Resin carbon anode base and its manufacturing method, base intermediate and its manufacturing method, carbon anode and its manufacturing method

Abstract

The present invention provides a resin carbon anode raw material. The resin carbon anode raw material is cured to obtain a resin carbon anode raw material intermediate, and the resin carbon anode raw material intermediate has the following pattern characteristics when tested by gas chromatography mass spectrometry: characteristic peaks at retention times of 4.95±0.3 min, 5.32±0.3 min, 5.47±0.3 min, and 5.92±0.3 min, respectively. The present invention also provides a method for producing the resin carbon anode raw material. The present invention also provides a resin carbon anode raw material intermediate, a resin carbon anode, and the corresponding methods for producing and using them.

Description

[Technical field]

[0001] The present invention relates to the technical field of carbon industry, in particular to a resin carbon anode base and its manufacturing method, a base intermediate and its manufacturing method, a carbon anode and its manufacturing method. [Background technology]

[0002] Prebaked anode is an anode material used in the electrolytic aluminum industry, which is used to produce metallic aluminum by electrolytic alumina. It is an important raw material in the electrolytic alumina industry. At present, the main raw material of anode is petroleum coke, which is bound with coal pitch and then molded, roasted and other steps are used to make it. Coal pitch is used as a binder, which releases harmful substances such as sulfur dioxide at high temperatures, pollutes the environment and reduces the product yield. In addition, in the process of using coal pitch to make anode, the temperature during molding is about 145℃, and after molding, it needs to be put into water and cooled to increase the strength, and then roasted for 20-30d to complete the anode product, so the process is complicated, the pass rate is low and the pollution is serious.

[0003] Phenolic resin is a polymer synthesized under alkaline or acidic conditions using phenol and formaldehyde as raw materials. It has good wettability with carbon materials and a large amount of carbon remaining at high temperatures. Currently, phenolic resin is widely used in fire-resistant and high-temperature resistant materials as a graphite infiltrating agent. In conventional technology, phenolic resin has a large amount of carbon remaining and at the same time has excellent wettability and adhesion to carbon materials, but phenolic resin contains a large amount of hard carbon after carbonization and is difficult to graphitize, resulting in high resistivity.

[0004] On the other hand, phenolic resin can effectively reduce the resistivity after carbonization after modification, but the currently modified phenolic resin contains a large amount of sulfur or metal ions, and when applied to aluminum anodes, it will cause secondary contamination of the anode. It is urgent to provide a phenolic resin with low sulfur and metal content and excellent low-temperature carbonization properties. Summary of the Invention

[0005] In order to solve the above problems, the present invention aims to provide a resin carbon anode green body that contains a modified phenolic resin having a low sulfur content, a low metal content, and excellent low-temperature carbonization properties, and that can detect the pattern characteristics of the phenolic resin by a gas chromatography mass spectrometry test after being treated under appropriate conditions, and a manufacturing method thereof.

[0006] 1. A resin carbon anode raw material, which is obtained by hardening the resin carbon anode raw material to obtain a resin carbon anode raw material intermediate, and which has a spectral characteristic having characteristic peaks with retention times of 4.95±0.3 min, 5.32±0.3 min, 5.47±0.3 min, and 5.92±0.3 min in the order thereof when tested by gas chromatography-mass spectrometry. 2. The resin carbon anode base intermediate has a spectral characteristic having characteristic peaks in the following order of retention times in gas chromatography mass spectrometry testing: 4.95±0.3 min, 5.32±0.3 min, 5.47±0.3 min, 5.92±0.3 min, 6.10±0.3 min, 6.40±0.3 min, and 6.50±0.3 min, as described in item 1. 3. The resin carbon anode base intermediate has a gas chromatography mass spectrometry spectrum as shown in FIG. 1, the resin carbon anode base described in item 1. 4. The resin carbon anode material described in any one of items 1-3, wherein the gas chromatograph mass spectrometer used in the gas chromatography mass spectrometry technical test is 7890B / 5977B GC / MSD, and the column is a VF-1701MS capillary column. 5. The resin carbon anode material according to any one of items 1 to 4, wherein the resin carbon anode material is obtained by kneading and molding a mixture containing a modified phenolic resin and an aggregate, and preferably, the modified phenolic resin is heated to 30 to 50°C before the kneading process.

[0007] 6. The modified phenolic resin is one or more of a lignin-modified phenolic resin, a polyphenol compound-modified phenolic resin, and a polyhydroxy compound-modified phenolic resin; Preferably, the lignin is acidic lignin, the polyphenol compound is one or more selected from pyrogallol, tea polyphenol, tannic acid and tannin extract, and the polyhydroxy compound is one or more selected from maltose, sucrose, glucose, fructose, oxidized starch, sorbitol, and dextrin. The resin carbon anode base according to item 5. 7. The aggregate is one or more of calcined coke with a particle size of 8 mm-5 mm, calcined coke with a particle size of 5 mm-3 mm, calcined coke with a particle size of 3-1 mm, calcined coke with a particle size of 1 mm-0 mm, and fine calcined coke with a particle size of less than 0.075 mm; Item 6. The resin carbon anode material according to item 5, wherein the mass ratio of the total weight of the aggregate is 5 to 20 wt% calcined coke having a particle diameter of 8 to 5 mm, 10 to 25 wt% calcined coke having a particle diameter of 5 to 3 mm, 15 to 30 wt% calcined coke having a particle diameter of 3 to 1 mm, 10 to 20 wt% calcined coke having a particle diameter of 1 to 0 mm, and 25 to 45 wt% fine calcined coke having a particle diameter of less than 0.075 mm. 8. In the kneading treatment, the kneading time is 10 to 100 minutes, the kneading temperature is 40 to 60°C, and the kneading time is preferably 20 to 60 minutes; Preferably, in the kneading step, the modified phenolic resin is added continuously within 10 minutes to 30 minutes until the addition is completed, More preferably, the flow rate of the modified phenolic resin during continuous addition is 1 kg / s to 3 kg / s. 9. The resin carbon anode base material according to any one of items 5 to 8, wherein the modified phenolic resin is 5 to 15 parts and the aggregate is 85 to 95 parts based on the total weight of the resin carbon anode base raw material. 10. The resin carbon anode material according to item 5, wherein the molding process is performed by using an electric screw press or a vibration press.

[0008] 11. The resin carbon anode material according to any one of items 1 to 10, wherein the resin carbon anode material is a mixture containing modified phenolic resin and aggregate, kneaded and molded, then cured, and then tested by gas chromatography-mass spectrometry, wherein the temperature of the curing process is 120 to 270°C, and the thermal decomposition temperature selected for the test is 600°C. 12. Material mixing: The materials to be mixed include modified phenolic resin and aggregate; Mixing process: Mixing time is 10-100min. Molding process: Molding with an electric screw press or a vibration press. Preferably, the modified phenolic resin is heated to 30 to 50° C. before the kneading treatment, More preferably, in the kneading step, the modified phenolic resin is added continuously within 10 min to 30 min until the addition is completed, and the mixing temperature is 40 to 60° C.; More preferably, the flow rate of the modified phenolic resin during continuous addition is 1 kg / s to 3 kg / s. 13. A resin carbon anode raw intermediate obtained by hardening the raw material described in any one of items 1 to 10, wherein the volatile content of the raw intermediate is 0.4-2%; Preferably, the bulk density of the dough intermediate is 1.6 to 1.8 g / m 3 and More preferably, the curing temperature is 120 to 270° C., and the curing time is 1 to 10 hours. 14. Material mixing: The materials to be mixed include modified phenolic resin and aggregate; Mixing process: Mixing time is 10-100min. Molding process: Molding with an electric screw press or a vibration press. Hardening: hardening temperature is 120-270℃, hardening time is 1-10h. Preferably, the modified phenolic resin is heated to 30 to 50° C. before the kneading treatment, More preferably, in the kneading step, the modified phenolic resin is added continuously within 10 min to 30 min until the addition is completed, and the mixing temperature is 40 to 60° C.; Item 14. The method for producing a resin carbon anode raw intermediate according to Item 13, wherein the flow rate of the modified phenolic resin during continuous addition is 1 kg / s to 3 kg / s. 15. A carbon anode obtained by kneading, molding, hardening, and roasting a mixed material containing a modified phenolic resin and an aggregate, or by hardening and roasting a resin carbon anode material described in any one of items 1 to 10, or by roasting a resin carbon anode material intermediate described in item 12.

[0009] 16. The modified phenolic resin is one or more of a lignin-modified phenolic resin, a polyphenol compound-modified phenolic resin, and a polyhydroxy compound-modified phenolic resin; Item 16. The carbon anode according to item 15, wherein the lignin is acidic lignin, the polyphenol compound is one or more selected from pyrogallol, tea polyphenol, tannic acid and tannin extract, and the polyhydroxy compound is one or more selected from maltose, sucrose, glucose, fructose, oxidized starch, sorbitol, and dextrin. 17. The aggregate is one or more of the following: calcined coke with a particle size of 8-5 mm, calcined coke with a particle size of 5-3 mm, calcined coke with a particle size of 3-1 mm, calcined coke with a particle size of 1-0 mm, and fine calcined coke with a particle size of less than 0.075 mm; Item 16. The carbon anode according to item 15, wherein the mass ratio of the total weight of the aggregate is 5 to 20 wt% calcined coke having a particle size of 8 to 5 mm, 10 to 25 wt% calcined coke having a particle size of 5 to 3 mm, 15 to 30 wt% calcined coke having a particle size of 3 to 1 mm, 10 to 20 wt% calcined coke having a particle size of 1 to 0 mm, and 25 to 45 wt% fine calcined coke having a particle size of less than 0.075 mm. 18. The resin carbon anode according to item 15, wherein the modified phenolic resin is 5 to 15 parts and the aggregate is 85 to 95 parts based on the total weight of the resin carbon anode raw material. 19. In the above kneading treatment, the kneading time is 10 to 100 min, the kneading temperature is 40 to 60° C., and the kneading time is preferably 20 to 60 min; Preferably, in the kneading step, the modified phenolic resin is added continuously within 10 minutes to 30 minutes until the addition is completed, More preferably, the flow rate of the modified phenolic resin during continuous addition is 1 kg / s to 3 kg / s. 20. The carbon anode according to item 16, wherein the molding process is carried out using an electric screw press or a vibration press.

[0010] 21. In the above hardening treatment, the hardening temperature is 120-270°C, and the hardening time is 1-10h; Preferably, the roasting treatment includes increasing the temperature from room temperature -270°C to 550-1100°C while the carbon is embedded, and setting the roasting treatment time to 20-250 hours; Preferably, the carbon anode has a loss on ignition of 2 to 6% compared to the carbon anode raw intermediate; More preferably, the roasting treatment is performed under carbon burial conditions or inert gas protection conditions; More preferably, the roasting treatment is a microwave roasting treatment, an oven roasting treatment, a tunnel kiln roasting treatment, a down-flame kiln roasting treatment, a multi-chamber ring roasting furnace roasting treatment, a muffle furnace roasting treatment or a roasting furnace roasting treatment. 22. The carbon anode according to item 21, wherein in the roasting treatment, the heating rate is 3-60°C / h in the stage of room temperature-270°C; 3-60°C / h in the stage of 270-500°C; 10-50°C / h in the stage of 500-800°C; and 10-30°C / h in the stage of 800-1100°C. 23. Material mixing: The mixed materials include modified phenolic resin and aggregate; Mixing process: Mixing time is 10-100min. Molding process: Molding with friction press or vibration press, Hardening: hardening temperature 120-270℃, hardening time 1-10h. 23. The method for producing a carbon anode according to any one of items 15 to 22, comprising a step of heating from room temperature -270°C to 550-1100°C. 24. Use of the carbon anode according to any one of items 15-22 or the carbon anode produced by the method according to item 23 in aluminum electrolysis.

[0011] The technical effects of the present invention are as follows: (1) When the resin carbon anode material described in the present invention is cured at a temperature of less than 270°C, the characteristic peak of phenol resin can be detected by gas chromatography-mass spectrometry. (2) The resin carbon anode raw intermediate described in the present invention has suitable compressive strength and bulk density before high-temperature roasting, which can reduce the crack defect rate during roasting, improve the pass rate of carbon anode products, and save the roasting time, greatly improving the production efficiency of carbon anode products. (3) The carbon anode described in the present invention adopts phenolic resin to largely or completely replace coal pitch, thereby improving the denseness of the structure of the carbon anode and at the same time improving the strength, and ensuring the conductivity of the carbon anode, so that good electrochemical properties can be obtained, the electrochemical reaction activity of the anode can be improved, the amount of electrical energy consumed during electrolysis can be reduced, and the cost efficiency can be improved. (4) In the present invention, phenolic resin is used as a binder, and there is no need to heat the material during the kneading and molding processes, which reduces the process steps; after the green carbon block hardens and solidifies, it has very high strength and dimensional stability, and can be heated rapidly at a temperature of 200-400°C, shortening the process time and reducing production costs. At the same time, the entire production process and electrolysis process are more environmentally friendly, and it has the prospect of wide application. (5) The carbon anode described in the present invention has excellent strength and electrical conductivity and can be used in the electrolysis of alumina, thereby improving the cost efficiency. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 is a diagram showing the gas chromatography mass spectrum of Example 2-1. [Diagram 2] FIG. 2 is a diagram showing a gas chromatography mass spectrum of Comparative Example 2-1. [Diagram 3] FIG. 3 is a diagram showing a gas chromatography mass spectrum of Comparative Example 3-1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. It should be noted that the terms "comprise", "consist" or "contain" referred to in the entire specification and claims are open terms, and should be interpreted as "including but not limited to". The specification later describes preferred embodiments for carrying out the present invention, but the description is intended for the general principles of the specification and is not intended to limit the scope of the present invention. The scope of protection of the present invention is subject to that defined by the appended claims.

[0014] In the present application, the formed phenolic resin has a hydroxyl-containing aromatic ring constituent unit mainly derived from a prepolymer formed from phenol and formaldehyde and lignin, and is represented by the following formula (I) (wherein R is a methylol group or a propyl group, and R' is a methoxy group or a methylene group), and further, the molecular weight range of a polymer containing a certain amount of this structure can be calculated. The molecular weight and molecular weight distribution of the obtained phenolic resin are measured using gel permeation chromatography, the area of ​​the molecular weight distribution of the phenolic resin polymer in a certain molecular weight range is analyzed, and the proportion of that area to the entire distribution area, i.e., the proportion of the polymer in the molecular weight range to the total weight of the phenolic resin, is calculated, and the weight proportion of the polymer having a certain amount of aromatic ring structure with a hydroxyl group is determined.

[0015] The resin carbon anode material provided by the present invention is cured to obtain a resin carbon anode intermediate, which has the following spectrum characteristics when measured by gas chromatography mass spectrometry: characteristic peaks at retention times of 4.95±0.3 min, 5.32±0.3 min, 5.47±0.3 min, and 5.92±0.3 min, in that order.

[0016] In one specific embodiment of the present invention, the resin carbon anode raw intermediate has the following spectral characteristics when tested by gas chromatography mass spectrometry: characteristic peaks with retention times in the order of 4.95±0.3 min, 5.32±0.3 min, 5.47±0.3 min, 5.92±0.3 min, 6.10±0.3 min, 6.40±0.3 min and 6.50±0.3 min.

[0017] In one specific embodiment of the present invention, in a test by gas chromatography mass spectrometry, there are no characteristic peaks at retention times of 9.7±0.3 min, 11.6±0.3 min, 12.9±0.3 min, and 15.9±0.3 min, i.e., no characteristic peaks belonging to coal pitch are detected.

[0018] In one specific embodiment of the present invention, the gas chromatography mass spectrometry result of the resin carbon anode raw material intermediate is shown in FIG. 1, and the specific analysis results of the characteristic peaks shown in FIG. 1 are shown in Table 1.

[0019] [Table 1-1]

[0020] [Table 1-2]

[0021] In some specific embodiments of the present invention, the gas chromatography mass spectrometry technique test conditions are test conditions known to those skilled in the art.

[0022] In some specific embodiments of the present invention, the test conditions of the gas chromatography mass spectrometry technique are as follows: the gas chromatograph mass spectrometer is a 7890B / 5977B GC / MSD equipped with an EGA / PY-3030D pyrolyzer and Masshunter collection and qualitative software; the column is a VF-1701MS capillary column.

[0023] In some specific embodiments of the present invention, the test conditions of the gas chromatography mass spectrometry technique are as follows: the gas chromatography mass spectrometer is an Agilent 5975C-7890 AGC-MS analyzer, and the chromatographic column is an HP-5MS 5% PhenylMethylSilox capillary column.

[0024] In some specific embodiments of the present invention, the test conditions of the gas chromatography mass spectrometry technique are as follows: the gas chromatograph mass spectrometer is Agilent 5975C-7890A; the column is HP-5MS capillary column.

[0025] In some specific embodiments of the present invention, the test conditions of the gas chromatography mass spectrometry technique are as follows: the gas chromatograph mass spectrometer is SHIMADU GCMS-QP2010Plus, and the column is DB-5HT.

[0026] In some specific embodiments of the invention, the samples are tested according to instructions, the embodiments comprising: Transferring a small amount of sample into a sample cup; Connecting the sample cup to a manual injector using a connecting rod and fixing the injector to the pyrolysis apparatus; Compiling and running gas chromatography sample sequences; After the pyrolysis software issues a sample injection warning, start the execution program, and the sample will start pyrolysis, enter the chromatography column for separation, and be detected by mass spectrometry; The detection results are then qualitatively analyzed.

[0027] In some specific embodiments of the present invention, the carbon anode material is obtained by kneading a mixture containing a modified phenolic resin and an aggregate, and then molding the mixture.

[0028] In some specific embodiments of the present invention, the modified phenolic resin is one or more of a lignin-modified phenolic resin, a polyphenol compound-modified phenolic resin, and a polyhydroxy compound-modified phenolic resin; Preferably, the lignin is acidic lignin, the polyphenol compound is one or more selected from pyrogallol, tea polyphenol, tannic acid and tannin extract, and the polyhydroxy compound is one or more selected from maltose, sucrose, glucose, fructose, oxidized starch, sorbitol and dextrin.

[0029] In one specific embodiment of the present invention, the modified phenolic resin may be modified by any method known to those skilled in the art.

[0030] In one specific embodiment of the present invention, the modified phenolic resin is obtained by reacting a phenolic compound, a hydroxy compound, an aldehyde compound, and a carbonization promoter under the action of a catalyst.

[0031] In one specific embodiment of the present invention, 100 parts of phenol and an appropriate amount of catalyst are charged into a reaction vessel, the temperature is raised to 90-120°C, 20-100 parts of lignin are added, phenolation is carried out for 1-5 hours, the temperature is lowered to 80-82°C, 100-150 parts of 37% formaldehyde and a modified carbonization accelerator are added, and after the addition is completed, the temperature is raised to 88-90°C, the viscosity is controlled to 100-350 cp, dehydration is performed to 3-9%, and the product is discharged.

[0032] In some specific embodiments of the present invention, the phenolic resin modified with lignin, polyphenolic compounds, or polyhydroxy compounds may be obtained by modification using methods known to those skilled in the art.

[0033] Put 100 parts of phenol and an appropriate amount of acid catalyst into a reaction vessel, heat to 90-120°C, add 20-100 parts of lignin, phenolize for 1-5 hours, cool to 80-82°C, add 100-150 parts of 37% formaldehyde and a modified carbonization accelerator, and after the addition is complete, heat to 88-90°C, control the viscosity to 100-350cp, dehydrate to 3-9%, and discharge the product.

[0034] In one specific embodiment of the present invention, 100 parts of phenol and an appropriate amount of catalyst are charged into a reaction vessel, the temperature is raised to 90-100°C, 10-60 parts of fructose and 10-20 parts of resorcinol are added, the temperature is maintained for 1-2 hours, the temperature is lowered to 80-82°C, 100-150 parts of 37% formaldehyde and a modified carbonization accelerator are added, and after the addition is completed, the temperature is raised to 90-95°C, the viscosity is controlled to 100-350 cp, the dehydration is adjusted to 3-9%, and the product is discharged.

[0035] In one specific embodiment of the present invention, 100 parts of phenol and an appropriate amount of catalyst are charged into a reaction vessel, the temperature is raised to 80-90°C, 110-180 parts of 37% formaldehyde and a modified carbonization accelerator are added, and after the addition is completed, the temperature is raised to 90-95°C and kept at that temperature for 1-3 hours, 30-70 parts of tannin extract are added, the viscosity is controlled to 100-350 cp, dehydration is adjusted to 3-9%, and the product is discharged.

[0036] In one specific embodiment of the present invention, the phenolic resin of the present invention contains about 0.2 to 1.5% by weight of a carbonization accelerator based on the total weight of the modified phenolic resin, and the carbonization accelerator is one or more of compounds formed from boron element or transition element that are soluble in water or phenolic resin, and the transition element does not include elements of group IB and IIB, and the transition element may be elements such as iron, manganese, cobalt, titanium, nickel, and molybdenum. Examples of the carbonization accelerator include ammonium ferric citrate, manganese nitrate, cobalt sulfate, ferric chloride, nickel perchlorate, ammonium molybdate, and nickel acetate. In the present application, the total content of the carbonization accelerator in the phenolic resin can be calculated based on the amount of the added carbonization accelerator and the total amount of all reactive components forming the phenolic resin, and the content of the selected carbonization accelerator in the phenolic resin can also be measured based on a method well known to those skilled in the art. By adding a carbonization promoter, a fusion with carbon can be formed at high temperatures, and carbon can be precipitated as graphite crystals due to rearrangement of atoms within the compound, thereby improving the conductivity of the anode to a certain extent.

[0037] In a preferred embodiment of the present invention, the modified phenolic resin is produced by reacting a phenolic compound, an aldehyde compound, lignin, and a modifier under the action of a basic catalyst, where the phenolic compound may be phenol, cresol, cassinol, resorcin, alkylphenol, xyresol, octylphenol, nonylphenol, tert-butylphenol, cashew oil, bisphenol A, etc., and the aldehyde compound may be formaldehyde, trioxymethylene, paraoxymethylene, acetaldehyde, paraaldehyde, butyral, furfural, benzaldehyde, etc.

[0038] In one specific embodiment of the invention, the lignin is prepared from phenol, dioxane, acidic lignin and polyhydroxy compounds.

[0039] In some embodiments of the present invention, the aggregate comprises one or more of calcined coke with a particle size of 8 to 5 mm, calcined coke with a particle size of 5 to 3 mm, calcined coke with a particle size of 3 to 1 mm, calcined coke with a particle size of 1 to 0 mm, and finely powdered calcined coke with a particle size of less than 0.075 mm; Calcined coke with a particle size of 8-5 mm means calcined coke with a particle size of 8-5 mm; calcined coke with a particle size of 5-3 mm means calcined coke with a particle size of 5-3 mm; calcined coke with a particle size of 3-1 mm means calcined coke with a particle size of 3-1 mm; calcined coke with a particle size of 1-0 mm means calcined coke with a particle size of 1-0 mm; fine calcined coke with a particle size of less than 0.075 mm means fine calcined coke with a particle size of less than 0.075 mm.

[0040] In some embodiments of the present invention, the mass percentages based on the total weight of the aggregate are 5 to 20 wt% calcined coke having a particle size of 8 to 5 mm, 10 to 25 wt% calcined coke having a particle size of 5 to 3 mm, 15 to 30 wt% calcined coke having a particle size of 3 to 1 mm, 10 to 20 wt% calcined coke having a particle size of 1 to 0 mm, and 25 to 45 wt% fine calcined coke with a particle size of less than 0.075 mm.

[0041] For example, the calcined coke having a particle size of 8-5 mm may be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 wt % or any range therebetween; The calcined coke having a particle size of 5-3 mm may be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 wt % or any range therebetween; The calcined coke having a particle size of 3-1 mm may be 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 wt % or any range therebetween; The calcined coke having a particle size of 1-0 mm may be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 wt % or any range therebetween; Fine calcined coke having a particle size of less than 0.075 mm may be 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45 wt % or any range therebetween.

[0042] In some embodiments of the present invention, the modified phenolic resin is 5-15 parts and the aggregate is 85-95 parts by weight of the total weight of the resin carbon anode blank; For example, the modified phenolic resin may be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts or any range therebetween; The aggregate may be 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95 parts or any range therebetween.

[0043] In some embodiments of the present invention, the modified phenolic resin is heated to 30 to 50° C. before being kneaded; For example, the modified phenolic resin can be heated to 30, 35, 40, 45, 50° C. or any range therebetween.

[0044] In some embodiments of the present invention, in the kneading process, the modified phenolic resin is added continuously for 10 min to 30 min until the addition is completed; preferably, the flow rate of the modified phenolic resin during the continuous addition is 1 kg / S to 3 kg / S.

[0045] In some embodiments of the present invention, the kneading temperature is 40-60° C., for example, the kneading temperature may be 40, 45, 50, 55, 60° C. or any range therebetween.

[0046] In some embodiments of the present invention, the kneading process includes a kneading time of 10-100 min, preferably 20-60 min. Specifically, kneading is performed using a kneader for 10-100 min, and the kneading time in this application can ensure the stability of the process. If the kneading time is less than 10 min, the mixed material consisting of modified phenolic resin and aggregate does not reach sufficient mixing and infiltration, which seriously affects the stability of the product and is disadvantageous to the subsequent process; however, if the kneading time is more than 100 min, such as 120 min, the kneading time is too long, which will cause pre-hardening of the modified phenolic resin, affecting the molding performance and strength of the product.

[0047] In some embodiments of the present invention, the compacting process employs compaction in an electric screw press or a vibratory press.

[0048] In some embodiments of the present invention, the hardening temperature is 120-270°C, and the hardening time is 1-10 hours. In the present application, the hardening temperature should not exceed 270°C. For example, if the hardening temperature is 300°C, the surface of the carbon block will be oxidized. The hardening time should not be so long as to be disadvantageous to molding.

[0049] For example, the temperature of the curing process may be 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270°C or any range therebetween; The time for the curing process may be 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h or any range therebetween.

[0050] In some specific embodiments of the present invention, the resin carbon anode base is obtained by kneading and molding a mixture containing modified phenolic resin and aggregate, and after hardening, it is tested by gas chromatography mass spectrometry, where the hardening temperature is 120-270°C, and the pyrolysis temperature selected for testing is 600°C.

[0051] The present invention provides a method for producing the above-mentioned resin carbon anode material, wherein: Material mixing: the materials to be mixed include modified phenolic resin and aggregate; Kneading process: kneading time is 10-100min; Forming process: Forming by electric screw press or vibration press; Preferably, the modified phenolic resin is heated to 30 to 50° C. before the kneading treatment; More preferably, in the kneading step, the modified phenolic resin is added continuously within 10 minutes to 30 minutes until the addition is completed, and the mixing temperature is 40 to 60°C; More preferably, the flow rate of the modified phenol resin during continuous addition is 1 kg / s to 3 kg / s.

[0052] The present invention provides a resin carbon anode raw intermediate obtained by hardening the raw material, wherein the hardening temperature is 120-270°C, and the hardening time is 1-10 hours.

[0053] In some specific embodiments of the present invention, the dough intermediate volatile content is 0.4 to 2%.

[0054] Wherein, the volatile content is the weight ratio lost after the carbon anode raw material is cured. In the present invention, the volatile content is the ratio of the weight of the molded carbon anode raw material to the weight of the intermediate product after curing to the weight of the molded carbon anode raw material.

[0055] In some specific embodiments of the present invention, the bulk density of the dough intermediate body is 1.6 to 1.8 g / m 3 That is, The bulk density of the dough intermediate is 1.69 to 1.75 g / m 3 It is preferable that:

[0056] Wherein, bulk density means volume density. In the present invention, bulk density is calculated by the ratio of the weight of the carbon anode raw material intermediate to the volume of the raw material intermediate. The bulk density test method refers to GBT24528-2009, the method for determining bulk density of carbon materials.

[0057] In some specific embodiments of the present invention, the resin carbon anode raw intermediate is kneaded, molded and cured with a mixture containing modified phenolic resin and aggregate, and then tested by gas chromatography mass spectrometry, where the curing temperature is 120-270°C, and the pyrolysis temperature selected for the test is 600°C.

[0058] The present invention provides a carbon anode obtained from a mixture containing a modified phenolic resin and an aggregate through kneading, molding, curing and roasting processes.

[0059] In some specific embodiments of the present invention, the modified phenolic resin is one or more of a lignin-modified phenolic resin, a polyphenol compound-modified phenolic resin, and a polyhydroxy compound-modified phenolic resin; Preferably, the lignin is acidic lignin, the polyphenol compound is one or more selected from pyrogallol, tea polyphenol, tannic acid and tannin extract, and the polyhydroxy compound is one or more selected from maltose, sucrose, glucose, fructose, oxidized starch, sorbitol and dextrin.

[0060] The process for the modified phenolic resin is as described above and will not be repeated here.

[0061] In some embodiments of the present invention, the aggregate comprises one or more of calcined coke with a particle size of 8 to 5 mm, calcined coke with a particle size of 5 to 3 mm, calcined coke with a particle size of 3 to 1 mm, calcined coke with a particle size of 1 to 0 mm, and finely powdered calcined coke with a particle size of less than 0.075 mm.

[0062] The specifications for calcined coke with a particle size of 8 to 5 mm, calcined coke with a particle size of 5 to 3 mm, calcined coke with a particle size of 3 to 1 mm, calcined coke with a particle size of 1 to 0 mm, and fine calcined coke with a particle size of less than 0.075 mm are as described above and will not be repeated here.

[0063] In some embodiments of the present invention, the mass percentages based on the total weight of the aggregate are 5 to 20 wt% calcined coke having a particle size of 8 to 5 mm, 10 to 25 wt% calcined coke having a particle size of 5 to 3 mm, 15 to 30 wt% calcined coke having a particle size of 3 to 1 mm, 10 to 20 wt% calcined coke having a particle size of 1 to 0 mm, and 25 to 45 wt% fine calcined coke with a particle size of less than 0.075 mm.

[0064] In some embodiments of the present invention, the modified phenolic resin is 5-15 parts and the aggregate is 85-95 parts based on the total weight of the carbon anode raw material.

[0065] In some embodiments of the present invention, the compacting process employs compaction in an electric screw press or a vibratory press.

[0066] In some specific embodiments of the present invention, the temperature for the hardening treatment is 120 to 270° C., and the time for the hardening treatment is 1 to 10 hours.

[0067] In some specific embodiments of the present invention, the roasting treatment is performed under carbon-embedding conditions, with the temperature increased from room temperature -270°C to 550-1100°C, and the roasting treatment time is 20-250 hours.

[0068] In some specific embodiments of the present invention, the roasting process is a microwave roasting process, an oven roasting process, a tunnel kiln roasting process, an inverted flame kiln roasting process, a multi-chamber ring roasting furnace roasting process, a muffle furnace roasting process, or a roasting furnace roasting process.

[0069] In some specific embodiments of the present invention, during the roasting treatment, the heating rate is 3-60°C / h at the stage of room temperature-270°C; 3-60°C / h at the stage of 270-500°C; 10-50°C / h at the stage of 500-800°C, and 10-30°C / h at the stage of 800-1100°C.

[0070] The present invention provides a method for producing the above carbon anode, comprising the steps of: Material mixing: the materials to be mixed include modified phenolic resin and aggregate; Kneading process: kneading time is 10-100min; Forming process: Forming by friction press or vibration press; Hardening: hardening temperature 120-270℃, hardening time 1-10h; Roasting process: The temperature is raised from room temperature -270℃ to 550-1100℃. In the roasting treatment, the temperature is raised from room temperature -270°C to 550 to 1100°C with carbon embedded, and the roasting treatment time is 20 to 250 hours. Preferably, the roasting process is a microwave roasting process, an oven roasting process, a tunnel kiln roasting process, an inverted flame kiln roasting process, a multi-chamber ring-type roasting furnace roasting process, a muffle furnace roasting process or a roasting furnace roasting process.

[0071] In some specific embodiments of the present invention, in the kneading process, the modified phenolic resin is added continuously for 10 min to 30 min until the addition is completed; preferably, the flow rate of the modified phenolic resin during the continuous addition is 1 kg / s to 3 kg / s.

[0072] In some specific embodiments of the present invention, the modified phenol resin is heated to 30 to 50° C. before being kneaded.

[0073] The present invention provides a carbon anode manufactured from the above resin carbon anode substrate.

[0074] The present invention provides a method for producing a carbon anode from the resin carbon anode raw material, which is obtained by hardening and baking the resin carbon anode raw material to obtain a carbon anode.

[0075] In the roasting treatment, the temperature is raised from room temperature -270°C to 550 to 1100°C with carbon embedded, and the roasting treatment time is 20 to 250 hours.

[0076] In some embodiments of the invention, the carbon anode has a loss on ignition of 2-6% compared to the raw carbon anode intermediate.

[0077] Wherein, the ignition loss is the weight ratio of the carbon anode raw intermediate lost after the roasting treatment. In the present invention, the ignition loss is the ratio of the difference between the weight of the molded carbon anode raw intermediate and the weight of the finished carbon anode after roasting to the weight of the carbon anode raw intermediate.

[0078] The present invention provides a carbon anode produced from the above resin carbon anode blank intermediate.

[0079] The present invention provides a method for producing a carbon anode from the resin carbon anode raw intermediate obtained after roasting treatment, and the resin carbon anode raw intermediate is roasted to obtain a carbon anode; In the roasting treatment, the temperature is raised from room temperature -270°C to 550 to 1100°C with carbon embedded, and the roasting treatment time is 20 to 250 hours.

[0080] The present invention also provides the use of the above carbon anode in aluminum electrolysis.

[0081] The resin carbon anode material provided by the present invention can detect the characteristic absorption peak of phenolic resin by gas chromatography mass spectrometry after curing treatment, and can obtain a carbon anode after curing treatment and roasting treatment. The bulk density and pressure resistance indexes of the obtained carbon anode have small variation and are of more stable quality. EXAMPLES

[0082] The present invention generally and / or specifically describes the materials and test methods used in the tests, and in the following examples, unless otherwise specified, % stands for wt%, i.e., weight percentage. The manufacturers of the reagents and instruments used are not specified, and all are ordinary reagent products available for purchase on the market, and Table 2 shows the sources of the raw materials used in the examples.

[0083] [Table 2]

[0084] Example 1-1 Preparation of resin carbon anode material (a) Preparation of aggregate: 10 parts of calcined coke with a particle size of 8 to 5 mm, 15 parts of calcined coke with a particle size of 5 to 3 mm, 20 parts of calcined coke with a particle size of 3 to 1 mm, 10 parts of calcined coke with a particle size of 1 to 0 mm, and 40 parts of finely powdered calcined coke with a particle size of less than 0.075 mm were weighed out and placed in a mixer to be mixed uniformly. (b) Preparation of lignin-modified phenolic resin: 100 parts of phenol and an appropriate amount of catalyst were put into a reaction vessel, heated to 100°C, 70 parts of lignin were added, and phenolization was carried out for 2 hours. The temperature was then lowered to 80-82°C, 130 parts of 37% formaldehyde and a modified carbonization accelerator were added, and after the addition was completed, the temperature was raised to 88-90°C, the viscosity was controlled to 180-280cp, dehydration was adjusted to 4-7%, and the product was discharged. (c) The modified phenolic resin obtained in step (b) was heated to 40°C, 95 parts of the aggregate obtained in step (a) and 10 parts of the modified phenolic resin obtained in step (b) were mixed, and the modified phenolic resin was added continuously within 20 minutes at a flow rate of 2 kg / s until the end of addition. A kneader was used, and the kneading time was 30 minutes and the kneading temperature was 50°C. (d) The kneaded material kneaded in step (c) was placed in a specific mold and pressed under a pressure of 2500 tons using an electric screw press to obtain a resin carbon anode material.

[0085] Example 1-2 Preparation of resin carbon anode material The only difference between Example 1-2 and Example 1-1 is that the kneading time in step (c) is 10 minutes, and all other conditions are the same.

[0086] Example 1-3 Preparation of resin carbon anode material The only difference between Example 1-3 and Example 1-1 is that the kneading time in step (c) is 100 minutes, and all other conditions are the same.

[0087] Examples 1-4 Preparation of resin carbon anode material The only difference between Example 1-4 and Example 1-1 is that the kneading time in step (c) is 120 minutes, and all other conditions are the same.

[0088] Examples 1-5 Preparation of resin carbon anode material The only difference between Example 1-5 and Example 1-1 is that in step (c), the modified phenolic resin was not heated to 40°C. In other words, 95 parts of the aggregate obtained in step (a) and 10 parts of the modified phenolic resin obtained in step (b) were mixed using a kneader for a kneading time of 30 minutes at a kneading temperature of 50°C under room temperature conditions.

[0089] Examples 1-6 Preparation of resin carbon anode material The only difference between Example 1-6 and Example 1-1 is that in step (c), the modified phenolic resin obtained in step (b) is heated to 40°C, 95 parts of the aggregate obtained in step (a) and 10 parts of the modified phenolic resin obtained in step (b) are mixed, and the entire amount of the modified phenolic resin is added at once using a kneader, the kneading time is 30 minutes, and the kneading temperature is 50°C.

[0090] Examples 1-7 Preparation of resin carbon anode material The only difference between Example 1-7 and Example 1-1 is the composition of the aggregate, which is specifically as follows: Step (a): Preparation of aggregates: The total parts of aggregates, 20 parts of 0-1 mm petroleum coke, 20 parts of 1-2 mm petroleum coke, 20 parts of 2-4 mm petroleum coke, 15 parts of 4-8 mm petroleum coke, 30 parts of 180 mesh finely powdered petroleum coke, 5 parts of crushed graphite, and 5 parts of carbon nanotubes, were weighed and put into a mixer to mix uniformly.

[0091] Examples 1-8 Preparation of resin carbon anode material The difference between Example 1-8 and Example 1-1 is that in step (c), the kneading temperature was room temperature, and all other conditions were the same.

[0092] Comparative Example 1-1 (a) Preparation of aggregate: 10 parts of calcined coke with a particle size of 8 to 5 mm, 15 parts of calcined coke with a particle size of 5 to 3 mm, 20 parts of calcined coke with a particle size of 3 to 1 mm, 10 parts of calcined coke with a particle size of 1 to 0 mm, and 40 parts of finely powdered calcined coke with a particle size of less than 0.075 mm were weighed out and placed in a mixer to be mixed uniformly. (b) 95 parts of the aggregate obtained in step (a) was heated to 150°C, 10 parts of coal pitch powder preheated to 140°C was added, and the mixture was kneaded at 140°C for 30 minutes. (c) The mixture obtained in step (b) is placed in a specific mold and press-molded using a vibration molding machine.

[0093] Table 3 shows important parameters of Examples 1-1 to 1-8 and Comparative Example 1-1.

[0094] [Table 3]

[0095] Example 2-1 Preparation of resin carbon anode raw intermediate The resin carbon anode raw material prepared in Example 1-1 was cured at a curing temperature of 150°C for 3 hours to obtain a resin carbon anode raw material intermediate. The weights of the raw material intermediate before and after curing were detected, and the volatile content data of the raw material intermediate was calculated based on the weight difference before and after curing. As a result, the volatile content of the raw material intermediate was 1.05%. The resin carbon anode raw intermediate obtained in Example 2-1 was then analyzed by gas chromatography mass spectrometry, and the resin carbon anode raw intermediate had the gas chromatography mass spectrum shown in FIG.

[0096] Example 2-2 Preparation of resin carbon anode base intermediate The resin carbon anode raw material prepared in Example 1-5 was cured at a curing temperature of 150°C for 3 hours to obtain a resin carbon anode raw material intermediate. The weights of the raw material intermediate before and after curing were detected, and the volatile content data of the raw material intermediate was calculated based on the weight difference before and after curing. As a result, the volatile content of the raw material intermediate was 1.02%.

[0097] Example 2-3 Preparation of resin carbon anode base intermediate The resin carbon anode raw material prepared in Examples 1-6 was cured at a curing temperature of 150°C for 3 hours to obtain a resin carbon anode raw material intermediate. The weights of the raw material intermediate before and after curing were detected, and the volatile content data of the raw material intermediate was calculated based on the weight difference before and after curing. As a result, the volatile content of the raw material intermediate was 0.98%.

[0098] Example 2-4 Preparation of resin carbon anode base intermediate The resin carbon anode raw material prepared in Examples 1-7 was cured at a curing temperature of 150°C for 3 hours to obtain a resin carbon anode raw material intermediate. The weight of the raw material intermediate before and after curing was detected, and the data of the volatile content of the raw material intermediate was calculated based on the weight difference before and after curing. As a result, the volatile content of the raw material intermediate was 0.97%.

[0099] Example 2-5 Preparation of resin carbon anode raw intermediate The resin carbon anode raw material prepared in Example 1-8 was cured at a curing temperature of 150°C for 3 hours to obtain a resin carbon anode raw material intermediate. The weights of the raw material intermediate before and after curing were detected, and the volatile content data of the raw material intermediate was calculated based on the weight difference before and after curing. As a result, the volatile content of the raw material intermediate was 0.98%.

[0100] Example 2-6 Preparation of resin carbon anode base intermediate The resin carbon anode raw material prepared in Example 1-1 was cured at a curing temperature of 300°C for 2 hours to obtain a resin carbon anode raw material intermediate. The weights of the raw material intermediate before and after curing were detected, and the volatile content data of the raw material intermediate was calculated based on the weight difference before and after curing. As a result, the volatile content of the raw material intermediate was 1.3%.

[0101] Example 2-7 Preparation of resin carbon anode base intermediate The resin carbon anode raw material prepared in Example 1-1 was cured at a curing temperature of 90°C for 12 hours to obtain a resin carbon anode raw material intermediate. The weights of the raw material intermediate before and after curing were detected, and the volatile content data of the raw material intermediate was calculated based on the weight difference before and after curing. As a result, the volatile content of the raw material intermediate was 0.4%.

[0102] Examples 2-8 The only difference between Example 2-8 and Example 2-1 is that the curing time is 8 hours and the volatile content of the dough intermediate is 1.3%.

[0103] Examples 2-9 The only difference between Example 2-9 and Example 2-1 is that the curing time is 30 minutes and the volatile content of the dough intermediate is 0.3%.

[0104] Comparative Example 2-1 The carbon anode raw intermediate press-molded in Comparative Example 1-1 was water-cooled for 12 hours, naturally dried, and then analyzed by gas chromatography-mass spectrometry. The carbon anode raw intermediate obtained in Comparative Example 2-1 was subjected to gas chromatography mass spectrometry as shown in FIG. 2, and the resin carbon anode raw intermediate had the gas chromatography mass spectrum shown in FIG.

[0105] [Table 4]

[0106] Example 3-1 Preparation of carbon anode The resin carbon anode raw intermediate prepared in Example 2-1 is put into a tunnel kiln for roasting treatment, in which the temperature is increased from room temperature to 1000°C under the condition of embedding carbon, in which the heating rate is 50°C / h at the stage of room temperature-270°C, the heating rate is 40°C / h at the stage of 270-500°C, the heating rate is 30°C / h at the stage of 500-800°C, and the heating rate is 25°C / h at the stage of 800-1000°C. Roasting is performed for 72 hours, and the weights of the carbon anode raw intermediate before and after roasting and the carbon anode finished product are weighed respectively, and the ignition loss of the carbon anode is 3.2% based on the weight difference between the two. After the roasting was completed, the temperature was gradually lowered and the product was removed from the oven to obtain the carbon anode.

[0107] Example 3-2 The resin carbon anode raw intermediate prepared in Example 2-2 is placed in a tunnel kiln and roasted under the same roasting conditions as in Example 3-1, and the ignition loss of the carbon anode is 3.2%.

[0108] Example 3-3 The resin carbon anode raw intermediate prepared in Example 2-3 is placed in a tunnel kiln and roasted under the same roasting conditions as in Example 3-1, and the ignition loss of the carbon anode is 3.3%.

[0109] Examples 3-4 The resin carbon anode raw intermediate prepared in Example 2-4 is placed in a tunnel kiln and roasted under the same roasting conditions as in Example 3-1, and the ignition loss of the carbon anode is 2.8%.

[0110] Examples 3-5 The intermediate resin carbon anode material prepared in Example 2-5 is placed in a tunnel kiln and roasted under the same roasting conditions as in Example 3-1, and the ignition loss of the carbon anode is 3.3%.

[0111] Examples 3-6 The intermediate resin carbon anode material prepared in Example 2-6 is placed in a tunnel kiln and roasted under the same roasting conditions as in Example 3-1, and the ignition loss of the carbon anode is 2.9%.

[0112] Examples 3-7 The resin carbon anode raw intermediate prepared in Example 2-7 is placed in a tunnel kiln and roasted, the roasting conditions are the same as those in Example 3-1, and the ignition loss of the carbon anode is 3.8%.

[0113] Examples 3-8 The resin carbon anode raw intermediate prepared in Example 2-8 is placed in a tunnel kiln and roasted, the roasting conditions are the same as those in Example 3-1, and the ignition loss of the carbon anode is 3.0%.

[0114] Examples 3-9 The resin carbon anode raw intermediate prepared in Example 2-9 is placed in a tunnel kiln and roasted, the roasting conditions are the same as those in Example 3-1, and the ignition loss of the carbon anode is 4.0%.

[0115] Examples 3-10 The intermediate resin carbon anode raw material prepared in Example 2-1 is put into a tunnel kiln to carry out roasting treatment, where the roasting treatment conditions are: under the condition of embedding carbon, heating from room temperature to 780°C, where the heating rate is 50°C / h at the stage of room temperature-270°C, the heating rate is 40°C / h at the stage of 270-500°C, and the heating rate is 30°C / h at the stage of 500-780°C. Roasting is carried out for 72 hours, and the weights of the intermediate carbon anode raw material and the finished carbon anode before and after roasting are weighed respectively, and the ignition loss of the carbon anode calculated based on the weight difference between the two is 2.7%.

[0116] Comparative Example 3-1 The carbon anode raw intermediate prepared in Comparative Example 2-1 is placed in a tunnel kiln and roasted, and the roasting process is the same as that in Example 3-1, and the ignition loss is 6.8%. The carbon anode raw intermediate obtained in Comparative Example 3-1 was analyzed by gas chromatography mass spectrometry, and the carbon anode raw intermediate had a gas chromatography mass spectrum as shown in FIG.

[0117] Comparative Example 3-2 The carbon anode raw intermediate prepared in Example 2-1 is roasted in a tunnel kiln, in which the roasting conditions are: carbon is embedded, the temperature is increased from room temperature to 500°C, in which the heating rate is 50°C / h from room temperature to 270°C; the heating rate is 40°C / h from 270°C to 500°C, and the roasting is performed for 72 hours, and the ignition loss is 1.8%.

[0118] [Table 5]

[0119] Experimental Example 1 The product obtained according to the present application, when tested by gas chromatography-mass spectrometry technique, has the following parameters: 1. Apparatus and Reagents 1.1 Gas chromatograph mass spectrometer: 7890B / 5977B GC / MSD, EGA / PY-3030D pyrolysis device and Masshunter collection and qualitative analysis software; 1.2 Column: VF-1701MS capillary column (30 m × 0.150 mm × 0.15 μ m); 1.3 High purity helium gas: 99.999%; 1.4 Sample cup: Eco-Cup LF; 1.5 Connecting rod: Ecostick SF, 1.6 Manual injector; 1.7 sample spoons. 2. Detection Method 2.1 Chromatography 2.1.1 Sample inlet temperature: 270℃; 2.1.2 Column 1 flow rate: 1ml / min; 2.1.3 Split ratio: 80:1; 2.1.4 Column temperature: initial temperature 60℃, kept for 0 minutes; heated to 260℃ at a heating rate of 20℃ / min, and kept for 30 minutes. 2.1.5 MSD transfer line temperature: 260℃. 2.2 Mass spectrometry 2.2.1 Ion source temperature: 230℃; 2.2.2 Quadrupole temperature: 150℃; 2.2.3 Ion source: Inert EI source; 2.2.4 Ionization energy: 70 eV; 2.2.3 Solvent delay: 0min; 2.2.4 Acquisition mode: Scan; 2.2.5 Scan range m / z: 10-500amu; 2.3 Pyrolysis method 2.3.1 Pyrolysis mode: single click; 2.3.2 Pyrolysis temperature: 600℃; 2.3.3 Pyrolysis time: 0.2min; 3. Sample Test 3.1 Carry out the methods for gas chromatography, mass spectrometry and pyrolysis equipment, and prepare the equipment. 3.2 Take a small amount of sample with the sample spoon and transfer it to the sample cup. 3.3 Connect the sample cup to the manual injector with a connecting rod and fix the injector to the pyrolysis apparatus. 3.4 Edit and run the sample injection sequence for the gas chromatography and pyrolysis software by clicking "Start". 3.5 When the instrument is ready, the pyrolysis software will issue a sample injection warning, then press the top button of the manual injector to drop the sample cup into the lining tube of the pyrolysis instrument, start the running program, and the sample will start pyrolysis, enter the chromatography column for separation, and be detected by the mass spectrometer. 3.6 Remove the sample cup after the run is completed. 3.7 Open the qualitative software to qualitatively analyze the measurement results.

[0120] The graph of the gas chromatography mass spectrometry of Example 2-1 is shown in FIG. 1; graphs similar to FIG. 1 can also be obtained for Examples 2-2 to 2-4.

[0121] The graph of gas chromatography mass spectrometry of Comparative Example 2-1 is shown in FIG. 2, and the test conditions of the gas chromatography mass spectrometry technique are the same as those in Example 2-1; The graph of gas chromatography mass spectrometry of Comparative Example 3-1 is shown in FIG. 3, and the test conditions of its gas chromatography mass spectrometry technique are the same as those in Example 2-1; Among them, in Figure 1, characteristic peaks clearly belonging to phenol resins can be seen. For example, characteristic peaks are observed at retention times of 4.95±0.3 min, 5.32±0.3 min, 5.47±0.3 min, 5.92±0.3 min, 6.10±0.3 min, 6.40±0.3 min, and 6.50±0.3 min. Table 1 shows that the characteristic groups corresponding to these characteristic peaks belong to the characteristic groups of phenol resins.

[0122] The specific analysis results of the characteristic peaks shown in FIG. 2 are shown in Table 6. Combining FIG. 2 with Table 6, it can be seen that in Comparative Example 2-1, without undergoing high-temperature roasting treatment, characteristic peaks that clearly belong to coal pitch can be obtained in the gas chromatography-mass spectrum. For example, characteristic peaks are found at retention times of 9.7±0.3 min, 11.6±0.3 min, 12.9±0.3 min, and 15.9±0.3 min, and Table 6 shows that the characteristic groups corresponding to these characteristic peaks all belong to the characteristic groups of coal pitch.

[0123] [Table 6-1]

[0124] [Table 6-2]

[0125] The specific analysis results of the characteristic peaks shown in FIG. 3 are shown in Table 7. Combining FIG. 3 and Table 7, in Comparative Example 3-1, after high-temperature roasting treatment at 1000°C, characteristic peaks of long-chain alkanes are observed in the gas chromatography-mass spectrum, for example, there are characteristic peaks at retention times of 1.56±0.3 min, 3.37±0.3 min, 4.88±0.3 min, and 5.60±0.3 min. According to Table 7, it can be seen that the characteristic groups corresponding to these characteristic peaks all belong to the characteristic groups of long-chain alkanes; characteristic peaks belonging to coal pitch are also observed, for example, there are characteristic peaks at retention times of 9.78±0.3 min, 10.53±0.3 min, 11.6±0.3 min, and 5.60±0.3 min. According to Table 7, it can be seen that the characteristic groups corresponding to these characteristic peaks all belong to the characteristic groups of coal pitch.

[0126] [Table 7-1]

[0127] [Table 7-2]

[0128] [Table 8]

[0129] Experimental Example 2: Indicator of intermediate dough The compressive strength of the intermediate body shall be inspected in accordance with the inspection method of YS / T285-2012.

[0130] [Table 9]

[0131] In Table 9, the absence of cracks or gaps in the outer shape of the resin carbon anode raw intermediate body and the outer shape being rounded was defined as 100%. Volatile content is an index of the degree of hardening. Volatile content is a characteristic value in principle, and it is most energy-saving to stop as soon as this value is reached. If the time is too short, the volatile content is low, and the impurities are not sufficiently volatilized at this temperature, which may cause anode cracking in the subsequent high-temperature roasting; if the time is too long, the volatile content will reach a certain value, but the energy consumption will increase.

[0132] Example 3 Carbon anode index Measure according to the bulk density measurement method YS / T285-2012.

[0133] [Table 10]

[0134] Although it has been made clear through the examples of this case that the above is not used to limit this case, a person having ordinary skill in the art may make some modifications and additions without departing from the spirit and scope of this case, and therefore the scope of protection of this case shall be based on that defined by the scope of the patent application attached later.

Claims

1. A resin carbon anode raw material, wherein the resin carbon anode raw material is cured to obtain a resin carbon anode raw material intermediate, and the resin carbon anode raw material intermediate has a spectral feature having characteristic peaks when the storage times are 4.95±0.3 min, 5.32±0.3 min, 5.47±0.3 min, and 5.92±0.3 min, respectively, in a test using gas chromatography-mass spectrometry.

2. The resin carbon anode raw material intermediate has a spectral feature with characteristic peaks at retention times of 4.95±0.3 min, 5.32±0.3 min, 5.47±0.3 min, 5.92±0.3 min, 6.10±0.3 min, 6.40±0.3 min and 6.50±0.3 min in gas chromatography-mass spectrometry; Preferably, the gas chromatograph mass spectrometer used in the gas chromatography mass spectrometry test is 7890B / 5977BGC / MSD, and the chromatography column is VF-1701MS capillary column; Preferably, the modified phenolic resin is obtained by kneading and molding a mixture containing a modified phenolic resin and an aggregate, and preferably, the modified phenolic resin is heated to 30 to 50°C before the kneading; Preferably, the modified phenolic resin is one or more of a lignin-modified phenolic resin, a polyphenol compound-modified phenolic resin, and a polyhydroxy compound-modified phenolic resin; Preferably, the lignin is acidic lignin, the polyphenol compound is one or more selected from pyrogallol, tea polyphenol, tannic acid and tannin extract, and the polyhydroxy compound is one or more selected from maltose, sucrose, glucose, fructose, oxidized starch, sorbitol and dextrin; Preferably, the aggregate is one or more of calcined coke with a particle size of 8 to 5 mm, calcined coke with a particle size of 5 to 3 mm, calcined coke with a particle size of 3 to 1 mm, calcined coke with a particle size of 1 to 0 mm, and finely powdered calcined coke with a particle size of less than 0.075 mm; Preferably, the mass proportions of the total weight of the aggregate are 5 to 20 wt% of calcined coke with a particle size of 8 to 5 mm, 10 to 25 wt% of calcined coke with a particle size of 5 to 3 mm, 15 to 30 wt% of calcined coke with a particle size of 3 to 1 mm, 10 to 20 wt% of calcined coke with a particle size of 1 to 0 mm, and 25 to 45 wt% of finely powdered calcined coke with a particle size of less than 0.075 mm; Preferably, in the kneading treatment, the kneading time is 10 to 100 minutes, the kneading temperature is 40 to 60°C, and the kneading time is preferably 20 to 60 minutes; Preferably, in the kneading step, the modified phenolic resin is added continuously within 10 to 30 minutes until the addition is completed; More preferably, the flow rate of the modified phenolic resin during continuous addition is 1 kg / s to 3 kg / s; Preferably, the modified phenolic resin is 5 to 15 parts and the aggregate is 85 to 95 parts based on the total weight of the resin carbon anode base raw material. The resin carbon anode fabric according to claim 1, characterized in that:

3. 3. The resin carbon anode material according to claim 2, wherein the molding process is carried out by an electric screw press or a vibration press.

4. The resin carbon anode material according to claim 1, characterized in that the resin carbon anode material is obtained by kneading and molding a mixture containing a modified phenolic resin and an aggregate, and is subjected to a gas chromatography mass spectrometry technical test after curing, the curing temperature being 120-270°C, and the pyrolysis temperature selected for the test being 600°C.

5. Material mixing: the materials to be mixed include modified phenolic resin and aggregate; Kneading treatment: kneading time is 10-100 min; Forming process: Forming by electric screw press or vibration press; Preferably, before the kneading treatment, the modified phenolic resin is heated to 30 to 50°C, More preferably, in the kneading step, the modified phenolic resin is continuously added at a mixing temperature of 40 to 60°C for 10 to 30 minutes until the addition is completed, More preferably, the flow rate of the modified phenolic resin during continuous addition is 1 kg / s to 3 kg / s, in accordance with the method for producing a resin carbon anode material according to any one of claims 1 to 4.

6. A resin carbon anode raw intermediate obtained by hardening the raw material according to claim 1, wherein the volatile content of the raw material intermediate is 0.4 to 2%; Preferably, the bulk density of the dough intermediate body is 1.6 to 1.8 g / m 3 and More preferably, the resin carbon anode raw intermediate is characterized in that the temperature for the curing treatment is 120 to 270°C and the time for the curing treatment is 1 to 10 hours.

7. Material mixing: the materials to be mixed include modified phenolic resin and aggregate; Kneading treatment: kneading time is 10-100 min; Forming process: Forming by electric screw press or vibration press; Hardening treatment: hardening temperature 120-270℃, hardening time 1-10h; Preferably, before the kneading treatment, the modified phenolic resin is heated to 30 to 50°C, More preferably, in the kneading step, the modified phenolic resin is continuously added at a mixing temperature of 40 to 60°C for 10 to 30 minutes until the addition is completed, More preferably, the flow rate of the modified phenolic resin during continuous addition is 1 kg / s to 3 kg / s.

8. A carbon anode obtained by subjecting a mixed material containing a modified phenolic resin and an aggregate to kneading, molding, hardening, and roasting treatments; or by subjecting the resin carbon anode raw material according to any one of claims 1 to 3 to hardening and roasting treatments; or by subjecting the resin carbon anode raw material intermediate according to claim 6 to roasting treatment.

9. The modified phenolic resin is one or more of a lignin-modified phenolic resin, a polyphenol compound-modified phenolic resin, and a polyhydroxy compound-modified phenolic resin, Preferably, the lignin is acidic lignin, the polyphenol compound is one or more selected from pyrogallol, tea polyphenol, tannic acid and tannin extract, and the polyhydroxy compound is one or more selected from maltose, sucrose, glucose, fructose, oxidized starch, sorbitol and dextrin; Preferably, the aggregate comprises one or more of the following: calcined coke with a particle size of 8-5 mm, calcined coke with a particle size of 5-3 mm, calcined coke with a particle size of 3-1 mm, calcined coke with a particle size of 1-0 mm, and finely ground calcined coke with a particle size of less than 0.075 mm; Preferably, the mass proportions of the total weight of the aggregate are 5 to 20 wt% of calcined coke with a particle size of 8 to 5 mm, 10 to 25 wt% of calcined coke with a particle size of 5 to 3 mm, 15 to 30 wt% of calcined coke with a particle size of 3 to 1 mm, 10 to 20 wt% of calcined coke with a particle size of 1 to 0 mm, and 25 to 45 wt% of finely powdered calcined coke with a particle size of less than 0.075 mm; Preferably, the modified phenolic resin is 5 to 15 parts and the aggregate is 85 to 95 parts based on the total weight of the carbon anode raw material. The carbon anode according to claim 8, characterized in that

10. In the kneading treatment, the kneading time is 10 to 100 minutes, and the kneading temperature is 40 to 60°C, preferably, the kneading time is 20 to 60 minutes; Preferably, in the kneading step, the modified phenolic resin is added continuously for 10 minutes to 30 minutes until the addition is completed, More preferably, the flow rate of the modified phenolic resin during continuous addition is 1 kg / s to 3 kg / s.

11. The carbon anode according to claim 9, wherein the molding process is carried out by an electric screw press or a vibration press.

12. The curing temperature is 120 to 270°C, and the curing time is 1 to 10 hours. Preferably, the roasting treatment is performed under the condition that the carbon is embedded, by increasing the temperature from room temperature -270°C to 550-1100°C, and the roasting treatment time is 20 to 250 hours; Preferably, the ignition loss of the carbon anode is 2 to 6% relative to the carbon anode raw intermediate; More preferably, the roasting treatment is carried out under carbon burial conditions or inert gas protection conditions, More preferably, the roasting treatment is a microwave roasting treatment, an oven roasting treatment, a tunnel kiln roasting treatment, a down-flame kiln roasting treatment, a multi-chamber ring roasting furnace roasting treatment, a muffle furnace roasting treatment, or a roasting furnace roasting treatment.

13. 13. The carbon anode according to claim 12, wherein, in the roasting treatment, the heating rate is 3-60°C / h in the stage from room temperature to 270°C; 3-60°C / h in the stage from 270 to 500°C; 10-50°C / h in the stage from 500 to 800°C; and 10-30°C / h in the stage from 800 to 1100°C.

14. Material mixing: the materials to be mixed include modified phenolic resin and aggregate; Mixing process: Mixing time is 10-100min; Forming process: forming by friction press or vibration press; Hardening: hardening temperature 120-270℃, hardening time 1-10h; 9. The method for producing a carbon anode according to claim 8, comprising: a roasting treatment: increasing the temperature from room temperature -270°C to 550-1100°C.

15. Use of the carbon anode according to claim 8 in aluminum electrolysis.

16. Use of a carbon anode produced by the method of claim 14 in aluminum electrolysis.

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