CN109365474B - Method for treating aluminum electrolysis waste cathode carbon blocks - Google Patents
Method for treating aluminum electrolysis waste cathode carbon blocks Download PDFInfo
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- CN109365474B CN109365474B CN201811216091.7A CN201811216091A CN109365474B CN 109365474 B CN109365474 B CN 109365474B CN 201811216091 A CN201811216091 A CN 201811216091A CN 109365474 B CN109365474 B CN 109365474B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 119
- 239000002699 waste material Substances 0.000 title claims abstract description 118
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 113
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000008188 pellet Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 22
- 229910052742 iron Inorganic materials 0.000 description 9
- 238000001514 detection method Methods 0.000 description 6
- 239000000571 coke Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
- C25C3/125—Anodes based on carbon
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to the technical field of harmless treatment and recycling of waste cathode carbon blocks in aluminum electrolysis, in particular to a method for treating waste cathode carbon blocks in aluminum electrolysis, which comprises the following steps: treating the aluminum electrolysis waste cathode carbon blocks by using an iron-making process, wherein furnace burden of the iron-making process comprises pellets, sinter and the aluminum electrolysis waste cathode carbon blocks; wherein, the furnace burden of the iron-making process comprises 18-32 parts of pellet ore, 64-80 parts of sinter ore and 0-6.4 parts of aluminum electrolysis waste cathode carbon blocks by mass; the sintered ore contains 0-30 parts of aluminum electrolysis waste cathode carbon blocks by 100 parts by mass; the content of the aluminum electrolysis waste cathode carbon blocks in the sintering ore and the content of the aluminum electrolysis waste cathode carbon blocks in the furnace burden of the iron-making process are not 0 at the same time. The invention can realize the industrial-scale harmless development and utilization of the waste cathode carbon blocks generated by aluminum electrolysis.
Description
Technical Field
The invention relates to the technical field of harmless treatment and recycling of waste cathode carbon blocks in aluminum electrolysis, in particular to a method for treating waste cathode carbon blocks in aluminum electrolysis.
Background
The electrolytic aluminum industry is the basic industry of national economy and plays an important role in the development of the current society. At present, the aluminum yield of China is the first in the world, and exceeds 1500 ten thousand tons, and the aluminum yield still has the tendency of rapid growth. Meanwhile, aluminum electrolysis brings a great amount of valuable aluminum ingots to national economy and pollution.
The accumulated discharge amount of the lining amount of the waste electrolytic cell reaches more than 700 million tons so far, the electrolytic aluminum plant in China mainly adopts a large prebaked anode electrolytic cell, the electrolytic cell needs to be overhauled when the service life of the electrolytic cell is reached, the lining of the electrolytic cell needs to be replaced during overhauling, and the materials generated during overhauling are called overhauled waste residues or waste lining of the electrolytic cell and the like. Wherein, the largest pollution source is the waste cathode after overhaul. Fluoride and cyanide in the waste cathode carbon blocks permeate into underground water when the waste cathode carbon blocks are stacked, and water sources are polluted. In addition, the fertilizer has great harm to surrounding animals and plants, influences the natural ecological balance and reduces the yield of crops, so the fertilizer needs to be treated.
Aluminum metal has become an important basic material for national economic development. However, in the aluminum smelting production process, due to the corrosion of electrolyte, about 30kg of waste cathode carbon blocks are generated every 1 ton of electrolytic aluminum is produced, and the waste cathode carbon blocks become main solid pollutants in the aluminum electrolysis industry. According to the calculation, the yield of electrolytic aluminum in 2015 in China reaches 3141 ten thousand tons, more than 90 thousand tons of waste cathode carbon blocks are produced, and the quantity of the waste cathode carbon blocks is huge and cannot be ignored.
In the waste cathode carbon blocks produced by aluminum electrolysis, the main components are carbon, cryolite, sodium fluoride, alumina and aluminum fluoride, and a small amount of aluminum carbide and sodium carbide. At present, the waste cathode carbon blocks are treated mainly by stacking or safe landfill, chemical separation and other methods in China. However, the carbon in the waste cathode carbon blocks accounts for 70 percent and is highly graphitized, and the rest is the electrolyte taking the cryolite as the main body, which is an available resource. Therefore, the recycling of the waste cathode carbon blocks has better development prospect.
However, in the prior art, how to effectively save energy, reduce emission and reduce cost is hardly considered, and the waste cathode carbon blocks generated by aluminum electrolysis are difficult to realize industrial-scale development and utilization.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for treating waste cathode carbon blocks in aluminum electrolysis, which can realize industrial-scale harmless development and utilization of the waste cathode carbon blocks generated in aluminum electrolysis.
The technical scheme adopted by the invention is as follows:
a method for treating aluminum electrolysis waste cathode carbon blocks comprises the following steps: treating the aluminum electrolysis waste cathode carbon blocks by using an iron-making process, wherein furnace burden of the iron-making process comprises pellets, sinter and the aluminum electrolysis waste cathode carbon blocks; wherein, the furnace burden of the iron-making process comprises 18-32 parts of pellet ore, 64-80 parts of sinter ore and 0-6.4 parts of aluminum electrolysis waste cathode carbon blocks by mass;
the sintered ore contains 0-30 parts of aluminum electrolysis waste cathode carbon blocks by 100 parts by mass;
the content of the aluminum electrolysis waste cathode carbon blocks in the sintering ore and the content of the aluminum electrolysis waste cathode carbon blocks in the furnace burden of the iron-making process are not 0 at the same time.
The grain size of the furnace charge in the iron-making process is not more than 40 mm.
The grain size of the aluminum electrolysis waste cathode carbon blocks in the sintering ore is not more than 3.0mm, and the content of the aluminum electrolysis waste cathode carbon blocks with the grain size of 3mm in the sintering ore is not less than 70 percent of the total mass of the aluminum electrolysis waste cathode carbon blocks in the sintering ore in percentage by mass.
The alkalinity of the pellets is 0.36-0.69; the pellet comprises the following components in 100 parts by mass: 49-60 parts of Fe, 5-15 parts of silicon dioxide, 4-12 parts of calcium oxide, 1-3 parts of aluminum oxide, no more than 0.07 part of sulfur, no more than 0.035 part of phosphorus and impurities.
The alkalinity of the sinter of the waste cathode carbon blocks without aluminum electrolysis is 1.45-1.79, and the sinter of the waste cathode carbon blocks without aluminum electrolysis comprises the following components in 100 parts by mass: 40-55 parts of Fe, 10-20 parts of calcium oxide, 5-15 parts of silicon dioxide, 1-3 parts of aluminum oxide, no more than 0.07 part of sulfur, no more than 0.035 part of phosphorus and impurities.
The aluminum electrolytic cell waste cathode carbon block comprises the following components in 100 parts by mass: 40-60 parts of C, 9-37 parts of F and 4 parts of SiO24-8.5 parts of Al, 5-15 parts of Na, not more than 0.5 part of S and impurities.
When the waste aluminum electrolysis cathode carbon blocks are treated by the iron-making process, the temperature rising system is as follows: when the temperature is less than 1200 ℃, the temperature is increased by 10 ℃ per minute, and the load is 0.7kg/cm2(ii) a When the temperature is more than or equal to 1200 ℃, the temperature is increased by 5 ℃ per minute, and the load is 1kg/cm2。
Compared with the prior art, the invention has the following beneficial effects:
the method for treating the aluminum electrolysis waste cathode carbon blocks utilizes the iron-making process to treat the aluminum electrolysis waste cathode carbon blocks, and furnace burden of the iron-making process contains the aluminum electrolysis waste cathode carbon blocks which mainly contain carbon and fluoride salt with a certain slagging function, thereby playing roles in recarburization, reduction, combustion and slagging. The method can effectively treat the waste aluminum electrolysis cathode carbon blocks in a harmless way and improve the resource utilization rate of the waste aluminum electrolysis cathode carbon blocks. According to the invention, the aluminum electrolysis waste hazardous waste is used as the raw material sintering ore for blast furnace ironmaking or is directly added into the raw material of the blast furnace, and the fluoride in the aluminum electrolysis waste cathode carbon block can be effectively converted into blast furnace flue gas and enters blast furnace slag through a pyrogenic process, so that the harm of the fluoride is effectively reduced, and the decomposition of cyanide in the aluminum electrolysis waste cathode carbon block is promoted under the high-temperature environment of the blast furnace. The waste cathode carbon blocks are added into blast furnace equipment, so that the harmless treatment of the aluminum electrolysis hazardous waste is reduced, and the aluminum electrolysis waste cathode carbon blocks are also used as fuel, reducing agent and recarburizing agent in the blast furnace, so that the resource recycling of the aluminum electrolysis hazardous solid waste is promoted.
Drawings
FIG. 1 is a route diagram of a treatment process for aluminum electrolysis waste cathode carbon blocks.
Detailed Description
The invention is further described below with reference to the figures and examples.
Referring to fig. 1, the method for treating the aluminum electrolysis waste cathode carbon blocks of the invention treats the aluminum electrolysis waste cathode carbon blocks by using an iron-making process, wherein furnace burden of the iron-making process comprises pellets, sinter and the aluminum electrolysis waste cathode carbon blocks; wherein, the furnace burden of the iron-making process comprises 18-32 parts of pellet ore, 64-80 parts of sinter ore and 0-6.4 parts of aluminum electrolysis waste cathode carbon blocks by mass; the sintered ore contains 0-30 parts of aluminum electrolysis waste cathode carbon blocks by 100 parts by mass; the content of the aluminum electrolysis waste cathode carbon blocks in the sintering ore and the content of the aluminum electrolysis waste cathode carbon blocks in the furnace burden of the iron-making process are not 0 at the same time.
Wherein the grain size of the furnace burden of the iron-making process is not more than 40 mm; the grain size of the aluminum electrolysis waste cathode carbon blocks in the sintering ore is not more than 3.0mm, and the content of the aluminum electrolysis waste cathode carbon blocks with the grain size of 3mm in the sintering ore is not less than 70 percent of the total mass of the aluminum electrolysis waste cathode carbon blocks in the sintering ore in percentage by mass;
the alkalinity of the pellet ore is 0.36-0.69; the pellet comprises the following components in 100 parts by mass: 49-60 parts of Fe, 5-15 parts of silicon dioxide, 4-12 parts of calcium oxide, 1-3 parts of aluminum oxide, no more than 0.07 part of sulfur, no more than 0.035 part of phosphorus and impurities;
the alkalinity of the sinter of the waste cathode carbon blocks without aluminum electrolysis is 1.45-1.79, and the sinter of the waste cathode carbon blocks without aluminum electrolysis comprises the following components in 100 parts by mass: 40-55 parts of Fe, 10-20 parts of calcium oxide, 5-15 parts of silicon dioxide, 1-3 parts of aluminum oxide, no more than 0.07 part of sulfur, no more than 0.035 part of phosphorus and impurities;
the aluminum electrolytic cell waste cathode carbon block comprises the following components in 100 parts by mass: 40-60 parts of C, 9-37 parts of F and 4 parts of SiO24-8.5 parts of Al, 5-15 parts of Na, not more than 0.5 part of S and impurities.
According to the invention, the waste aluminum electrolysis cathode carbon blocks are used as iron-making raw materials according to an iron-making process, and harmful elements in the waste aluminum electrolysis cathode carbon blocks are removed through the iron-making process, so that harmless treatment and resource utilization of hazardous solid wastes are achieved. The invention takes the aluminum electrolysis waste cathode carbon blocks as sintering ore raw materials, blast furnace raw materials, iron coke or hot-pressing carbon-containing pellets, foundry ladle pretreatment auxiliary materials and the like in the iron-making process, and the waste cathode carbon blocks are crushed to a certain granularity and pretreated for the production of the iron-making process (as shown in figure 1).
Example 1:
the method for treating the aluminum electrolysis waste cathode carbon blocks in the embodiment is to treat the aluminum electrolysis waste cathode carbon blocks by using an iron-making process, wherein furnace burden proportion of the iron-making process (shown in table 1) is directly added with 6.4 parts of aluminum electrolysis waste cathode carbon blocks, 18 parts of pellet ore and 75.6 parts of sinter ore of a blast furnace; the sintered ore contains 0 part of aluminum electrolysis waste cathode carbon block by 100 parts of mass unit.
The test method of this example was carried out according to the following procedure:
(1) crushing and grinding the raw materials, wherein the granularity of the aluminum electrolysis waste cathode carbon blocks serving as the raw materials of the sinter is controlled to be not more than 3mm, and the content of the aluminum electrolysis waste cathode carbon blocks with the grain size of 3mm in the sinter is not less than 70 percent of the total mass of the aluminum electrolysis waste cathode carbon blocks in the sinter in percentage by mass; in the embodiment, the granularity of the blast furnace raw material (namely the furnace charge) directly used as the blast furnace raw material is controlled to be 10-12.5mm, and the moisture content is below 12 percent of the total mass; description of the drawings: due to the limitation of the size of test equipment, in all the embodiments of the invention, the granularity of the blast furnace raw material is controlled to be 10-12.5mm, and for the actual iron-making process, the granularity of the blast furnace raw material is not more than 40 mm;
(2) weighing the raw materials treated in the step (1) according to the composition mass of the raw materials, and then manually and mechanically mixing for 10-20 minutes to obtain a mixed raw material;
(3) and (3) filling the mixed raw materials obtained in the step (2) into a high-purity graphite crucible, wherein the inner shape size of the high-purity graphite crucible is as follows: the diameter is 48mm multiplied by the height is 180mm, and 9 holes with the inner diameter of 8mm are arranged below the base; before the mixed raw materials are put into a high-purity graphite crucible, coke with the granularity of 15-20mm and the thickness of 30mm is firstly put on the bottom of the crucible, 200 g of the mixed raw materials with the granularity of 10-12.5mm are put on the coke, and the height of the mixed raw materials is 70-77 mm; a coke layer is laid on the material layer for 20mm, and the total material column height is 120mm-130 mm; the coke used in the experimental process of the embodiment of the invention is a raw material for conventional blast furnace ironmaking.
(4) Heating at 10 deg.C per minute before 1200 deg.C, and loading at 0.7kg/cm2(ii) a After 1200 ℃, the temperature is raised by 5 ℃ per minute, and the load is 1kg/cm2. The ventilation volume is as follows: introducing nitrogen gas at 700 deg.C for 1L/min, introducing reducing gas at 700 deg.C for 8L/min, wherein the reducing gas contains 69% N by volume2And 31% CO. And (3) cooling: after dropping, the pressure bar is lifted by 40mm, and nitrogen is introduced at 3L/min for 30min for cooling.
(5) And (4) measuring the dripping performance parameters of the blast furnace raw materials.
The performance parameters of this example as blast furnace iron making raw materials are shown in table 1.
Example 2:
the method for treating the aluminum electrolysis waste cathode carbon blocks provided by the embodiment is based on 5 parts of waste cathode carbon blocks, 25 parts of pellet ore and 70 parts of sinter ore which are directly added into a blast furnace, wherein the sinter ore contains the aluminum electrolysis waste cathode carbon blocks with the mass of 8% of the total mass of the sinter ore.
The detection method and the use method of the embodiment are the same as those of the embodiment 1.
The performance parameters of this example as blast furnace iron making raw materials are shown in table 1.
Example 3:
the method for treating the aluminum electrolysis waste cathode carbon blocks provided by the embodiment is based on 4 parts of waste cathode carbon blocks, 32 parts of pellet ore and 64 parts of sinter ore which are directly added into a blast furnace, wherein the sinter ore contains 3% of the aluminum electrolysis waste cathode carbon blocks of the total mass of the sinter ore.
The detection method and the use method of the embodiment are the same as those of the embodiment 1.
The performance parameters of this example as blast furnace iron making raw materials are shown in table 1.
Example 4:
the method for treating the aluminum electrolysis waste cathode carbon blocks provided by the embodiment is based on 20 parts of pellet and 80 parts of sinter, wherein the sinter contains 20% of the aluminum electrolysis waste cathode carbon blocks based on the total mass of the sinter.
The detection method and the use method of the embodiment are the same as those of the embodiment 1.
The performance parameters of this example as blast furnace iron making raw materials are shown in table 1.
Example 5:
the method for treating the aluminum electrolysis waste cathode carbon blocks provided by the embodiment is based on 3 parts of waste cathode carbon blocks, 31 parts of pellet ore and 66 parts of sinter ore which are directly added into a blast furnace, wherein the sinter ore contains the aluminum electrolysis waste cathode carbon blocks accounting for 15% of the total mass of the sinter ore.
The detection method and the use method of the embodiment are the same as those of the embodiment 1.
The performance parameters of this example as blast furnace iron making raw materials are shown in table 1.
Example 6:
the method for treating the aluminum electrolysis waste cathode carbon blocks provided by the embodiment is based on 6 parts of waste cathode carbon blocks, 30 parts of pellet ore and 64 parts of sinter ore which are directly added into a blast furnace, wherein the sinter ore contains 10% of the aluminum electrolysis waste cathode carbon blocks of the total mass of the sinter ore.
The detection method and the use method of the embodiment are the same as those of the embodiment 1.
The performance parameters of this example as blast furnace iron making raw materials are shown in table 1.
Example 7:
the method for treating the aluminum electrolysis waste cathode carbon blocks provided by the embodiment is based on 1 part of waste cathode carbon blocks, 32 parts of pellet ore and 67 parts of sinter ore which are directly added into a blast furnace, wherein the sinter ore contains 30% of the aluminum electrolysis waste cathode carbon blocks of the total mass of the sinter ore.
The detection method and the use method of the embodiment are the same as those of the embodiment 1.
The performance parameters of this example as blast furnace iron making raw materials are shown in table 1.
TABLE 1
In the table, T10％Is the softening onset temperature; t isSIs the melting onset temperature; delta T is a molten drop temperature interval and represents the thickness of the worst interval of the air permeability of the reflow layer; s is a molten drop characteristic index; t isDTo start the dripping temperature; delta PmaxThe maximum differential pressure corresponds to the peak value of the highest differential pressure occurring during the test of the mineral aggregate, which is similar to the maximum value of the mineral aggregate pressure resistance in the blast furnace.
As can be seen from Table 1, the temperature range of the molten drops is effectively reduced, which is beneficial to improving the air permeability of the furnace and the efficiency of the furnace. The aluminum electrolysis waste cathode carbon blocks can effectively reduce the melting point of the raw materials, and the more the cathode carbon blocks are added, the lower the melting temperature of the blast furnace raw materials is. Therefore, according to experimental data, the aluminum electrolysis waste carbon blocks as the raw materials of the sinter cannot be higher than 30% of the total mass of the sinter. The waste carbon blocks from aluminum electrolysis are directly used as blast furnace raw materials, and the adding amount of the waste carbon blocks from aluminum electrolysis cannot be higher than 6.4 percent of the total mass of the blast furnace raw materials.
As can be seen from Table 1, the main components of the aluminum electrolysis waste cathode carbon block contain carbon and fluoride, so that the fluidity, carburetion, reducibility, fuel and heat preservation of molten iron can be effectively improved, and the aluminum electrolysis waste cathode carbon block has good temperature raising effect and slag melting effect on sinter and molten aluminum. The aluminum electrolysis waste cathode carbon blocks are treated by the iron-making process flow, so that the recycling of solid waste in the aluminum electrolysis process is increased, and the additional value of the aluminum electrolysis solid waste in the iron-making process is improved.
It should be noted that the above-mentioned embodiments of the present invention are merely preferred examples of the present invention, and are not intended to limit the scope of the invention, so that the equivalent changes made by the contents of the claims of the present invention should be included in the scope of the claims of the present invention.
Claims (2)
1. A method for processing aluminum electrolysis waste cathode carbon blocks is characterized in that the aluminum electrolysis waste cathode carbon blocks are processed by an iron-making process, and furnace burden of the iron-making process comprises pellets, sinter and the aluminum electrolysis waste cathode carbon blocks; wherein, the furnace burden of the iron-making process comprises 18-32 parts of pellet ore, 64-80 parts of sinter ore and 0-6.4 parts of aluminum electrolysis waste cathode carbon blocks by mass;
the sintered ore contains 0-30 parts of aluminum electrolysis waste cathode carbon blocks by 100 parts by mass;
the content of the aluminum electrolysis waste cathode carbon blocks in the sintering ore and the content of the aluminum electrolysis waste cathode carbon blocks in the furnace burden of the iron-making process are not 0 simultaneously;
the grain size of the furnace burden of the iron-making process is not more than 40 mm;
the grain size of the aluminum electrolysis waste cathode carbon blocks in the sintering ore is not more than 3.0mm, and the content of the aluminum electrolysis waste cathode carbon blocks with the grain size of 3mm in the sintering ore is not less than 70 percent of the total mass of the aluminum electrolysis waste cathode carbon blocks in the sintering ore in percentage by mass;
the aluminum electrolysis waste cathode carbon block comprises the following components in 100 parts by mass: 40-60 parts of C, 9-37 parts of F and 4 parts of SiO24-8.5 parts of Al, 5-15 parts of Na, not more than 0.5 part of S and impurities;
the alkalinity of the pellets is 0.36-0.69; the pellet comprises the following components in 100 parts by mass: 49-60 parts of Fe, 5-15 parts of silicon dioxide, 4-12 parts of calcium oxide, 1-3 parts of aluminum oxide, no more than 0.07 part of sulfur, no more than 0.035 part of phosphorus and impurities;
the alkalinity of the sinter of the waste cathode carbon blocks without aluminum electrolysis is 1.45-1.79, and the sinter of the waste cathode carbon blocks without aluminum electrolysis comprises the following components in 100 parts by mass: 40-55 parts of Fe, 10-20 parts of calcium oxide, 5-15 parts of silicon dioxide, 1-3 parts of aluminum oxide, no more than 0.07 part of sulfur, no more than 0.035 part of phosphorus and impurities.
2. The method for treating the aluminum electrolysis waste cathode carbon blocks as claimed in claim 1, wherein the temperature rising system is as follows when the aluminum electrolysis waste cathode carbon blocks are treated by the iron-making process: when the temperature is less than 1200 ℃, the temperature is increased by 10 ℃ per minute, and the load is 0.7kg/cm2(ii) a When the temperature is more than or equal to 1200 ℃, the temperature is increased by 5 ℃ per minute, and the load is 1kg/cm2。
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