CN116409994A - Resin carbon anode green body and preparation method thereof, green body intermediate and preparation method thereof, carbon anode and preparation method thereof - Google Patents
Resin carbon anode green body and preparation method thereof, green body intermediate and preparation method thereof, carbon anode and preparation method thereof Download PDFInfo
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- CN116409994A CN116409994A CN202310018135.XA CN202310018135A CN116409994A CN 116409994 A CN116409994 A CN 116409994A CN 202310018135 A CN202310018135 A CN 202310018135A CN 116409994 A CN116409994 A CN 116409994A
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- carbon anode
- resin
- kneading
- phenolic resin
- modified phenolic
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 104
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- 229940078494 nickel acetate Drugs 0.000 description 1
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
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Abstract
The application provides a resin carbon anode green compact, resin carbon anode green compact obtains resin carbon anode green compact midbody after the hardening treatment, resin carbon anode green compact midbody has following spectrum characteristic when passing gas chromatography-mass spectrometry and combining technical test: characteristic peaks are present at retention times of 8.28.+ -. 0.3min, 12.7.+ -. 0.3min, 14.6.+ -. 0.3min and 19.0.+ -. 0.3min in this order. The invention also provides a preparation method of the resin carbon anode green body. In addition, the invention also provides a resin carbon anode green compact intermediate, a resin carbon anode, and a corresponding preparation method and application thereof.
Description
Technical Field
The invention relates to the technical field of carbon industry, in particular to a resin carbon anode green body and a preparation method thereof, a green body intermediate and a preparation method thereof, a carbon anode and a preparation method thereof.
Background
The prebaked anode is an anode material used in the electrolytic aluminum industry, is used for electrolyzing aluminum oxide to produce metal aluminum, and is an important raw material in the electrolytic aluminum oxide industry. At present, the main raw material of the anode is petroleum coke, which is prepared by combining coal pitch, forming and roasting. And coal pitch is used as an adhesive, harmful substances such as sulfur dioxide and the like can be emitted at high temperature, the environment is polluted, and the product yield is reduced. In addition, in the process of preparing the anode by using coal tar pitch, the temperature is about 145 ℃ during molding, the anode is required to be put into water after molding, water cooling is needed to improve the strength, and the anode finished product can be prepared by roasting for 20-30 days, so that the process is complex, the qualification rate is low, and the pollution is serious.
The phenolic resin is a high-molecular polymer synthesized by taking phenol formaldehyde as a raw material under the condition of alkali or acid, and has the characteristics of good wettability with carbon materials and high-temperature carbon residue. Phenolic resin is widely used as a sizing agent of graphite in refractory materials and high-temperature resistant materials at present. In the prior art, although the phenolic resin has higher carbon residue and excellent infiltration performance and bonding performance on carbon materials, the phenolic resin contains a large amount of hard carbon after carbonization, is difficult to graphitize, and has higher resistivity;
the modified phenolic resin can effectively reduce the resistivity of the carbonized phenolic resin, but the modified phenolic resin contains more sulfur content or metal ions, and secondary pollution is generated to the anode when the modified phenolic resin is applied to the anode for aluminum. There is a need to provide a phenolic resin having a low sulfur content, a low metal content and good low-temperature carbonization performance.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a resin carbon anode green body and a preparation method thereof, wherein the resin carbon anode green body contains modified phenolic resin with low sulfur content, less metal components and good low-temperature carbonization performance, and after being treated by adopting proper conditions, the spectrum characteristics of the phenolic resin can be detected through gas chromatography-mass spectrometry combined technology test.
The technical proposal of the invention is as follows
1. The resin carbon anode green compact is subjected to hardening treatment to obtain a resin carbon anode green compact intermediate, and the resin carbon anode green compact intermediate has the following spectrum characteristics when tested by a gas chromatography-mass spectrometry technology: characteristic peaks are present at retention times of 8.28.+ -. 0.3min, 12.7.+ -. 0.3min, 14.6.+ -. 0.3min and 19.0.+ -. 0.3min in this order.
2. The green resin carbon anode of item 1, which has the following profile characteristics when tested by gas chromatography-mass spectrometry techniques: characteristic peaks are arranged at the positions of retention time of 8.28+/-0.3 min, 10.34+/-0.3 min, 12.7+/-0.3 min, 14.6+/-0.3 min, 17.7+/-0.3 min and 19.0+/-0.3 min in sequence.
3. The green resin carbon anode of item 1, which has the following profile characteristics when tested by gas chromatography-mass spectrometry techniques: characteristic peaks are arranged at the positions of 8.28+/-0.3 min, 10.34+/-0.3 min, 12.7+/-0.3 min, 14.6+/-0.3 min, 17.7+/-0.3 min, 19.0+/-0.3 min, 26.5+/-0.3 min and 29.6+/-0.3 min in sequence.
4. The resin carbon anode green body of item 1, which has a gas chromatography-mass spectrometry spectrum as shown in fig. 1 or fig. 2.
5. The green resin carbon anode of any one of items 1 to 4, wherein a gas chromatograph-mass spectrometer used in the gas chromatograph-mass spectrometer test is 7890B/5977B GC/MSD, and the chromatographic column is a VF-1701MS capillary column.
6. The resin carbon anode green compact according to any one of items 1 to 3, which is obtained by kneading and molding a mixture comprising a modified phenolic resin, coal pitch, and an aggregate;
preferably, the modified phenolic resin is warmed to 30-50 ℃ prior to the kneading treatment.
7. The resin carbon anode green body according to item 6, wherein the modified phenolic resin is one or two or more selected from lignin-modified phenolic resins, polyphenol-modified phenolic resins, and polyol-modified phenolic resins;
preferably, the lignin is acidic lignin, the polyphenol compound is selected from one or more of pyrogallol, tea polyphenol, tannic acid and baking gum, and the polyhydroxy compound is selected from one or more of maltose, sucrose, glucose, fructose, oxidized starch, sorbitol and dextrin.
8. The resin carbon anode green compact of item 6, wherein the aggregate comprises one or more of calcined coke having a particle diameter of 8 to 5mm, calcined coke having a particle diameter of 5 to 3mm, calcined coke having a particle diameter of 3 to 1mm, calcined coke having a particle diameter of 1 to 0mm, and fine calcined coke having a particle diameter of less than 0.075 mm;
Preferably, the weight percentage of calcined coke with the particle size of 8-5mm is 5-20wt%, calcined coke with the particle size of 5-3mm is 10-25wt%, calcined coke with the particle size of 3-1mm is 15-30wt%, calcined coke with the particle size of 1-0mm is 10-20wt%, and fine powder calcined coke with the particle size of less than 0.075mm is 25-45wt%, based on the total weight of the aggregate.
9. The resin carbon anode green body according to item 6,
in the kneading treatment, the kneading time is 10-100min, the kneading temperature is 40-60 ℃, and the kneading time is preferably 20-60min;
preferably, in the kneading treatment step, the modified phenolic resin is continuously added within 10-30 min until the addition is completed;
further preferably, the flow rate of the modified phenolic resin is 1kg/s to 3kg/s when continuously added.
10. The resin carbon anode green body according to any one of claims 6 to 9, wherein the modified phenolic resin is 6 to 12wt%, the coal pitch is 1 to 5wt% and the aggregate is 83 to 93wt%, based on the total weight of the resin carbon anode green body raw material.
11. The resin carbon anode green body according to item 6, wherein the molding treatment is performed on an electric screw press or a vibration press.
12. The resin carbon anode green compact according to any one of claims 1 to 11, which is produced by subjecting a mixture comprising a modified phenolic resin, coal pitch and an aggregate to kneading treatment and molding treatment, and subjecting the mixture to a gas chromatography-mass spectrometry combined technical test after hardening treatment, wherein the hardening treatment temperature is 120 to 270 ℃ and the cracking temperature selected for the test is 600 ℃.
13. A method for producing a green resinous carbon anode according to any one of claims 1 to 12, wherein,
mixing materials: the mixed material comprises modified phenolic resin, coal pitch and aggregate;
kneading: kneading time is 10-100min;
and (3) forming: the method is characterized in that the molding is carried out on an electric screw press or a vibration press;
preferably, the modified phenolic resin is heated to 30-50 ℃ before the kneading treatment;
further preferably, in the kneading treatment step, the modified phenolic resin is continuously added within 10-30 min until the addition is completed, and the kneading temperature is 40-60 ℃;
further preferably, the flow rate of the modified phenolic resin is 1kg/s to 3kg/s when continuously added.
14. A resin carbon anode green body intermediate, obtained by hardening the green body according to any one of items 1 to 12, wherein the green body intermediate has a volatile content of 0 to 3.0%;
preferably, the green intermediate body density is 1.6-1.8g/m 3 ；
It is further preferable that the hardening treatment temperature is 120 to 270℃and the hardening treatment time is 1 to 10 hours.
15. A method of preparing the resin carbon anode green compact of claim 14, wherein,
mixing materials: the mixed material comprises modified phenolic resin, coal pitch and aggregate;
Kneading: kneading time is 10-100min;
and (3) forming: the method is characterized in that the molding is carried out on an electric screw press or a vibration press;
hardening treatment: the hardening treatment temperature is 120-270 ℃, and the hardening treatment time is 1-10h;
preferably, the modified phenolic resin is heated to 30-50 ℃ before the kneading treatment;
further preferably, in the kneading treatment step, the modified phenolic resin is continuously added within 10-30 min until the addition is completed, and the kneading temperature is 40-60 ℃;
further preferably, the flow rate of the modified phenolic resin is 1kg/s to 3kg/s when continuously added.
16. A carbon anode is prepared from the mixture of modified phenolic resin, coal pitch and aggregate through kneading, shaping, hardening and calcining; or the resin carbon anode green body of any one of the items 1 to 11 is obtained by hardening treatment and roasting treatment; or the resin carbon anode green compact intermediate according to item 13 is obtained by baking.
17. The carbon anode of item 16,
the modified phenolic resin is selected from one or more than two of lignin modified phenolic resin, polyphenol compound modified phenolic resin and polyhydroxy compound modified phenolic resin;
Preferably, the lignin is acidic lignin, the polyphenol compound is selected from one or more of pyrogallol, tea polyphenol, tannic acid and baking gum, and the polyhydroxy compound is selected from one or more of maltose, sucrose, glucose, fructose, oxidized starch, sorbitol and dextrin.
18. A carbon anode as in item 17,
the aggregate comprises one or more of calcined coke with particle size of 8-5mm, calcined coke with particle size of 5-3mm, calcined coke with particle size of 3-1mm, calcined coke with particle size of 1-0mm and fine powder calcined coke with particle size of less than 0.075 mm;
preferably, the weight percentage of calcined coke with the particle size of 8-5mm is 5-20wt%, calcined coke with the particle size of 5-3mm is 10-25wt%, calcined coke with the particle size of 3-1mm is 15-30wt%, calcined coke with the particle size of 1-0mm is 10-20wt%, and fine powder calcined coke with the particle size of less than 0.075mm is 25-45wt%, based on the total weight of the aggregate.
19. The carbon anode of item 16, wherein the modified phenolic resin is 6 to 12wt%, the coal pitch is 1 to 5wt%, and the aggregate is 83 to 93wt%, based on the total weight of the carbon anode raw material.
20. The carbon anode of item 16,
in the kneading treatment, the kneading time is 10-100min, the kneading temperature is 40-60 ℃, and the kneading time is preferably 20-60min;
Preferably, in the kneading treatment step, the modified phenolic resin is continuously added within 10-30 min until the addition is completed;
further preferably, the flow rate of the modified phenolic resin is 1kg/s to 3kg/s when continuously added.
21. The carbon anode of item 18, wherein the shaping process is performed on an electric screw press or a vibratory press.
22. The carbon anode of item 18, wherein in the hardening treatment: the hardening treatment temperature is 120-270 ℃, and the hardening treatment time is 1-10h;
preferably, the firing process includes: under the condition of carbon burying, the temperature is raised to 550-1100 ℃ from the room temperature to 270 ℃ and the roasting treatment time is 20-250h;
preferably, the carbon anode loss on ignition is from 2 to 7.5% compared to the carbon anode green intermediate;
further preferably, the roasting treatment is a treatment under a carbon burying condition or under an inert gas protection condition;
more preferably, the firing process is a microwave firing process, an oven firing process, a tunnel kiln firing process, a down-draft kiln firing process, a multi-chamber ring-type firing furnace firing process, a muffle furnace firing process, or a firing furnace firing process.
23. The carbon anode of item 22, wherein during the calcination treatment, the temperature is raised at a rate of 3 to 60 ℃/h at a temperature of between room temperature and 270 ℃;270-500 ℃ and the heating rate is 3-60 ℃/h; the temperature rising rate is 10-50 ℃/h in the 500-800 ℃ stage, and is 10-30 ℃/h in the 800-1100 ℃ stage.
24. A method of making the carbon anode of any one of claims 16-23, comprising the steps of:
mixing materials: the mixed material comprises modified phenolic resin and aggregate;
kneading: kneading time is 10-100min;
and (3) forming: forming on a friction press or a vibration press;
hardening treatment: the hardening treatment temperature is 120-270 ℃, and the hardening treatment time is 1-10h;
roasting: raising the temperature from room temperature to 270 ℃ to 550 to 1100 ℃.
25. Use of a carbon anode according to any one of claims 16-23, a carbon anode prepared according to the method of claim 24, for the electrolysis of aluminum.
The invention has the following technical effects:
(1) When the hardening treatment temperature is lower than 270 ℃, the characteristic peaks of phenolic resin and coal tar pitch can be detected by gas chromatography-mass spectrometry.
(2) The carbon anode adopts phenolic resin to replace coal pitch in a large amount or completely replace coal pitch, so that the structural compactness of the carbon anode is improved, the strength is improved, the conductivity of the carbon anode is ensured, the carbon anode has good electrochemical performance, the electrochemical reaction activity of the anode is improved, the consumption of electric energy in the electrolysis process is reduced, and the economic benefit is improved;
(3) According to the invention, phenolic resin is used as a binder, and the material is not required to be subjected to heating treatment in the kneading and forming processes, so that the process steps are reduced; after the raw carbon block is hardened and solidified, the strength and the dimensional stability are very high, the temperature can be quickly increased in the temperature stage of 200-400 ℃, the process time is shortened, the production cost is reduced, and meanwhile, the whole production process and the electrolysis process are more environment-friendly, so that the method has a great application prospect;
(4) The carbon anode has excellent strength and conductivity, can be used for electrolyzing aluminum oxide, and improves economic benefit.
Drawings
FIG. 1 shows a gas chromatograph-mass spectrum of example 2-1;
FIG. 2 shows the gas chromatography-mass spectrometry spectra of examples 2-8;
FIG. 3 shows a gas chromatograph-mass spectrum of comparative example 2-1;
FIG. 4 shows a gas chromatograph-mass spectrum of comparative example 3-1.
Detailed Description
The present invention will be described in detail below. It should be noted that, throughout the specification and claims, the terms "include," "comprising," or "includes" are to be construed as open-ended terms, and thus should be interpreted to mean "include, but not limited to. The description hereinafter sets forth a preferred embodiment for practicing the invention, but is not intended to limit the scope of the invention, as the description proceeds with reference to the general principles of the description. The scope of the invention is defined by the appended claims.
In the present application, the phenolic resin formed has hydroxyl-containing aromatic ring structural units mainly derived from a prepolymer formed from phenol and formaldehyde and lignin, and can be represented by the following formula (I) (wherein R is hydroxymethyl or propyl, and R' is methoxy or methylene), and thus the molecular weight range of a polymer containing a certain structure can be calculated; the molecular weight and molecular weight distribution of the obtained phenolic resin are determined by adopting gel permeation chromatography, the molecular weight distribution area of the phenolic resin polymer in a certain molecular weight range is analyzed, and the ratio of the area to the whole distribution area is calculated, namely the total weight percentage of the phenolic resin in the molecular weight range is calculated, so that the weight percentage of the polymer containing a certain number of aromatic ring structures with hydroxyl groups is determined.
The resin carbon anode green compact provided by the invention is subjected to hardening treatment to obtain a resin carbon anode green compact intermediate, and the resin carbon anode green compact intermediate has the following spectrum characteristics when tested by a gas chromatography-mass spectrometry technology: characteristic peaks are present at retention times of 8.28.+ -. 0.3min, 12.7.+ -. 0.3min, 14.6.+ -. 0.3min and 19.0.+ -. 0.3min in this order.
In some embodiments of the invention, the resin carbon anode green intermediate has the following profile when tested by gas chromatography-mass spectrometry techniques: characteristic peaks are arranged at the positions of retention time of 8.28+/-0.3 min, 10.34+/-0.3 min, 12.7+/-0.3 min, 14.6+/-0.3 min, 17.7+/-0.3 min and 19.0+/-0.3 min in sequence.
In some embodiments of the invention, the resin carbon anode green intermediate has the following profile when tested by gas chromatography-mass spectrometry techniques: characteristic peaks are arranged at the positions of 8.28+/-0.3 min, 10.34+/-0.3 min, 12.7+/-0.3 min, 14.6+/-0.3 min, 17.7+/-0.3 min, 19.0+/-0.3 min, 26.5+/-0.3 min and 29.6+/-0.3 min in sequence.
In some embodiments of the invention, the resin carbon anode green intermediate has a gas chromatograph-mass spectrum as shown in fig. 1 or fig. 2, wherein the specific analysis results of the characteristic peaks shown in fig. 1 are shown in table 1, and wherein the specific analysis results of the characteristic peaks shown in fig. 2 are shown in table 2.
TABLE 1 gas chromatography-mass spectrometry analysis results for resin carbon anode green compact intermediates corresponding to FIG. 1
TABLE 2 gas chromatography-mass spectrometry analysis results for resin carbon anode green compact intermediates corresponding to FIG. 2
In some embodiments of the invention, the gas chromatography-mass spectrometry combined technical test conditions are test conditions that can be known to those skilled in the art.
In some embodiments of the invention, the gas chromatography-mass spectrometry combined technical test conditions are as follows: the gas chromatograph-mass spectrometer is 7890B/5977B GC/MSD, matched with EGA/PY-3030D cracker and Masshunter acquisition and qualitative software; the chromatographic column is VF-1701MS capillary column.
In some embodiments of the invention, the gas chromatography-mass spectrometry combined technical test conditions are as follows: the gas chromatograph is Agilent5975C-7890AGC-MS, and the chromatographic column is HP-5MS5%PhenylMethylSilox capillary column.
In some embodiments of the invention, the gas chromatography-mass spectrometry combined technical test conditions are as follows: the gas chromatograph-mass spectrometer is Agilent5975C-7890A; the chromatographic column is HP-5MS capillary chromatographic column.
In some embodiments of the invention, the gas chromatography-mass spectrometry combined technical test conditions are as follows: the gas chromatograph is SHIMDU GCMS-QP2010Plus, and the chromatographic column is DB-5HT.
In some embodiments of the invention, the sample is tested according to instructions for use, wherein embodiments include the following:
Taking a small amount of sample and transferring the sample into a sample cup;
connecting a sample cup to a manual sample injector by a connecting rod, and fixing the sample injector to a cracking instrument;
editing a gas chromatography sample injection sequence and operating;
after the cracking software sends out a sample injection warning, starting an operation program, and starting to crack a sample and enter a chromatographic column for separation, wherein the sample is detected by mass spectrum;
and carrying out qualitative analysis on the detection result.
In some specific embodiments of the invention, the carbon anode green body is obtained by kneading and molding a mixed material comprising modified phenolic resin, coal pitch and aggregate.
In some embodiments of the invention, the modified phenolic resin is selected from one or more of lignin modified phenolic resin, polyphenol compound modified phenolic resin, polyhydroxy compound modified phenolic resin;
preferably, the lignin is acidic lignin, the polyphenol compound is selected from one or more of pyrogallol, tea polyphenol, tannic acid and baking gum, and the polyhydroxy compound is selected from one or more of maltose, sucrose, glucose, fructose, oxidized starch, sorbitol and dextrin.
In one embodiment of the present invention, the modified phenolic resin may be modified by methods known to those skilled in the art.
In one specific embodiment of the invention, the modified phenolic resin is prepared by reacting a phenolic compound, a hydroxyl compound and an aldehyde compound as a carbon forming agent under the action of a catalyst.
In a specific embodiment of the invention, 100 parts of phenol and a proper amount of catalyst are put into a reaction kettle, the temperature is raised to 90-120 ℃, 20-100 parts of lignin is added, the temperature is reduced to 80-82 ℃ for 1-5 hours, 100-150 parts of 37% formaldehyde and modified into a carbon agent are added, after the addition is finished, the temperature is raised to 88-90 ℃, the viscosity is controlled to 100-350cp, and the mixture is dehydrated to 3-9% and discharged.
In some embodiments of the present invention, lignin-modified phenolic resins, polyphenol-modified phenolic resins, polyhydroxy-modified phenolic resins may be modified by methods known to those skilled in the art.
Adding 100 parts of phenol and a proper amount of acid catalyst into a reaction kettle, heating to 90-120 ℃, adding 20-100 parts of lignin, phenolizing for 1-5h, cooling to 80-82 ℃, adding 100-150 parts of 37% formaldehyde and modified carbon forming agent, heating to 88-90 ℃ after the addition, controlling the viscosity to 100-350cp, dehydrating to 3-9%, discharging
In a specific embodiment of the invention, 100 parts of phenol and a proper amount of catalyst are put into a reaction kettle, the temperature is raised to 90-100 ℃, 10-60 parts of fructose and 10-20 parts of resorcinol are added, the temperature is kept for 1-2 hours, the temperature is reduced to 80-82 ℃, 100-150 parts of 37% formaldehyde and modified carbon agent are added, the temperature is raised to 90-95 ℃ after the addition is finished, the viscosity is controlled to 100-350cp, the dehydration is carried out to 3-9%, and the material is discharged.
In a specific embodiment of the invention, 100 parts of phenol and a proper amount of catalyst are put into a reaction kettle, the temperature is raised to 80-90 ℃, 110-180 parts of 37% formaldehyde and modified carbon agents are added, after the addition is finished, the temperature is raised to 90-95 ℃, the temperature is kept for 1-3 hours, 30-70 parts of baking glue is added, the medium-control viscosity is raised to 100-350cp, the dehydration is carried out to 3-9%, and the material is discharged.
In one embodiment of the present invention, the phenolic resin of the present invention contains about 0.2 to 1.5 wt% of a carbon former based on the total weight of the modified phenolic resin, the carbon former being one or more of boron or a water-soluble or phenolic resin compound formed by a transition element, and the transition element not including elements other than group ib and group ib, the transition element being an element such as iron, manganese, cobalt, titanium, nickel, molybdenum, or the like. The carbon forming agent may be, for example, ferric citrate amine, manganese nitrate, cobalt sulfate, ferric chloride, nickel perchlorate, ammonium molybdate, nickel acetate, and the like. In this application, the total amount of the char-forming agent in the phenolic resin may be calculated based on the amount of the char-forming agent added and the total amount of all the reaction components forming the phenolic resin, or the amount of the selected char-forming agent in the phenolic resin may be measured based on methods well known to those skilled in the art. The addition of the carbon forming agent can form fusion with carbon at high temperature, and carbon is crystallized and precipitated as graphite through rearrangement of atoms in the compound, so that the conductivity of the anode can be improved to a certain extent.
In a preferred embodiment of the present invention, the modified phenolic resin is prepared by reacting a phenolic compound, an aldehyde compound, lignin and a modifier in the presence of a basic catalyst. Wherein the phenolic compound can be phenol, cresol, cardanol, resorcinol, alkylphenol, xylenol, octylphenol, nonylphenol, tertiary butylphenol, cashew oil, bisphenol A and the like, and the aldehyde compound can be formaldehyde, trioxymethylene, paraformaldehyde, acetaldehyde, paraldehyde, butyraldehyde, furfural, benzaldehyde and the like.
In one embodiment of the invention, the lignin is made from phenol, dioxane, acid lignin and polyols.
In some embodiments of the invention, the aggregate comprises one or more of calcined coke with a particle size of 8-5mm, calcined coke with a particle size of 5-3mm, calcined coke with a particle size of 3-1mm, calcined coke with a particle size of 1-0mm, and fine calcined coke with a particle size of less than 0.075 mm;
calcined coke with the particle size of 8-5 mm; calcined coke with the particle size of 8-5 mm; the calcined coke with the particle size of 5-3mm refers to calcined coke with the particle size of 5-3 mm; the calcined coke with the particle size of 3-1mm refers to calcined coke with the particle size of 3-1 mm; the calcined coke with the particle size of 1-0mm refers to calcined coke with the particle size of 1-0 mm; the fine powder calcined coke with the particle size smaller than 0.075mm refers to the fine powder calcined coke with the particle size smaller than 0.075 mm.
In some embodiments of the invention, the weight percentage of calcined coke with the particle size of 8-5mm is 5-20wt%, the weight percentage of calcined coke with the particle size of 5-3mm is 10-25wt%, the weight percentage of calcined coke with the particle size of 3-1mm is 15-30wt%, the weight percentage of calcined coke with the particle size of 1-0mm is 10-20wt%, and the weight percentage of fine powder calcined coke with the particle size of less than 0.075mm is 25-45wt%.
For example, the calcined coke having a particle size of 8-5mm may be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20wt% or any range therebetween;
the calcined coke with the particle diameter of 5-3mm can be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25wt% or any range between the calcined coke and the calcined coke;
the calcined coke with the particle size of 3-1mm can be 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 weight percent or any range between the calcined coke and the calcined coke;
the calcined coke with the particle size of 1-0mm can be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 weight percent or any range between the calcined coke and the calcined coke;
the fine calcined coke having a particle size of less than 0.075mm may be 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45wt% or any range therebetween.
In some embodiments of the invention, the modified phenolic resin is 6-12wt%, the coal pitch is 1-5wt% and the aggregate is 83-93wt% based on the total weight of resin carbon anode green stock;
for example, the modified phenolic resin may be 6, 7, 8, 9, 10, 11, 12wt% or any range therebetween;
the coal pitch may be 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5wt% or any range therebetween;
the aggregate may be 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93wt% or any range therebetween.
In some embodiments of the invention, the modified phenolic resin is warmed to 30-50 ℃ prior to the kneading process;
for example, the modified phenolic resin may be warmed to 30, 35, 40, 45, 50 ℃ or any range therebetween.
In some embodiments of the invention, in the kneading treatment step, the modified phenolic resin is continuously added within 10min-30min until the addition is completed; preferably, the flow rate of the modified phenolic resin is 1kg/S to 3kg/S when continuously added.
In some embodiments of the invention, the kneading temperature is 40-60 ℃, e.g., the kneading temperature may be 40, 45, 50, 55, 60 ℃ or any range therebetween.
In some embodiments of the invention, the kneading process comprises: the kneading time is 10-100min, preferably 20-60min. Specifically, the kneading machine is adopted for kneading for 10-100min, and the kneading time in the application is that the stability of the process can be ensured. If the kneading time is less than 10min, the mixed materials consisting of the modified phenolic resin, the coal pitch and the aggregate cannot be fully mixed and infiltrated, so that the stability of the product is seriously affected, and the subsequent process is not facilitated; however, when the kneading time exceeds 100min, for example, 120min, the kneading time is too long, which causes pre-curing of the modified phenolic resin and affects the molding performance and strength of the product.
In some embodiments of the invention, the shaping process is performed on an electric screw press or a vibratory press.
In some embodiments of the invention, the hardening treatment comprises: the hardening treatment temperature is 120-270 ℃, the hardening treatment time is 1-10 hours, in the application, the hardening temperature cannot exceed 270 ℃, for example, when the hardening temperature is 300 ℃, the surface of the carbon block is oxidized; the hardening treatment time cannot be too long, which is unfavorable for molding.
For example, the hardening treatment temperature may be 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270 ℃ or any range therebetween;
The hardening treatment time may be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or any range therebetween.
In some specific embodiments of the invention, the resin carbon anode green body is prepared from a mixture comprising modified phenolic resin, coal pitch and aggregate through kneading treatment, forming treatment, hardening treatment and gas chromatography-mass spectrometry combined technical test, wherein the hardening treatment temperature is 120-270 ℃, and the cracking temperature selected for the test is 600 ℃.
The invention provides a method for preparing the resin carbon anode green body, wherein,
mixing materials: the mixed material comprises modified phenolic resin and aggregate;
kneading: kneading time is 10-100min;
and (3) forming: the method is characterized in that the molding is carried out on an electric screw press or a vibration press;
preferably, the modified phenolic resin is heated to 30-50 ℃ before the kneading treatment;
further preferably, in the kneading treatment step, the modified phenolic resin is continuously added within 10-30 min until the addition is completed, and the kneading temperature is 40-60 ℃;
further preferably, the flow rate of the modified phenolic resin is 1kg/s to 3kg/s when continuously added.
The invention provides a resin carbon anode green body intermediate, which is obtained by hardening the green body, wherein the hardening temperature is 120-270 ℃ and the hardening time is 1-10h.
In some embodiments of the invention, the green intermediate volatiles are in the range of 0-3.0%.
Wherein the volatile component refers to the weight percentage of the carbon anode green body which is lost after hardening treatment. In the present invention, the volatile component is the ratio of the weight difference between the green weight of the shaped carbon anode and the hardened green intermediate to the weight of the shaped carbon anode green.
In some embodiments of the invention, the green intermediate body density is from 1.6 to 1.8g/m 3 。
The bulk density refers to the bulk density, and in the invention, the bulk density is calculated by the ratio of the weight of a green body intermediate of a carbon anode to the volume of the green body intermediate, and the bulk density test method refers to the GBT24528-2009 carbon material bulk density measurement method.
In some specific embodiments of the invention, the resin carbon anode green body intermediate is tested by gas chromatography-mass spectrometry after mixing, kneading, forming and hardening treatment of a mixture comprising modified phenolic resin, coal pitch and aggregate, wherein the hardening treatment temperature is 120-270 ℃, and the cracking temperature selected for testing is 600 ℃.
The invention provides a carbon anode which is prepared by mixing, kneading, molding, hardening and roasting a mixed material comprising modified phenolic resin, coal pitch and aggregate.
In some embodiments of the invention, the modified phenolic resin comprises lignin, polyphenolic compounds, and polyhydroxy compound modified phenolic resins;
preferably, the lignin is acidic lignin, the polyphenol compound is selected from one or more of pyrogallol, tea polyphenol, tannic acid and baking gum, and the polyhydroxy compound is selected from one or more of maltose, sucrose, glucose, fructose, oxidized starch, sorbitol and dextrin.
The process of the modified phenolic resin is as described above and will not be described in detail herein.
In some embodiments of the invention, the aggregate comprises one or more of calcined coke having a particle size of 8-5mm, calcined coke having a particle size of 5-3mm, calcined coke having a particle size of 3-1mm, calcined coke having a particle size of 1-0mm, and fine calcined coke having a particle size of less than 0.075 mm.
The specifications of the calcined coke with the particle size of 8-5mm, the calcined coke with the particle size of 5-3mm, the calcined coke with the particle size of 3-1mm, the calcined coke with the particle size of 1-0mm and the fine powder calcined coke with the particle size of less than 0.075mm are as described above, and are not repeated here.
In some embodiments of the invention, the weight percentage of calcined coke with the particle size of 8-5mm is 5-20wt%, the weight percentage of calcined coke with the particle size of 5-3mm is 10-25wt%, the weight percentage of calcined coke with the particle size of 3-1mm is 15-30wt%, the weight percentage of calcined coke with the particle size of 1-0mm is 10-20wt%, and the weight percentage of fine powder calcined coke with the particle size of less than 0.075mm is 25-45wt%.
In some embodiments of the invention, the modified phenolic resin is 6 to 12wt%, the coal pitch is 1 to 5wt% and the aggregate is 83 to 93wt%, based on the total weight of the carbon anode feedstock.
In some embodiments of the invention, the shaping process is performed on an electric screw press or a vibratory press.
In some embodiments of the invention, the hardening treatment temperature is 120-270 ℃ and the hardening treatment time is 1-10 hours.
In some embodiments of the invention, the firing process comprises: under the condition of carbon burying, the temperature is raised to 550-1100 ℃ from the room temperature to 270 ℃ and the roasting treatment time is 20-250h; .
In some embodiments of the invention, the firing process is a microwave firing process, an oven firing process, a tunnel kiln firing process, a down-draft kiln firing process, a multi-chamber ring firing furnace firing process, a muffle firing process, or a firing furnace firing process.
In some embodiments of the invention, the temperature rise rate is 3-60 ℃/h at the room temperature-270 ℃ stage in the roasting treatment process; 270-500 ℃ and the heating rate is 3-60 ℃/h; the temperature rising rate is 10-50 ℃/h in the 500-800 ℃ stage, and is 10-30 ℃/h in the 800-1100 ℃ stage.
The invention provides a method for preparing the carbon anode, wherein,
mixing materials: the mixed material comprises modified phenolic resin, coal pitch and aggregate;
kneading: kneading time is 10-100min;
and (3) forming: forming on a friction press or a vibration press;
hardening treatment: the hardening treatment temperature is 120-270 ℃, and the hardening treatment time is 1-10h;
roasting: heating from room temperature to 270 ℃ to 550-1100 ℃;
the roasting treatment comprises the steps of heating to 550-1100 ℃ from room temperature to 270 ℃ under the condition of carbon burying, wherein the roasting treatment time is 20-250h;
preferably, the baking treatment is a microwave baking treatment, an oven baking treatment, a tunnel kiln baking treatment, a down-draft kiln baking treatment, a multi-chamber ring baking furnace baking treatment, a muffle baking treatment, or a baking furnace baking treatment.
In some embodiments of the invention, in the kneading treatment step, the modified phenolic resin is continuously added within 10min-30min until the addition is completed; preferably, the modified phenolic resin flow rate is 1kg/s to 3kg/s when continuously added.
In some embodiments of the invention, the modified phenolic resin is warmed to 30-50 ℃ prior to the kneading process.
The invention provides a carbon anode prepared from the resin carbon anode green body.
The invention provides a method for preparing a carbon anode from the resin carbon anode green body, wherein the resin carbon anode green body is subjected to hardening treatment and roasting treatment to obtain the carbon anode;
the baking treatment includes: under the condition of carbon burying, the temperature is raised to 550-1100 ℃ from the room temperature to 270 ℃ under the condition of carbon burying, and the roasting treatment time is 20-250h.
In some embodiments of the invention, the carbon anode body has a loss on ignition of 2 to 7.5% compared to the carbon anode green intermediate.
Wherein, the loss on ignition refers to the weight percentage of the carbon anode green body intermediate body lost after roasting treatment. In the present invention, the loss on ignition is the ratio of the weight difference between the formed green carbon anode body and the baked finished carbon anode product to the weight of the green carbon anode body.
The invention provides a carbon anode prepared from the resin carbon anode green compact intermediate.
The invention provides a method for preparing a carbon anode from the resin carbon anode green compact intermediate, wherein the resin carbon anode green compact intermediate is roasted to obtain the carbon anode;
The baking treatment includes: under the condition of carbon burying, the temperature is raised to 550-1100 ℃ from the room temperature to 270 ℃ under the condition of carbon burying, and the roasting treatment time is 20-250h.
The invention also provides application of the carbon anode in aluminum electrolysis.
After the resin carbon anode green compact provided by the invention is subjected to hardening treatment, characteristic absorption peaks of phenolic resin and coal tar pitch can be detected when the resin carbon anode green compact is tested by a gas chromatography-mass spectrometry technology, and the carbon anode can be obtained after the resin carbon anode green compact is subjected to hardening treatment and roasting treatment, so that the obtained carbon anode has good effect.
Examples
The materials used in the test and the test methods are described generally and/or specifically in the examples which follow,% represents wt%, i.e. weight percent, unless otherwise specified. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge, wherein Table 2 shows the sources of the raw materials used in the examples.
Table 3 sources of raw materials used in the examples
| Raw materials | Model/purity | Manufacturing factories |
| Lignin | Industrial use | Are commonly purchased in the market |
| Calcined coke | Industrial use | Are commonly purchased in the market |
| Catalyst | Industrial use | TIANJIN DAMAO CHEMICAL REAGENT FACTORY |
| Phenolic resin | Industrial use | Shandong Shengquan New Material stock Co., ltd |
| Coal pitch powder | Industrial use | Are commonly purchased in the market |
EXAMPLE 1-1 preparation of resin carbon anode Green compact
(a) Preparing aggregate: weighing 10 parts of calcined coke with the particle diameter of 8-5mm, 15 parts of calcined coke with the particle diameter of 5-3mm, 20 parts of calcined coke with the particle diameter of 3-1mm, 10 parts of calcined coke with the particle diameter of 1-0mm and 40 parts of fine powder calcined coke with the particle diameter of less than 0.075mm, and uniformly mixing in a mixer.
(b) Preparing lignin modified phenolic resin: adding 100 parts of phenol and a proper amount of catalyst into a reaction kettle, heating to 100 ℃, adding 70 parts of lignin, phenolizing for 2 hours, cooling to 80-82 ℃, adding 130 parts of 37% formaldehyde and a modified carbon agent, heating to 88-90 ℃ after the addition is finished, controlling the viscosity to 180-280cp, dehydrating to 4-7%, and discharging.
(c) Heating the modified phenolic resin obtained in the step (b) to 40 ℃, mixing 91g of aggregate obtained in the step (a), 8g of modified phenolic resin obtained in the step (b) and 1g of coal tar pitch (particle size 0.1-0.2 mm), continuously adding the modified phenolic resin within 20min, wherein the flow rate of the modified phenolic resin is 2kg/s until the addition is completed, and then adopting a kneader, wherein the kneading time is 30min, and the kneading temperature is 50 ℃.
(d) Placing the mixed material kneaded in the step (c) into a specific die, and performing compression molding under the pressure of 2500 tons by using an electric screw press to obtain the resin carbon anode green compact.
Examples 1-2 preparation of resin carbon anode green bodies
Examples 1-2 differ from examples 1-1 only in that: in the step (c), the kneading time was 10min, and the other conditions were the same.
Examples 1-3 preparation of resin carbon anode green bodies
Examples 1-3 differ from example 1-1 only in that: in the step (c), the kneading time was 100min, and the other conditions were the same.
Examples 1-4 preparation of resin carbon anode green bodies
Examples 1-4 differ from example 1-1 only in that: in the step (c), the kneading time was 120min, and the other conditions were the same.
Examples 1-5 preparation of resin carbon anode green bodies
Examples 1-5 differ from example 1-1 only in that: in the step (c), 89g of the aggregate obtained in the step (a), 8g of the modified phenolic resin obtained in the step (b) and 3g of coal tar pitch (particle size 0.1mm to 0.2 mm) were mixed, and the remainder was the same as in example 1-1.
EXAMPLES 1-6 preparation of resin carbon anode green compact
Examples 1-6 differ from example 1-1 only in that: in the step (c), 86g of the aggregate obtained in the step (a), 8g of the modified phenolic resin obtained in the step (b) and 6g of coal tar pitch (particle size 0.1mm to 0.2 mm) were mixed, and the remainder was the same as in example 1-1.
EXAMPLES 1-7 preparation of resin carbon anode Green bodies
Examples 1-7 differ from example 1-1 only in that: the aggregate has different components, and is concretely as follows: step (a): preparing aggregate: weighing 20 parts of petroleum coke with the size of 0-1mm, 20 parts of petroleum coke with the size of 1-2mm, 20 parts of petroleum coke with the size of 2-4mm, 15 parts of petroleum coke with the size of 4-8mm, 30 parts of petroleum coke with the size of 180 meshes, 5 parts of crushed graphite and 5 parts of carbon nano tubes by the total weight of aggregate, and putting the materials into a mixer for uniform mixing.
Examples 1-8 preparation of resin carbon anode green bodies
Examples 1-8 differ from example 1-1 only in that: in the step (c), 91g of the aggregate obtained in the step (a), 8g of the modified phenolic resin obtained in the step (b) and 1g of coal tar pitch (particle size 0.1-0.2 mm) are mixed under the condition of room temperature without heating the modified phenolic resin to 40 ℃, and then a kneader is adopted, wherein the kneading time is 30min, and the kneading temperature is 50 ℃.
EXAMPLES 1-9 preparation of resin carbon anode Green bodies
Examples 1-9 differ from example 1-1 only in that: in the step (c), the modified phenolic resin obtained in the step (b) is heated to 40 ℃, 91g of aggregate obtained in the step (a), 8g of modified phenolic resin obtained in the step (b) and 1g of coal tar pitch (particle size of 0.1-0.2 mm) are mixed, the modified phenolic resin is added all at once, and then a kneader is adopted, the kneading time is 30min, and the kneading temperature is 50 ℃.
Comparative examples 1 to 1
Comparative example 1-1 differs from example 1-1 only in that: in the step (b), the modified phenolic resin is replaced by coal pitch, 9g of coal pitch is preheated to 140 ℃, and kneaded for 30min at 140 ℃.
(c) Placing the mixed material kneaded in the step (b) into a specific mold, and pressing and forming by using a vibration forming machine.
Comparative examples 1 to 2
Comparative example 1-2 differs from example 1-1 only in that: in the step (b), 9g of modified phenolic resin preheated to 40 ℃ is added into 91g of the aggregate obtained in the step (a), the modified phenolic resin is continuously added within 20min, the flow rate of the modified phenolic resin is 2kg/s until the addition is completed, the kneading time is 30min, and the kneading temperature is 50 ℃.
The important parameters of examples 1-1 to 1-9 and comparative examples 1-2 are shown in Table 4
TABLE 4 Table 4
Example 2-1 preparation of resin carbon anode green intermediate
And (3) placing the resin carbon anode green compact prepared in the embodiment 1-1 in a microwave oven for hardening treatment, wherein in the hardening treatment, the hardening treatment temperature is 150 ℃, the hardening treatment time is 3 hours, and the resin carbon anode green compact intermediate is obtained, the weights of the green compact intermediate before and after hardening are respectively detected, and the data of the volatile matters of the green compact intermediate are calculated based on the weight difference before and after hardening, so that the volatile matters of the green compact intermediate are 1.3%.
The resin carbon anode green compact intermediate obtained in example 2-1, which has a gas chromatography-mass spectrometry spectrum as shown in fig. 1, was then subjected to gas chromatography-mass spectrometry analysis.
EXAMPLE 2-2 preparation of resin carbon anode green intermediate
And (3) carrying out hardening treatment on the resin carbon anode green compact prepared in the examples 1-8, wherein in the hardening treatment, the hardening treatment temperature is 150 ℃, the hardening treatment time is 3 hours, and the resin carbon anode green compact intermediate is obtained, the weights of the green compact intermediate before and after hardening are respectively detected, and the data of the green compact intermediate volatile is calculated based on the weight difference before and after hardening, so that the result shows that the green compact intermediate volatile is 1.02%.
Examples 2-3 preparation of resin carbon anode green intermediates
And (3) carrying out hardening treatment on the resin carbon anode green compact prepared in the examples 1-9, wherein in the hardening treatment, the hardening treatment temperature is 150 ℃, the hardening treatment time is 3 hours, and the resin carbon anode green compact intermediate is obtained, the weights of the green compact intermediate before and after hardening are respectively detected, and the data of the green compact intermediate volatile is calculated based on the weight difference before and after hardening, so that the result shows that the green compact intermediate volatile is 0.98%.
EXAMPLES 2-4 preparation of resin carbon anode Green intermediate
And (3) carrying out hardening treatment on the resin carbon anode green compact prepared in the embodiment 1-1, wherein in the hardening treatment, the hardening treatment temperature is 300 ℃, the hardening treatment time is 2 hours, and the resin carbon anode green compact intermediate is obtained, the weights of the green compact intermediate before and after hardening are respectively detected, and the data of the green compact intermediate volatile is calculated based on the weight difference before and after hardening, so that the result shows that the green compact intermediate volatile is 1.2%.
EXAMPLES 2-5 preparation of resin carbon anode Green intermediate
And (3) carrying out hardening treatment on the resin carbon anode green compact prepared in the embodiment 1-1, wherein in the hardening treatment, the hardening treatment temperature is 90 ℃, the hardening treatment time is 12 hours, and the resin carbon anode green compact intermediate is obtained, the weights of the green compact intermediate before and after hardening are respectively detected, and the data of the green compact intermediate volatile is calculated based on the weight difference before and after hardening, so that the result shows that the green compact intermediate volatile is 0.92%.
Examples 2 to 6
Examples 2 to 6 differ from example 2 to 1 only in that the hardening treatment temperature was 150℃and the hardening treatment time was 8 hours, the weights of the green intermediate before and after hardening were each measured, and the data of the green intermediate volatiles were calculated based on the weight difference before and after hardening, and as a result, the green intermediate volatiles were shown to be 1.45%.
Examples 2 to 7
Examples 2 to 7 differ from example 2 to 1 only in that the hardening treatment temperature was 300℃and the hardening treatment time was 8 hours, the weights of the green intermediate before and after hardening were each measured, and the data of the green intermediate volatiles were calculated based on the weight difference before and after hardening, and as a result, the green intermediate volatiles were shown to be 2.2%.
Examples 2 to 8
And (3) carrying out hardening treatment on the resin carbon anode green compact prepared in the examples 1-6, wherein in the hardening treatment, the hardening treatment temperature is 150 ℃, the hardening treatment time is 3 hours, and the resin carbon anode green compact intermediate is obtained, the weights of the green compact intermediate before and after hardening are respectively detected, and the data of the green compact intermediate volatile is calculated based on the weight difference before and after hardening, so that the result shows that the green compact intermediate volatile is 1.23%.
The resin carbon anode green intermediates obtained in examples 2 to 8, which had a gas chromatography-mass spectrometry spectrum as shown in fig. 2, were then subjected to gas chromatography-mass spectrometry analysis.
Comparative example 2-1
And (3) hardening the pitch carbon anode green compact prepared in the comparative example 1-1, placing the pitch carbon anode green compact into a water tank for water cooling for 3 hours to obtain a pitch carbon anode green compact intermediate, respectively detecting the weights of the green compact intermediate before and after hardening, and calculating the data of the volatile matters of the green compact intermediate based on the weight difference before and after hardening, wherein the result shows that the volatile matters of the green compact intermediate are 0.05%.
The pitch carbon anode green compact intermediate obtained in comparative example 2-1, which had a gas chromatography-mass spectrometry spectrum as shown in fig. 3, was then subjected to gas chromatography-mass spectrometry analysis.
Comparative examples 2 to 2
And (3) carrying out hardening treatment on the resin carbon anode green compact prepared in the comparative example 2-2, wherein in the hardening treatment, the hardening treatment temperature is 150 ℃, the hardening treatment time is 3 hours, and the resin carbon anode green compact intermediate is obtained, the weights of the green compact intermediate before and after hardening are respectively detected, and the data of the green compact intermediate volatile is calculated based on the weight difference before and after hardening, so that the result shows that the green compact intermediate volatile is 0.85%.
TABLE 5
Example 3-1 preparation of carbon anodes
The resin carbon anode green compact prepared in example 2-1 is placed in a tunnel kiln for roasting treatment, wherein: under the condition of carbon burying, the temperature is increased from 150 ℃ to 950 ℃, wherein the temperature increasing rate is 10 ℃/h in the stage of 150-400 ℃; the heating rate is 15 ℃/h in the stage of 400-750 ℃, the heating rate is 20 ℃/h in the stage of 750-950 ℃, the baking is kept for 72h, the weights of the carbon anode green compact intermediate and the carbon anode finished product before and after the baking are respectively weighed, and the loss on ignition of the carbon anode is calculated to be 4.5% based on the weight difference of the two.
And slowly cooling after roasting, and discharging from the kiln to obtain the carbon anode.
Example 3-2
The resin carbon anode green compact prepared in example 2-2 was placed in a tunnel kiln for firing treatment, wherein the firing treatment was the same as that of example 3-1.
Examples 3 to 3
The resin carbon anode green compact prepared in example 2-3 was placed in a tunnel kiln for firing treatment, wherein the firing treatment was the same as that of example 3-1.
Examples 3 to 4
The resin carbon anode green compact prepared in example 2-4 was placed in a tunnel kiln for firing treatment, wherein the firing treatment was the same as that of example 3-1.
Examples 3 to 5
The resin carbon anode green compact prepared in example 2-5 was put in a tunnel kiln to perform a firing treatment, wherein the firing treatment was the same as that of example 3-1.
Examples 3 to 6
The resin carbon anode green compact prepared in example 2-6 was placed in a tunnel kiln for firing treatment, wherein the firing treatment was the same as that of example 3-1.
Examples 3 to 7
The resin carbon anode green compact prepared in example 2-7 was placed in a tunnel kiln for firing treatment, wherein the firing treatment was the same as that of example 3-1.
Examples 3 to 8
The resin carbon anode green compact prepared in example 2-8 was placed in a tunnel kiln for firing treatment, wherein the firing treatment was the same as that of example 3-1.
Comparative example 3-1
The pitch carbon anode green compact prepared in comparative example 2-1 was put in a tunnel kiln to conduct a firing treatment, wherein the firing treatment was the same as in example 3-1.
The resin carbon anode green compact intermediate obtained in comparative example 3-1, which has a gas chromatography-mass spectrometry spectrum as shown in fig. 4, was then subjected to gas chromatography-mass spectrometry analysis.
Comparative example 3-2
The resin carbon anode green compact prepared in comparative example 2-2 was placed in a tunnel kiln to conduct a firing treatment, wherein the firing treatment was the same as that of example 3-1.
Comparative examples 3 to 3
The resin carbon anode green body prepared in the example 2-1 is placed in a tunnel kiln for roasting treatment, and roasting conditions are as follows: at the room temperature of between 270 ℃ and 3 to 60 ℃ per hour; at 270-500 deg.c, the temperature raising rate is 3-60 deg.c/hr and roasting is maintained for 72 hr. TABLE 6
Experimental example 1
When the product obtained by the application is tested by a gas chromatography-mass spectrometry technology, the parameters are as follows:
1. instrument reagent
1.1 gas chromatograph-mass spectrometer: 7890B/5977B GC/MSD, EGA/PY-3030D cracker and Masshunter acquisition and characterization software;
1.2 chromatography column: VF-1701MS capillary column (30 m 0.150mm 0.15 μm);
1.3 high purity helium: 99.999%;
1.4 sample cup: eco-Cup LF;
1.5 connecting rod: eco-Stick SF;
1.6 a manual sample injector;
1.7 sample spoon.
2. Detection method
2.1 chromatography methods
2.1.1 sample inlet temperature: 270 ℃;
2.1.2 column 1 flow: 1ml/min;
2.1.3 split ratio: 80:1;
2.1.4 column box temperature: the initial temperature is 40 ℃, and the temperature is kept for 2min; raising the temperature to 260 ℃ at a heating rate of 20 ℃/min, and keeping for 30min.
2.1.5MSD transmission line temperature: 260 ℃.
2.2 Mass Spectrometry methods
2.2.1 ion source temperature: 230 ℃;
2.2.2 four-stage bar temperature: 150 ℃;
2.2.3 ion source: an Inert EI source;
2.2.4 ionization energy: 70eV;
2.2.3 solvent delay: 0min;
2.2.4 acquisition mode: scanning;
2.2.5 scan range m/z:10-500amu;
2.3 cleavage Process
2.3.1 cleavage mode: clicking;
2.3.2 cleavage temperature: 600 ℃;
2.3.3 cleavage time: 0.2min;
3. sample testing
3.1 operating gas phase, mass spectrometry and fragmentation instrument methods, the instrument was ready.
3.2 a small sample is taken with a sample spoon and transferred into a sample cup.
3.3 connecting the sample cup to the manual sample injector with a connecting rod, fixing the injector to the lysis instrument.
3.4 editing the gas chromatography sample injection sequence and running, clicking the cracking software "start".
3.5 when the instrument is ready, after the cracking software sends out a sample injection warning, the top button of the manual sample injector is pressed, so that the sample cup falls into the liner tube of the cracking instrument, the running procedure is started, and the sample starts to crack and enters the chromatographic column to be separated, and is detected by mass spectrum.
3.6 taking out the sample cup after the operation is finished.
And 3.7, opening qualitative software to perform qualitative analysis on the detection result.
The gas chromatography-mass spectrometry of example 2-1 is shown in FIG. 1;
the gas chromatography-mass spectra of examples 2-8 are shown in FIG. 2;
the gas chromatography-mass spectrometry of comparative example 2-1 is shown in FIG. 3, and the gas chromatography-mass spectrometry combined technical test conditions are the same as those in example 2-1;
the gas chromatography-mass spectrometry of comparative example 3-1 is shown in FIG. 4, and the gas chromatography-mass spectrometry combined technical test conditions are the same as those in example 2-1;
wherein in FIGS. 1 and 2, characteristic peaks belonging to phenolic resin and coal pitch are clearly seen, for example, characteristic peaks are seen in retention time of 8.28+ -0.3 min, 10.34+ -0.3 min, 12.7+ -0.3 min, 14.6+ -0.3 min, 17.7+ -0.3 min, 19.0+ -0.3 min, 26.5+ -0.3 min, 29.6+ -0.3 min, and according to Table 1, characteristic groups corresponding to retention time of 8.28+ -0.3 min, 10.34+ -0.3 min are all characteristic groups belonging to phenolic resin, and characteristic groups corresponding to retention time of 12.7+ -0.3 min, 14.6+ -0.3 min, 17.7+ -0.3 min, 19.0+ -0.3 min, 26.5+ -0.3 min, 29.6+ -0.3 min are all characteristic groups belonging to coal pitch
The specific analysis results of the characteristic peaks shown in fig. 3 are shown in table 7, and it can be seen from table 7 that in comparative example 2-1, characteristic peaks belonging to coal tar pitch can be obtained remarkably in the gas chromatograph-mass spectrogram without high temperature roasting treatment, and that according to table 7, characteristic groups corresponding to the characteristic peaks are all characteristic groups belonging to coal tar pitch, and no characteristic peaks belonging to phenolic resin are found.
TABLE 7 results of gas chromatography-mass spectrometry analysis of green intermediates prepared in comparative example 2-1
The specific analysis results of the characteristic peaks shown in fig. 4 are shown in table 8, and in fig. 4, in combination with table 8, it can be seen that in comparative example 3-1, characteristic peaks of long-chain alkane can be seen in the gas chromatograph-mass spectrogram after high temperature roasting at 950 ℃, for example, characteristic peaks are found in retention time of 1.56±0.3min, 3.37±0.3min, 4.88±0.3min, 5.60±0.3min, and according to table 8, characteristic groups corresponding to the characteristic peaks are all characteristic groups of long-chain alkane and condensed ring compound; characteristic peaks belonging to coal tar pitch can also be seen, and it can be seen from table 8 that characteristic groups corresponding to these characteristic peaks all belong to the characteristic groups of coal tar pitch.
TABLE 8 results of gas chromatography-mass spectrometry analysis of the green compacts prepared in comparative example 3-1
Experimental example 2 green body and intermediate result data
The compressive strength of the intermediate was measured according to the test method in YS/T285-2012.
TABLE 9 Green Effect index
In table 9, the resin carbon anode green body was defined as 100% in appearance with no cracks and no gaps and round appearance.
Table 10 intermediate index
| Compressive Strength (Mpa) | Volatile component | |
| Example 2-1 | 42 | 1.3％ |
| Example 2-2 | 40 | 1.02％ |
| Examples 2 to 3 | 41 | 0.98％ |
| Examples 2 to 4 | 44 | 1.2％ |
| Examples2-5 | 38 | 0.92％ |
| Examples 2 to 6 | 45 | 1.45％ |
| Examples 2 to 7 | 41 | 2.2％ |
| Examples 2 to 8 | 36 | 1.23％ |
| Comparative example 2-1 | 32 | 0.05％ |
| Comparative examples 2 to 2 | 38 | 0.85％ |
Volatile is an indicator of the degree of hardening. In principle volatile is a characteristic value, and it is most energy efficient to stop immediately once this specific value is reached. If the volatile fraction is too short, the impurities at this temperature do not volatilize sufficiently, and subsequent high-temperature calcination may cause anode cracking, if the volatile fraction reaches a specific value for too long, but the energy consumption is increased.
EXAMPLE 3 carbon anode index
The bulk density detection method is carried out according to the detection method in YS/T285-2012
For the person skilled in the art, a bulk density of 1.70g/m is achieved 3 Is a very difficult indicator. In addition, anotherIn addition, the bulk density is increased by 0.01g/m 3 It is difficult for a person skilled in the art to increase the resistivity by 1uΩ.m, rather than within the instrument error. In example 3, each data in table 11 was averaged three times, wherein each set of data for bulk density and resistivity was identical, rather than an average value from up and down fluctuations.
TABLE 11 carbon anode index
Although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but rather is capable of modification and variation without departing from the spirit and scope of the present invention as defined in the following claims.
Claims (10)
1. The resin carbon anode green compact is characterized in that the resin carbon anode green compact is subjected to hardening treatment to obtain a resin carbon anode green compact intermediate, and the resin carbon anode green compact intermediate has the following spectrum characteristics when tested by a gas chromatography-mass spectrometry technology: at retention time of 8.28 + -. Sequentially
Characteristic peaks are present at 0.3min, 12.7+ -0.3 min, 14.6+ -0.3 min and 19.0+ -0.3 min.
2. The green resin carbon anode of claim 1, wherein the green resin carbon anode intermediate has the following profile characteristics when tested by gas chromatography-mass spectrometry techniques: characteristic peaks are arranged at the positions of retention time of 8.28+/-0.3 min, 10.34+/-0.3 min, 12.7+/-0.3 min, 14.6+/-0.3 min, 17.7+/-0.3 min and 19.0+/-0.3 min in sequence.
3. The green resin carbon anode of claim 1, wherein the green resin carbon anode intermediate has a gas chromatography-mass spectrometry spectrum as shown in fig. 1 or fig. 2.
4. A green resin carbon anode according to any one of claims 1 to 3, wherein the gas chromatograph-mass spectrometer used in the gas chromatograph-mass spectrometer test is 7890B/5977BGC/MSD and the chromatographic column is a VF-1701MS capillary column.
5. A method for producing a resin carbon anode green body as claimed in any one of claims 1 to 4, wherein,
mixing materials: the mixed material comprises modified phenolic resin, coal pitch and aggregate;
kneading: kneading time is 10-100min;
and (3) forming: the method is characterized in that the molding is carried out on an electric screw press or a vibration press;
preferably, the modified phenolic resin is heated to 30-50 ℃ before the kneading treatment;
further preferably, in the kneading treatment step, the modified phenolic resin is continuously added within 10-30 min until the addition is completed, and the kneading temperature is 40-60 ℃;
further preferably, the flow rate of the modified phenolic resin is 1kg/s to 3kg/s when continuously added.
6. A resin carbon anode green body intermediate, characterized in that the green body according to any one of claims 1 to 4 is obtained by hardening treatment, wherein the volatile component of the green body intermediate is 0 to 3.0%;
preferably, the green intermediate body density is 1.6-1.8g/m 3 ；
It is further preferable that the hardening treatment temperature is 120 to 270℃and the hardening treatment time is 1 to 10 hours.
7. A method for preparing the resin carbon anode green body intermediate of claim 6, wherein,
Mixing materials: the mixed material comprises modified phenolic resin, coal pitch and aggregate;
kneading: kneading time is 10-100min;
and (3) forming: the method is characterized in that the molding is carried out on an electric screw press or a vibration press;
hardening treatment: the hardening treatment temperature is 120-270 ℃, and the hardening treatment time is 1-10h;
preferably, the modified phenolic resin is heated to 30-50 ℃ before the kneading treatment;
further preferably, in the kneading treatment step, the modified phenolic resin is continuously added within 10-30 min until the addition is completed, and the kneading temperature is 40-60 ℃;
further preferably, the flow rate of the modified phenolic resin is 1kg/s to 3kg/s when continuously added.
8. A carbon anode is prepared from the mixture of modified phenolic resin, coal pitch and aggregate through kneading, shaping, hardening and calcining; or the resin carbon anode green body is obtained by hardening treatment and roasting treatment according to any one of claims 1-4; or from the resin carbon anode green body intermediate according to claim 6 by roasting treatment.
9. A method of making the carbon anode of claim 8, comprising the steps of:
Mixing materials: the mixed material comprises modified phenolic resin and aggregate;
kneading: kneading time is 10-100min;
and (3) forming: forming on a friction press or a vibration press;
hardening treatment: the hardening treatment temperature is 120-270 ℃, and the hardening treatment time is 1-10h;
roasting: raising the temperature from room temperature to 270 ℃ to 550 to 1100 ℃.
10. Use of a carbon anode according to claim 8, prepared according to the method of claim 9, for the electrolysis of aluminium.
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