S1, the electrolysis temperature of the electrolysis method is selected from 20 to 200 ℃.
15. The method according to claim 1, wherein in step S1, the electrolytic method controls the current density to be between 0.1 and 100A/cm 2.
16. The method according to claim 15, wherein in step S1, the power source used for the electrolytic method is selected from a direct current power source and an alternating current power source.
17. The method according to claim 15, wherein in step S1, the power source used for the electrolytic method is selected from a direct current power source.
18. The method for high-value processing according to claim 17, wherein the dc power supply is selected from a constant current dc power supply and a constant voltage dc power supply.
19. The method according to claim 18, wherein the constant current dc power supply has a current of 4 to 20A.
20. The method for high-value processing according to claim 18, wherein the constant voltage dc power supply has a voltage of 0.1 to 100V.
21. The method according to claim 1, wherein in step S1, the cathode material used in the electrolytic method is selected from a metal and a conductive ceramic.
22. The method of claim 21, wherein the metal is selected from the group consisting of iron (Fe), tungsten (W), copper (Cu), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), titanium (Ti), zirconium (Zr), lead (Pd), cadmium (Cd), niobium (Nb), yttrium (Y), rhodium (Rh), tantalum (Ta), platinum (Pt), and germanium (Ge).
23. The method of claim 21, wherein the conductive ceramic is selected from WC、TiC、NbC、Cr3C2、Mo2C、VC、ZrC、SiC、V2O5、Ag2S、TiO2、Nb2O5、CdO、CsO、MoO3、CdS、WO3、BaO、SnO2、Ta2O5、BaTiO3、PbCrO4、ZnO、ZnF2、Fe2O3、 and Cr2O3、MnO、CoO、NiO、Cu2O、SnO、Pr2O3、Sb2S3、MoO2、SiC、Co3O4、TiS2、Mn3O4、WC、TiC、NbC、Cr3C2、Mo2C、VC、ZrC、SiC、CuAl2O4、NiAl2O4、CuCr2O4、NiCr2O4、ZnCr2O4、FeAl2O4、CrB2、TaB2、ZrB2、TiB2、ReB2、Mo2FeB2、Mo2NiB2、WCoB、CaB6、NiFe2O4 and CuFe 2O4.
24. The method for high-value processing according to claim 1, wherein in step S2, the solid-liquid separation is performed by at least one means selected from the group consisting of filtration, centrifugation, sedimentation and decantation.
25. The method according to claim 1, wherein in step S2, the liquid obtained by subjecting the solid-liquid mixture to solid-liquid separation is subjected to oxidation treatment and then recycled as the electrolyte solution in step S1.
26. The high value treatment method according to claim 1, characterized in that in step S3, the concentration of the flotation is selected from 5-50wt%.
27. The method according to claim 26, wherein in step S3, the flotation process includes roughing, refining and scavenging; wherein the number of roughings, the carefully chosen and the number of sweeps are each independently selected from 1, 2, 3, 4 or 5.
28. The method of claim 26, wherein in step S3, the agent for flotation contains a collector and a foaming agent.
29. The high value processing method of claim 28, wherein said collector is selected from the group consisting of diesel.
30. The method of claim 28, wherein the foaming agent is selected from the group consisting of pinitol oils.
31. The method of claim 26, wherein in step S3, the pH of the flotation is selected from the range of 5 to 11.
32. The method according to claim 26, wherein in step S3, the stirring speed of the flotation is 1000-3000r/min.
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