CN113337676A - Modifier for deep desulfurization of ferrophosphorus ring - Google Patents
Modifier for deep desulfurization of ferrophosphorus ring Download PDFInfo
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- CN113337676A CN113337676A CN202110635686.1A CN202110635686A CN113337676A CN 113337676 A CN113337676 A CN 113337676A CN 202110635686 A CN202110635686 A CN 202110635686A CN 113337676 A CN113337676 A CN 113337676A
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- ferrophosphorus
- modifier
- deep desulfurization
- ferrophosphorus ring
- rare earth
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/064—Dephosphorising; Desulfurising
- C21C7/0645—Agents used for dephosphorising or desulfurising
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a rare earth element mineral serving as a modifier for deep desulfurization of a ferrophosphorus ring, wherein the modifier is a mixture comprising a specific rare earth element mineral and a calcium-phosphorus-containing mineral. The modifier for ferrophosphorus ring deep desulfurization can realize the aim of low-sulfur ferrophosphorus ring deep desulfurization, and the desulfurization rate can reach over 72 percent.
Description
Technical Field
The invention relates to the fields of metal smelting and raw material preparation, in particular to a modifier for deep desulfurization of a ferrophosphorus ring.
Background
The ferrophosphorus ring is a key part for connecting the anode carbon block and the guide rod in the production of electrolytic aluminum, and needs to be replaced periodically. The recycling and regeneration of the waste ferrophosphorus ring becomes a key point and a difficult point of research and development, for the recycling and regeneration of the waste ferrophosphorus ring, the content control of sulfur is a key point and a key point, and the conductivity is reduced and the smelting viscosity is increased after the content of sulfur is increased. The existing regeneration process is to carry out desulfurization operation by melting and refining waste ferrophosphorus rings and a regulator together, but because the sulfur content in the recycled ferrophosphorus rings is less than or equal to 0.05 wt%, the cost required by the existing desulfurizing agent to achieve the purpose is high, and the alkalinity of the desulfurizing agent is high, so that a furnace lining is easy to corrode, and a deep desulfurization modifier with low cost and good desulfurization effect needs to be developed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a modifier for realizing the deep desulfurization of a ferrophosphorus ring.
To achieve the above effects, the present invention is implemented by the following schemes:
the ferrophosphorus ring deep desulfurization modifier comprises the following components: the mixture of the rare earth element ore and the calcium-phosphorus-containing mineral comprises the following components in percentage by weight: (2-5): 1.
preferably, the rare earth element ore is a mineral containing rare earth oxide, silicon dioxide and ferric oxide.
Preferably, the rare earth element ore comprises the following components: RE2O3：10～20wt％，SiO2：20～45wt％，Fe2O3: 30 to 40 wt%, and the balance unavoidable impurities.
Preferably, the calcium-phosphorus-containing mineral comprises the following components: 50 to 60 wt%, P2O3: 30 to 50 wt%, and the balance unavoidable impurities.
Preferably, the rare earth element ore is portobeite or cerite.
Preferably, the calcium-containing phosphorus mineral is apatite.
A preparation method of a ferrophosphorus ring deep desulfurization modifier comprises the following steps:
step 1: mechanically grinding the rare earth element ore, screening after grinding, screening through a sieve mesh of 50-100 meshes to obtain rare earth element ore particles, placing the screened rare earth element ore particles in a muffle furnace, drying at the temperature of 150-300 ℃ for 0.5-1.5 h, and removing a crystal water component.
Step 2: and grinding the calcium-containing phosphate ore, screening after grinding, and screening through a sieve mesh of 100-200 meshes to obtain calcium-containing and phosphorus-containing mineral powder.
And step 3: and (3) mechanically mixing the calcium-containing phosphorite powder obtained in the step (2) with the rare earth element ore particles obtained in the step (1) according to the weight part ratio of the calcium-containing phosphorite powder to the rare earth element ore particles of 1 (2-5) to obtain the ferrophosphorus ring deep desulfurization modifier.
Preferably, the granularity of the rare earth element ore is 0.15-0.3 mm, and the granularity of the calcium-phosphorus-containing mineral is less than 0.15 mm.
A method for treating waste ferrophosphorus rings by using a ferrophosphorus ring deep desulfurization modifier comprises the following steps:
step a, preparing the ferrophosphorus ring deep desulfurization modifier by using the preparation method, wherein the mass ratio of the addition amount of the ferrophosphorus ring deep desulfurization modifier to the total addition amount of the waste ferrophosphorus rings is (1-3): 100.
Step b: weighing the waste ferrophosphorus rings, placing the waste ferrophosphorus rings in an induction furnace for melting, wherein the melting temperature of the induction furnace is 1400-1500 ℃, and melting the waste ferrophosphorus rings to be liquid.
Step c: and (b) completely adding the ferrophosphorus ring deep desulfurization modifier obtained in the step a into the induction furnace in the step b, melting the ferrophosphorus ring deep desulfurization modifier on the surface of the waste ferrophosphorus ring melt, refining for 5-10 min after the ferrophosphorus ring deep desulfurization modifier is melted, and then increasing the temperature of the induction furnace to the tapping temperature: and (4) slagging off at 1450-1550 ℃, and discharging to obtain the deep-desulfurization ferrophosphorus ring molten iron.
The invention has the technical effects that:
the invention can control the sulfur content in the ferrophosphorus ring at a lower level by mixing the rare earth minerals and the calcium-containing phosphorus minerals as the deep desulfurization modifier. This is because the rare earth minerals exist in the form of rare earth oxides in a molten state, and they can react with sulfur in molten iron to produce sulfur-oxidized rare earth element substances. The chemical reaction formula is as follows:
(Re2O3)+[S]+[Si]＝(Re2O2S)+(SiO2)。
the Gibbs free energy of the reaction is lower, so that an ideal effect can be achieved for the molten iron desulphurization process with low sulphur content.
The invention adds the calcium and phosphorus mineral (preferably apatite) as an important auxiliary material into the deep desulfurization modifier, and has the effects that the calcium and phosphorus mineral, particularly the apatite, contains CaO, and the existence of CaO improves the desulfurization effect of the ferro-phosphorus ring; secondly, the content of phosphorus in the minerals containing calcium and phosphorus, especially the apatite can inhibit the oxidation loss of phosphorus in the ferrophosphorus molten iron, thereby achieving the effect of improving the deep desulfurization of the rare earth oxides without bringing the loss of elements such as phosphorus and the like, and having close coordination with the rare earth ore.
Research shows that when the sulfur content in the ferrophosphorus ring is higher than 0.1 wt%, the activity of calcium oxide and the activity of sulfur are high, and desulfurization reaction is easy to occur, and when the sulfur content is reduced to be less than 0.1 wt%, the activity of sulfur content is reduced, and at the moment, if the content of calcium oxide is increased, the phenomenon that the addition amount of a desulfurizing agent is too high can occur. Therefore, rare earth element minerals are mixed with the apatite, and the specific content proportion of the invention is matched, so that the waste of excessive rare earth elements is effectively avoided, and the use efficiency of the apatite is effectively improved.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The invention respectively carries out the comparison experiment on the addition of the apatite and the rare earth mineral, and the initial sulfur content is about 0.10 wt% under the condition of low sulfur, and the comparison experiment is carried out under the condition of the same addition amount. If only rare earth ore is added, the desulfurization efficiency is 62 percent; if only the apatite is added, the desulfurization efficiency is 12 percent; when the mixture of rare earth ore and apatite is added, the desulfurization efficiency can reach 73 percent, which is increased by 11 percent compared with the method of only adding rare earth ore, and finally the sulfur content in the ferrophosphorus ring is reduced to 0.033wt percent. The specific comparative test cases are as follows:
example 1
In the embodiment, a medium frequency induction furnace is adopted, and S in the initial waste ferrophosphorus ring element content of the embodiment is 0.121 wt%. The dosage of the ferrophosphorus ring is 450kg, wherein the proportion of the deep desulfurization modifier is as follows: 70 wt% of cerite, apatite: 30 wt%. The addition amount of the ferrophosphorus ring deep desulfurization modifier is 2.0 wt%.
Melting 450kg of waste ferrophosphorus ring in an induction furnace, wherein the melting temperature of the induction furnace is 1430 ℃, melting the waste ferrophosphorus ring to be liquid, and adding the ferrophosphorus ring deep desulfurization modifier into the induction furnace. After the modifier is melted into liquid, 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, S: 0.045 wt%.
Comparative example 1
The modifier prepared in the comparative example only contains apatite, and the other setting modes are the same as those of the example 1, so that the ferrophosphorus ring molten iron is obtained. Sampling and measuring the content of the ferrophosphorus ring elements after refining, S: 0.104 wt%.
Comparative example 2
The regulator of the mixture of the comparative example only contains the cerite, 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, S: 0.057 wt%.
The specific S contents of the above examples and comparative examples are shown in table 1:
TABLE 1
As can be seen from the test results, the desulfurization effect is not obvious only by adding apatite; only adding the cerite has relative desulfurization effect, and the desulfurization efficiency is 53 percent; when the apatite and the cerite are added and the content proportion in the numerical range of the invention is adopted, the obvious desulfurization effect is shown, and the desulfurization efficiency is 63 percent, compared with the method, the desulfurization efficiency can be greatly improved by more than 10 percent by adding the mixture.
Example 2
The method adopts a medium-frequency induction furnace, and the initial low-sulfur ferrophosphorus ring element content is as follows, S: 0.097 wt%. The dosage of the ferrophosphorus ring is 450kg, wherein the used ferrophosphorus ring deep desulfurization modifier comprises the following components in percentage by weight: 80 wt% of cerite, apatite: 20 wt%. The addition amount of the ferrophosphorus ring deep desulfurization modifier is 3 wt% of the dosage of the ferrophosphorus ring. After the ferrophosphorus ring is melted by an induction furnace, adding a ferrophosphorus ring deep desulfurization modifier, taking out the ferrophosphorus ring 10min after complete melting, sampling and measuring the element content of the refined ferrophosphorus ring, S: 0.032 wt%.
Example 3
The method adopts a medium-frequency induction furnace, and the initial low-sulfur ferrophosphorus ring element content is as follows, S: 0.088 wt%. The dosage of the ferrophosphorus ring is 450kg, wherein the used ferrophosphorus ring deep desulfurization modifier comprises the following components in percentage by weight: 75 wt% of brown cord stone, apatite: 25 wt%. The addition amount of the ferrophosphorus ring deep desulfurization modifier is 1 wt% of the dosage of the ferrophosphorus ring. After the ferrophosphorus ring is melted by an induction furnace, adding a ferrophosphorus ring deep desulfurization modifier, taking out the ferrophosphorus ring from the furnace 10min after complete melting, sampling and measuring the element content of the refined ferrophosphorus ring, S: 0.020 wt%.
Claims (9)
1. The ferrophosphorus ring deep desulfurization modifier is characterized by comprising rare earth element ore and calcium-phosphorus-containing mineral, wherein the weight ratio of the rare earth element ore to the calcium-phosphorus-containing mineral is as follows: (2-5): 1.
2. the improver for deep desulfurization of a ferrophosphorus ring according to claim 1, wherein said rare earth element ore is a mineral containing rare earth oxide, silica and iron sesquioxide.
3. The ferrophosphorus ring deep desulfurization improver as recited in claim 1, wherein the rare earth element ore comprises the following components: RE2O3：10～20wt％，SiO2：20～45wt％，Fe2O3: 30 to 40 wt%, and the balance unavoidable impurities.
4. The improver for deep desulfurization of a ferrophosphorus ring according to claim 1, wherein the calcium-phosphorus-containing mineral comprises CaO: 50 to 60 wt%, P2O3: 30 to 50 wt%, and the balance unavoidable impurities.
5. The agent as claimed in claim 2, 3 or 4, wherein the rare earth element ore is brownish curtain stone or cerite.
6. The improver for deep desulfurization of a ferrophosphorus ring according to claim 2, 3 or 4, wherein the calcium-phosphorus-containing mineral is apatite.
7. A preparation method of a ferrophosphorus ring deep desulfurization modifier, which is characterized in that the ferrophosphorus ring deep desulfurization modifier is the ferrophosphorus ring deep desulfurization modifier of any one of claims 1 to 6, and the preparation method comprises the following steps:
step 1: mechanically grinding the rare earth element ore, screening after grinding, screening through a sieve mesh of 50-100 meshes to obtain rare earth element ore particles, placing the screened rare earth element ore particles in a muffle furnace, drying at the temperature of 150-300 ℃ for 0.5-1.5 h, and removing a crystal water component;
step 2: grinding the calcium-containing phosphate ore, screening after grinding, and screening through a sieve mesh of 100-200 meshes to obtain calcium-containing and phosphorus-containing mineral powder;
and step 3: and (3) mechanically mixing the calcium-containing phosphorite powder obtained in the step (2) with the rare earth element ore particles obtained in the step (1) according to the weight part ratio of the calcium-containing phosphorite powder to the rare earth element ore particles of 1 (2-5) to obtain the ferrophosphorus ring deep desulfurization modifier.
8. The preparation method of the ferrophosphorus ring deep desulfurization modifier according to claim 7, wherein the particle size of the rare earth element ore is 0.15-0.3 mm, and the particle size of the calcium-phosphorus-containing mineral is less than 0.15 mm.
9. A method for treating waste ferrophosphorus rings by using a ferrophosphorus ring deep desulfurization modifier is characterized by comprising the following steps:
step a, the ferrophosphorus ring deep desulfurization modifier in any one of claims 1 to 6 is prepared by using the preparation method in claim 7 or 8, so that the mass ratio of the addition amount of the ferrophosphorus ring deep desulfurization modifier to the total addition amount of the waste ferrophosphorus rings is (1-3): 100;
step b: weighing waste ferrophosphorus rings, placing the waste ferrophosphorus rings in an induction furnace for melting, wherein the melting temperature of the induction furnace is 1400-1500 ℃, and melting the waste ferrophosphorus rings to a liquid state;
step c: and (b) completely adding the ferrophosphorus ring deep desulfurization modifier obtained in the step a into the induction furnace in the step b, melting the ferrophosphorus ring deep desulfurization modifier on the surface of the waste ferrophosphorus ring melt, refining for 5-10 min after the ferrophosphorus ring deep desulfurization modifier is melted, and then increasing the temperature of the induction furnace to the tapping temperature: and (4) slagging off at about 1450-1550 ℃, and discharging to obtain the deep-desulfurization ferrophosphorus ring molten iron.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3492118A (en) * | 1966-05-24 | 1970-01-27 | Foote Mineral Co | Process for production of as-cast nodular iron |
| CN101376917A (en) * | 2008-09-23 | 2009-03-04 | 兰州连城陇兴铝业有限责任公司 | Phosphorus pig iron additive for aluminum electrolysis |
| CN101397643A (en) * | 2008-09-23 | 2009-04-01 | 兰州连城陇兴铝业有限责任公司 | Novel phosphorus and sulphur pig iron for aluminum electrolysis |
| CN101705334A (en) * | 2009-11-13 | 2010-05-12 | 江苏大学 | Aluminum-calcium-magnesium-cerium composite alloy used for strong desulfurization, final desoxidation, and quenching and tempering of liquid steel |
| CN109722498A (en) * | 2019-02-28 | 2019-05-07 | 河南师范大学新联学院 | A kind of waste and old phosphorus pig iron desulfurizing agent and its desulfurization carburetion method |
| CN111485051A (en) * | 2020-06-12 | 2020-08-04 | 韩波 | Phosphorus pig iron high-efficiency desulfurizer for aluminum electrolysis |
-
2021
- 2021-06-08 CN CN202110635686.1A patent/CN113337676B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3492118A (en) * | 1966-05-24 | 1970-01-27 | Foote Mineral Co | Process for production of as-cast nodular iron |
| CN101376917A (en) * | 2008-09-23 | 2009-03-04 | 兰州连城陇兴铝业有限责任公司 | Phosphorus pig iron additive for aluminum electrolysis |
| CN101397643A (en) * | 2008-09-23 | 2009-04-01 | 兰州连城陇兴铝业有限责任公司 | Novel phosphorus and sulphur pig iron for aluminum electrolysis |
| CN101705334A (en) * | 2009-11-13 | 2010-05-12 | 江苏大学 | Aluminum-calcium-magnesium-cerium composite alloy used for strong desulfurization, final desoxidation, and quenching and tempering of liquid steel |
| CN109722498A (en) * | 2019-02-28 | 2019-05-07 | 河南师范大学新联学院 | A kind of waste and old phosphorus pig iron desulfurizing agent and its desulfurization carburetion method |
| CN111485051A (en) * | 2020-06-12 | 2020-08-04 | 韩波 | Phosphorus pig iron high-efficiency desulfurizer for aluminum electrolysis |
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Inventor after: Wang Haijuan Inventor after: Han Yu Inventor after: Chang Chao Inventor after: Liu Linhu Inventor after: Lu Yongjun Inventor after: Lu Conghui Inventor after: Duan Xinle Inventor before: Wang Haijuan Inventor before: Han Yu Inventor before: Chang Chao Inventor before: Lu Yongjun Inventor before: Lu Conghui Inventor before: Duan Xinle |
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