CN113308636B - Method for preparing calcium-phosphorus-free iron ring regulator based on solid waste - Google Patents
Method for preparing calcium-phosphorus-free iron ring regulator based on solid waste Download PDFInfo
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- CN113308636B CN113308636B CN202110582135.3A CN202110582135A CN113308636B CN 113308636 B CN113308636 B CN 113308636B CN 202110582135 A CN202110582135 A CN 202110582135A CN 113308636 B CN113308636 B CN 113308636B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- 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
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Abstract
The invention discloses a method for preparing a calcium-free phosphorus iron ring regulator based on solid waste, wherein the regulator comprises bauxite, silica sand, ferromanganese and a recarburizing agent, and the components are treated and then uniformly mixed in proportion to obtain the uniform phosphorus iron ring regulator. The slag phase viscosity can be increased by adding the solid waste bauxite and reasonably proportioning and mixing the solid waste bauxite and the components, the resulfurization phenomenon after desulfurization is avoided, the effects of recarburization desulfurization and slag conglomeration are realized in one step, the operation is simple, and the industrialization is easy to realize.
Description
Technical Field
The invention relates to the field of metal smelting and raw material preparation, in particular to a method for preparing a calcium-phosphorus-free iron ring regulator based on solid wastes.
Background
The electrolytic aluminum production capacity in China is 4000 ten thousand tons per year, and about 80 ten thousand tons of waste phosphorus iron rings need to be treated every year. The ferrophosphorus ring is a core component for connecting the anode carbon block and the guide rod in the production process of electrolytic aluminum, graphite is gradually lost in the electrolytic process, harmful elements are enriched on the ferrophosphorus ring, the steel claw is protected, and the ferrophosphorus ring needs to be replaced regularly. With the improvement of environmental protection requirements, various aluminum plants gradually begin to recycle and regenerate the waste ferrophosphorus rings. The service environment of the ferrophosphorus ring requires that the control of the content of five major elements (C, S, P, Mn and Si) is strict. The regeneration process at present is to melt and refine the waste ferrophosphorus ring and the regulator together, and then pour and recycle the waste ferrophosphorus ring and the regulator. However, the prior problems are that the recarburization operation and the desulfurization operation are carried out step by step in the refining process of the ferrophosphorus ring, so that the smelting time is increased, the labor intensity is increased, and slag is difficult to remove or slag is difficult to remove without slag accumulation after desulfurization.
Bauxite is a solid waste resource (solid waste), the bauxite resource in China is rich, about 37 hundred million tons exists in the front of the world, and the bauxite solid waste is utilized at a high value, so that the bauxite solid waste is of great significance to the environment.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a calcium-free ferrophosphorus ring regulator based on solid waste bauxite, which uses the bauxite as the ferrophosphorus ring regulator. The invention applies the bauxite which is taken as the solid waste to the regulator to prepare the calcium-phosphorus-free iron ring regulator. The invention mainly comprises a preparation method and a use method of the regulator.
The method is realized by the following technical means:
a method for preparing a calcium-phosphorus-free iron ring regulator based on solid waste comprises the following steps:
step 1: 10-40 parts by weight of bauxite; 10-30 parts of silica sand; 10-50 parts of ferromanganese; 10-40 parts of carburant by weight, and preparing materials.
Step 2: mechanically grinding the bauxite, screening the bauxite after grinding, screening the bauxite into a screen with 20-100 meshes to obtain bauxite particles, drying the screened bauxite particles in a muffle furnace at the temperature of 150-300 ℃ for 0.5-1.5 h, and removing water from the bauxite particles.
And step 3: uniformly mixing silica sand with the granularity of 1-3 mm, ferromanganese with the granularity of 1-3 mm and a carburant with the granularity of 1-3 mm in a mechanical mixing mode to obtain a mixture.
And 4, step 4: and (3) covering the bauxite particles obtained in the step (2) on the mixture obtained in the step (3), and packaging to obtain the calcium-phosphorus-free iron ring regulator.
Preferably, the bauxite comprises the following components: al (Al)2O3：70～80wt％，Fe2O3:10 to 20 wt%, and the balance unavoidable impurities.
Preferably, the inevitable impurities include moisture and SiO2、MgO。
Preferably, the ferromanganese is a ferromanganese alloy, wherein the manganese content is 60-65 wt%, and the balance is iron and inevitable impurities.
Preferably, the recarburizing agent is graphite electrode crushed or graphitized petroleum coke, and the carbon content of the recarburizing agent is 96-99 wt%.
A method for modifying a ferrophosphorus ring by a calcium-free ferrophosphorus ring modifier comprises the following steps:
step a: the calcium-phosphorus-free iron ring regulator prepared by the signing method is configured, so that the mass ratio of the total addition amount of the calcium-phosphorus-free iron ring regulator to the total addition amount of the waste iron rings is (1-3): 100.
Step b: melting 10-30 wt% of the waste ferrophosphorus ring in the total addition amount by an induction furnace, wherein the melting temperature of the induction furnace is 1400-1500 ℃, melting the waste ferrophosphorus ring to be in a liquid state, and the waste ferrophosphorus ring which is melted to be in the liquid state accounts for 15-20% of the capacity of the induction furnace.
Step c: and c, adding the calcium-phosphorus-free iron ring regulator which accounts for 28-32% of the total addition amount into the induction furnace in the step b.
Step d: c, adding the rest waste ferrophosphorus rings into the induction furnace in the step c, wherein the melting temperature of the induction furnace is 1400-1500 ℃, and adding the rest 68-72% of calcium-free ferrophosphorus ring regulator into the induction furnace after the added waste ferrophosphorus rings are completely melted into a liquid state; performing melt refining for 5-10 min, discharging after slagging off, and increasing the temperature of the induction furnace to the discharging temperature: and 1450-1550 ℃ to obtain the improved ferrophosphorus ring molten iron.
Preferably, the induction furnace is a medium frequency induction furnace.
The calcium-phosphorus-free iron ring regulator is prepared by the method and comprises the following components: 10-40 wt% of bauxite with the particle size of 0.5-3 mm; silica sand with granularity of 1-3 mm: 10-30 wt%; ferromanganese with a particle size of 1-3 mm: 10 to 50 wt%; a carburant with a particle size of 1-3 mm: 10 to 40 wt%.
The invention has the technical effects that:
according to the invention, the addition amount of bauxite is adjusted reasonably and simultaneously matched with the content of silica sand and ferromanganese, so that the slag conglomeration and bonding phenomenon is greatly improved after the regulator is added into the molten alloy liquid. This is because bauxite contains Al as a main component2O3So that the melting point of the bauxite is higher, about 1800-1900 ℃, and the bauxite shows a sticky state in an induction furnace, and the refined slag phase is obtainedSo as to bind and aggregate, and avoid resulfurization. The influence of the addition amount of bauxite on the slag phase bonding effect is large, and researches show that if the addition amount is too small, the slag phase bonding degree is low, the melting point is low, and slagging-off is still difficult to carry out; if the addition amount is too large, the slag phase cohesiveness is too high, the melting point is too high, the refining temperature and energy consumption are increased, and the slag phase slag amount is too large, so that slagging-off is more difficult to carry out, thereby greatly reducing the final effect. Therefore, the invention determines that the addition amount of the bauxite is within the range set by the invention through creative development.
According to the invention, the research shows that the recarburization and desulfurization effect is not caused by only adding bauxite; the recarburization and desulfurization effects can be achieved by only adding silica sand, ferromanganese and recarburization agent, and the desulfurization efficiency is over 21 percent; for the final effect, no bauxite was added: the aggregation effect of the surface slag phase is poor, and the melting point of the slag phase is low. Adding bauxite: the slag phase has obvious adhesion phenomenon, black substances are increased, and the melting point of the slag phase is increased. Therefore, when the bauxite, the silica sand, the ferromanganese and the carburant are added simultaneously and the content of the bauxite, the silica sand, the ferromanganese and the carburant is limited within the numerical range of the invention, the obvious recarburization and desulfurization effect is shown, and the desulfurization efficiency is more than 34 percent, namely the addition of the bauxite and the reasonable specific limitation on the content of each component can improve the desulfurization efficiency by more than 13 percent.
When the calcium-phosphorus-free iron ring regulator is prepared, bauxite particles with specific granularity are laid on a mixture of silica sand, ferromanganese and a recarburizing agent with specific granularity (by matching the content ratio of each component), so that the regulator can effectively bond and conglomerate slag, simplify slagging operation and improve desulfurization effect when applied.
Drawings
FIG. 1 is a diagram of a molten sample of comparative example 1 of the present invention.
FIG. 2 is a drawing of a molten sample of example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
In the embodiment, a medium-frequency induction furnace is adopted, and C in the initial waste ferrophosphorus ring element content is 2.01 wt%; s is 0.642 wt%. The dosage of the ferrophosphorus ring is 400kg, wherein the proportion of the calcium-free ferrophosphorus ring regulator is as follows: 30wt% of bauxite, 10 wt% of silica sand, 30wt% of ferromanganese and 30wt% of carburant. The amount of the modifier added was 2.0 wt%.
60kg of waste ferrophosphorus rings are melted by an induction furnace, the melting temperature of the induction furnace is 1430 ℃, the waste ferrophosphorus rings are melted to be in a liquid state, and the waste ferrophosphorus rings melted to be in the liquid state account for 16% of the capacity of the induction furnace.
The calcium phosphorus free iron ring conditioner was added to the induction furnace at 30% of the total addition.
Adding the rest waste ferrophosphorus ring into an induction furnace, wherein the melting temperature of the induction furnace is 1435 ℃, and adding the rest 70% of calcium-free ferrophosphorus ring regulator into the induction furnace after the added waste ferrophosphorus ring is completely melted into a liquid state; carrying out melt refining for 8min, discharging after slagging off, and increasing the temperature of the induction furnace to the discharging temperature: 1500 ℃ in the presence of a catalyst. Obtaining the improved ferrophosphorus ring molten iron. Sampling and measuring the content of the ferrophosphorus ring elements after refining, C: 2.35 wt%, S: 0.421 wt%.
Comparative example 1
The regulator of the mixture of the comparative example does not contain bauxite, and the other setting modes are the same as the example 1, so that the ferrophosphorus ring molten iron is obtained. Sampling and measuring the content of the ferrophosphorus ring elements after refining, C: 2.34 wt%, S: 0.508 wt%.
Comparative example 2
The regulator of the mixture of the comparative example only contains bauxite, and the other setting modes are the same as the example 1, so that the ferrophosphorus ring molten iron is obtained. Sampling and measuring the content of the ferrophosphorus ring elements after refining, C: 1.98 wt%, S: 0.641 wt%.
The specific C and S contents of the above examples and comparative examples are shown in table 1:
TABLE 1
The test result shows that the carbon increasing and desulfurizing effect is not obvious only by adding bauxite; only adding silica sand, ferromanganese and carburant has certain carburant and desulfurization effects, and the desulfurization efficiency is 21%; when bauxite, silica sand, ferromanganese and carburant are added and the content proportion in the numerical range of the invention is adopted, obvious carburant desulfurization effect is shown, and the desulfurization efficiency is 34%, compared with the bauxite, the desulfurization efficiency can be improved by 13%. From the results of the above comparative experiment, in combination with the comparison of fig. 1 and 2, it can be obtained that no bauxite was added: the aggregation effect of the surface slag phase is poor, and the melting point of the slag phase is low. Adding bauxite: the slag phase has obvious adhesion phenomenon, black substances are increased, and the melting point of the slag phase is increased. The reasonable proportion of the bauxite, the silica sand, the ferromanganese and the carburant shows that the bauxite not only can effectively bond and gather slag, simplify the slag skimming operation, but also can improve the desulfurization effect.
Example 2
In the embodiment, a medium-frequency induction furnace is adopted, and the content of C in the initial waste ferrophosphorus ring element is 2.46 wt%; s is 0.342 wt%. The dosage of the ferrophosphorus ring is 400kg, wherein the proportion of the calcium-free ferrophosphorus ring regulator is as follows: 30wt% of bauxite, 20 wt% of silica sand, 20 wt% of ferromanganese and 30wt% of carburant. The amount of the modifier added was 1.5 wt%.
80kg of waste ferrophosphorus rings are melted by an induction furnace, the melting temperature of the induction furnace is 1450 ℃, the waste ferrophosphorus rings are melted to be in a liquid state, and the waste ferrophosphorus rings melted to be in the liquid state account for 18 percent of the capacity of the induction furnace.
The calcium phosphorus free iron ring conditioner was added to the induction furnace at 30% of the total addition.
Adding the rest waste ferrophosphorus rings into an induction furnace, wherein the melting temperature of the induction furnace is 1455 ℃, and adding the rest 70% of calcium-free ferrophosphorus ring regulator into the induction furnace after the added waste ferrophosphorus rings are completely melted into liquid; carrying out melt refining for 6min, discharging after slagging off, and increasing the temperature of the induction furnace to the discharging temperature: 1530 ℃. Obtaining the improved ferrophosphorus ring molten iron. Sampling and measuring the content of the ferrophosphorus ring elements after refining, C: 2.78 wt%, S: 0.114 wt%.
Example 3
In the content of the initial waste ferrophosphorus ring element of this embodiment, C: 2.02 wt%; s: 0.538 wt%. The dosage of the ferrophosphorus ring is 400kg, wherein the proportion of the calcium-free ferrophosphorus ring regulator is as follows: 15 wt% of bauxite, 15 wt% of silica sand, 20 wt% of ferromanganese and 50 wt% of carburant. The addition amount of the calcium-phosphorus-free iron ring regulator is 2 wt%.
The melting addition procedure and parameters were the same as in example 2, and the content of the ferrophosphorus ring element after refining was determined by sampling, C: 2.33 wt%, S: 0.267 wt%.
Example 4
The initial ferrophosphorus ring element content of this example is as follows, C: 3.18 wt%; s: 0.211 wt%. The dosage of the ferrophosphorus ring is 400kg, wherein the proportion of the calcium-free ferrophosphorus ring regulator is as follows: 15 wt% of bauxite, 20 wt% of silica sand, 25 wt% of ferromanganese and 40 wt% of carburant. The total addition amount of the calcium-phosphorus-free iron ring regulator is 3 wt%. The melting addition procedure and parameters were the same as in example 2, and the content of the ferrophosphorus ring element after refining was determined by sampling, C: 3.34 wt%, S: 0.087 wt%.
Example 5
The method for preparing the calcium-phosphorus-free iron ring regulator by using bauxite treated as solid waste conventionally as a main raw material comprises the following steps:
step 1: taking 30 parts by weight of bauxite; 20 parts of silica sand; 30 parts of ferromanganese; 20 parts of carburant by weight, and preparing materials;
wherein the bauxite comprises the following components: al (Al)2O3：70～80wt％，Fe2O3:10 to 20 wt%, the balance being water and SiO2And MgO, etc. The ferromanganese is ferromanganese alloy, wherein the manganese content is 63 wt%, and the balance is iron and inevitable impurities. The recarburizing agent is graphite electrode scraps, and the carbon content of the recarburizing agent is 98 wt%.
Step 2: mechanically grinding bauxite, screening the ground bauxite to obtain bauxite particles with the granularity of 20-100 meshes (the particle size of the bauxite particles is different from that of a mixture), placing the screened bauxite particles in a muffle furnace, drying the bauxite particles for 1h at the temperature of 200 ℃, and removing the moisture of the bauxite particles;
and step 3: uniformly mixing silica sand with the granularity of 1-3 mm, ferromanganese with the granularity of 1-3 mm and a carburant with the granularity of 1-3 mm in a mechanical mixing mode to obtain a mixture;
and 4, step 4: and (3) covering the bauxite particles obtained in the step (2) on the mixture obtained in the step (3), and packaging to obtain the calcium-phosphorus-free iron ring regulator.
Claims (8)
1. A method for preparing a calcium-phosphorus-free iron ring regulator based on solid waste is characterized by comprising the following steps:
step 1: 10-40 parts by weight of bauxite; 10-30 parts of silica sand; 10-50 parts of ferromanganese; 10-40 parts by weight of carburant, and preparing materials;
step 2: mechanically grinding bauxite, screening the ground bauxite to obtain bauxite particles with the granularity of 20-100 meshes, drying the screened bauxite particles in a muffle furnace at the temperature of 150-300 ℃ for 0.5-1.5 h, and removing water from the bauxite particles;
and step 3: uniformly mixing silica sand with the granularity of 1-3 mm, ferromanganese with the granularity of 1-3 mm and a carburant with the granularity of 1-3 mm in a mechanical mixing mode to obtain a mixture;
and 4, step 4: and (3) covering the bauxite particles obtained in the step (2) on the mixture obtained in the step (3), and packaging to obtain the calcium-phosphorus-free iron ring regulator.
2. The method for preparing calcium-phosphorus-free iron ring regulator based on solid waste according to claim 1, wherein the bauxite comprises the following components: al (Al)2O3：70~80 wt%，Fe2O3:10 to 20 wt%, and the balance unavoidable impurities.
3. The method for preparing calcium-phosphorus-free iron ring modifier based on solid waste according to claim 2, wherein the inevitable impurities comprise moisture and SiO2、MgO。
4. The method for preparing a calcium-phosphorus-free iron ring modifier based on solid wastes according to claim 1, wherein the ferromanganese is a ferromanganese alloy with a manganese content of 60 to 65 wt%, and the balance of iron and inevitable impurities.
5. The method for preparing the calcium-phosphorus-free iron ring modifier based on the solid waste according to claim 1, wherein the carburant is graphite electrode crumbs or graphitized petroleum coke, and the carbon content of the carburant is 96-99 wt%.
6. A method for improving a ferrophosphorus ring by a calcium-free ferrophosphorus ring regulator is characterized by comprising the following steps:
step a: configuring the calcium-phosphorus-free iron ring regulator prepared according to any one of claims 1 to 5, wherein the mass ratio of the total addition amount of the calcium-phosphorus-free iron ring regulator to the total addition amount of the waste iron phosphorus ring regulator is (1-3): 100;
step b: melting 10-30 wt% of the waste ferrophosphorus ring in the total addition amount by an induction furnace, wherein the melting temperature of the induction furnace is 1400-1500 ℃, melting the waste ferrophosphorus ring to a liquid state, and the waste ferrophosphorus ring which is melted to the liquid state accounts for 15-20% of the capacity of the induction furnace;
step c: adding 28-32% of the total addition amount of the calcium-phosphorus-free iron ring regulator into the induction furnace in the step b;
step d: c, adding the rest waste ferrophosphorus rings into the induction furnace in the step c, wherein the melting temperature of the induction furnace is 1400-1500 ℃, and adding the rest 68-72% of calcium-free ferrophosphorus ring regulator into the induction furnace after the added waste ferrophosphorus rings are completely melted into a liquid state; melting and refining for 5-10 min, and increasing the temperature of the induction furnace to the tapping temperature: and (4) discharging the slag at 1450-1550 ℃ to obtain the improved ferrophosphorus ring molten iron.
7. The method of modifying a ferrophosphorus ring with a calcium free ferrophosphorus ring modifier as claimed in claim 6, wherein the induction furnace is a medium frequency induction furnace.
8. A calcium-phosphorus-free iron ring regulator, which is prepared by the method of any one of claims 1 to 5 and comprises the following components: 10-40 wt% of bauxite with the particle size of 0.5-3 mm; silica sand with granularity of 1-3 mm: 10-30 wt%; ferromanganese with a particle size of 1-3 mm: 10 to 50 wt%; a carburant with a particle size of 1-3 mm: 10 to 40 wt%.
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