CN1006810B - Refined re ore slag electric arc furnace smelting rare earth intermediate alloy - Google Patents
Refined re ore slag electric arc furnace smelting rare earth intermediate alloyInfo
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- CN1006810B CN1006810B CN 85103958 CN85103958A CN1006810B CN 1006810 B CN1006810 B CN 1006810B CN 85103958 CN85103958 CN 85103958 CN 85103958 A CN85103958 A CN 85103958A CN 1006810 B CN1006810 B CN 1006810B
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- rare earth
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Abstract
Refined re ore slag electric arc furnace smelting rare earth intermediate alloy belongs to ferroalloy smelting.Adopt refined re ore slag electric arc furnace silicothermic process to produce low titanium alloy of high rare earth (RE30～46%, Ti＜1%); Rare earth, silicon, iron respectively account for 1/3rd, the rare-earth low titanium alloy of Ti＜0.5% and rare earth calcium alloy.The present invention has improved the rare earth grade of alloy, reduced the titanium content in the alloy, capture rare earth ore concentrate and directly smelted rare earth intermediate alloy product atomizing difficulty, and it is easy and simple to handle, power consumption is low, production efficiency height, good product quality, economic and technical norms are reasonable, and the gained rare earth intermediate alloy is as steel additive agent.
Description
The present invention is the rare earth intermediate alloy that is used for steel additive agent, belongs to ferroalloy smelting.
Smelt rare earth intermediate alloy, past continues to use always and contains that poor iron ore lean ore rare earth slag in blast furnace deferrization production is a raw material in the rare earth, and lime is sludging flux, and ferrosilicon is a reductive agent, carries out reducing and smelting by certain ratio of components in electric arc furnace, produces rare earth intermediate alloy.Middle lean ore rare earth slag is because of containing rare earth oxide grade lower (REO10～15%), so not only limited the add-on of reductive agent ferrosilicon, production efficiency is low; And make the rare earth intermediate alloy rare earth grade of producing carry not high (RE＜30%).Carry out under high basicity because of smelting the rare earth intermediate alloy operational requirement again, so also need increase the add-on of lime, this has correspondingly reduced the content of slag middle-weight rare earths oxide compound again, and prolonged tap to tap time, power consumption increases, and this brings many difficulties to reducing and smelting.If produce rare earth 30～33% alloys with this slag, yield rate only reaches 50%, and in the alloy titanium content greater than 1.5%.Want to produce rare earth greater than 33%, titanium is impossible less than 1% rare earth intermediate alloy.If in steel, do additive greater than 1% rare earth intermediate alloy with titanium, because titanium forms tiny Ti(C, N in steel) compound, though the energy crystal grain thinning, it is bad to reducing the brittle transition temperature effect, so applying unit all requires to reduce the titanium content in the rare earth alloy, general requirement is less than 1%.
Also the someone studies with the method for rare earth ore concentrate directly into stove smelting and preparing rare earth intermediate alloy, but owing to not only contain 5～11% ferric oxide in the rare earth ore concentrate, also contain mineral such as higher phosphorus, manganese, titanium simultaneously, when direct reducing and smelting, iron, manganese, titanium elements are easy to reduction and enter in the alloy, also not only consume a large amount of reductive agent (ferrosilicon), reduce the utilization ratio of effective silicon and the ability of reduction of rare earth, carry not high thereby have influence on alloy middle-weight rare earths content.In addition, because the phosphide of high level exists, caused the efflorescence of rare earth intermediate alloy product.
Also having some producer is raw material with the rare earth oxide, is reductive agent with ferrosilicon-aluminium, produces rare earth intermediate alloy in electric arc furnace or induction furnace.But this method is because the expense of rare earths material accounts for 80% of rare earth alloy product cost, and therefore, economic benefit is unfavorable.
Purpose of the present invention, be that employing 30～60% refined re ore slags are raw material (method for formulating of this slag is described in the CN1003865B of authorization on April 12nd, 1989 bulletin), produce rare earth intermediate alloy cost-effectively, not only improved the rare earth grade of alloy, reduce the titanium content in the alloy, and solved the alloy pulverization problem.
The detailed content of invention:
Producing of rare earth intermediate alloy adopted the silicothermic process reducing and smelting, is reductive agent with ferrosilicon, and rare earth ferrosilicon alloy is produced in reduction from mixed rare-earth oxide; Add flux lime, improve furnace charge basicity, for reducing and smelting creates conditions smoothly.
The ferrosilicon reduction of rare earth oxides is undertaken by following formula:
Having under the CaO existence condition, can make SiO
2Generate Calucium Silicate powder with CaO, help reaction and carry out to the right.
By requirement of the present invention, raw materials used should possess following condition:
Refined re ore slag major ingredient: rare earth oxide 30～60%, calcium oxide 15～30%, silicon-dioxide 6～15%, fluorine 6～17%; Foreign matter content meets the following requirements: full iron is converted to the iron amount less than the 0.5%(ferric oxide), titanium dioxide is less than 0.3%, and Vanadium Pentoxide in FLAKES is less than 0.5%.
Granularity: less than 150 millimeters.
Other ingredient requirement is:
Lime: CaO＞85%, bulk is no more than 10% less than 20 mm particle sizes,
Ferrosilicon: Si＞72%, granularity: 50～200 millimeters,
Rare earth intermediate alloy is smelted and to be carried out in electric arc furnace, carbonaceous furnace lining, Graphite Electrodes, body of heater be fixed on can before and after on the camber frame that fascinates, the electrode automatic lifting is reconciled power supply, adopts semicontinuous production.
The smelting technology flow process of rare earth intermediate alloy is seen Figure of description.
By ratio of components, at first refined re ore slag and lime are mixed in the adding electric arc furnace, send electrofusion, between melting period, constantly push the furnace charge around in the stove to high-temperature zone, when treating that material fusing 85% is above, again with in the reductive agent ferrosilicon adding stove, ferrosilicon has melted, and furnace temperature rises to more than 1400 ℃, the dense smoke of emerging in the stove, the slag surface is the boiling shape, and the effusion bubble, have a power failure immediately, mention electrode, insert agitator, logical pressurized air stirs.The purpose that stirs is the surface reaction that increases reductive agent and slag, and fast reaction speed makes it abundant reduction, improves the rare earth grade.Revert to terminal point, continue feeding temperature-raising, get the liquid alloy sample, both analysis, grade is qualified can come out of the stove.Tapping temperature is controlled at about 1450 ℃, and like this, slag has good flowability, the separating of guarantee to come out of the stove back alloy and waste residue.
The batching of producing rare earth intermediate alloy is relevant with raw material middle-weight rare earths oxide content.The rare earth ore concentrate quantity of slag is the actual content calculating by slag middle-weight rare earths oxide compound; Reductive agent is pressed the actual silicon content of ferrosilicon and is added.Here introduce a slag agent than notion, the slag agent than the ratio that is meant rare earth oxide in the refined re ore slag and reductive agent silicon (be the slag agent than=REO/Si).The slag agent is than the grade that has determined to smelt rare earth intermediate alloy, and the slag agent is than high, and reductive agent silicon fully is utilized, and the rare earth grade of alloy smelting is also high; Slag agent ratio is too high, and under silicon quantity not sufficient situation, the more rare earth oxide of residue is not reduced out in the slag, causes rare earth yield not high, and economic target is also unreasonable.Make flux with addition of lime, adjust basicity of slag.The height of basicity of slag directly influences reduction effect, and suitable batching basicity can make reducing and smelting carry out towards the abundant reductive direction of rare earth.Fluorine content 6～17% in the refined re ore slag, in slag with CaF
2Form exists, and analyzes CaO content in the slag, is all by CaO, comprising CaF all calcium
2Calcium, the effective concentration of actual CaO should be to analyze CaO percentage ratio to deduct CaF
2The amount of suitable CaO, i.e. CaO-1.47F.The batching free basicity also is the ratio of the efficient oxidation calcium concn and silicon-dioxide total amount in the furnace charge, and calculating formula is:
Free basicity=(CaO-1.47F)/(SiO2)
Produce the rare earth intermediate alloy of different components, adopt following ratio of components:
(1) produces RE30～46%, Si30～40%, the rare-earth low titanium alloy of Ti＜1.0%.
Slag agent ratio: (REO)/(Si)=1.0～2.1
Free basicity: (CaO-1.47F)/(SiO
2)=4.7～6.2
(2) produce RE30～35%, Si30～35%, Fe27～35%, the rare-earth low titanium alloy of Ti＜0.5%.
Slag agent ratio: (REO)/(Si)=1.0～1.3
Free basicity: (CaO-1.47F)/(SiO
2)=5.5～6.3
Iron silicon ratio: (Fe)/(Si)=0.1～0.2
The iron silicon ratio (Fe/Si) of above-mentioned batching regulation is meant the ratio of silicone content in total iron amount and the reductive agent.Under the prerequisite that guarantees alloy middle-weight rare earths grade, increase iron level and can increase alloy proportion, be useful to being used as the additive treating molten steel.Adding iron behind reducing and smelting is perfect method, so neither can water down the content of the effective silicon of reductive agent, and rare earth is fully reduced, and improves rare earth yield.
(3) produce RE10～25%, Ca7～15%, the rare earth calcium alloy of Si40～60%.
Make the secondary slag that bright higher-grade rare earth alloy is obtained, still contain higher rare earth oxide (REO8～12%), free basicity 2～2.5, produce rare earth calcium alloy with this slag, can significantly reduce lime adding amount, further reclaim the rare earth in the slag, reduce cost of alloy.Its batching condition is:
Ferrosilicon/secondary slag=0.1～0.4
Lime/secondary slag=0.3～0.6
With the refined re ore slag is raw material, also can stablize and produce above-mentioned rare earth calcium alloy.Its batching condition is as follows:
Slag agent ratio: (REO)/(Si)=0.2～0.8
Free basicity: (CaO-1.47F)/(SiO
2)=3～5
Enforcement shows, advantage of the present invention be solved in the past with in the lean ore rare earth slag can not produce RE＞30%, the rare-earth low titanium alloy problem of Ti＜1% has been captured rare earth ore concentrate smelting rare earth intermediate alloy product atomizing difficulty.Can stablize with refined re ore slag and to produce low titanium alloy of high rare earth; Rare earth, silicon, iron respectively are 30～35%, the rare-earth low titanium alloy of Ti＜0.5% and rare earth calcium alloy.The present invention produces stable, and is easy and simple to handle, and power consumption is low, alloy productive rate height, and good product quality, technico-economical comparison is reasonable.
The explanation of rare earth ore concentrate slag melting rare earth intermediate alloy process flow diagram:
The primary smelting of rare earth ore concentrate slag melting rare earth intermediate alloy can be produced low titanium alloy of high rare earth; Rare earth, silicon, iron respectively account for 1/3rd, and titanium is less than 0.5% rare-earth low titanium alloy; Rare earth calcium alloy.Come out of the stove after slag iron separates, the liquid alloy after the separation is annotated the alloy pig of 80～150 mm thick, the alloy pig finishing of condensation, fragmentation, puts in storage through quality test.Produce low titanium alloy of high rare earth, the secondary slag needs through secondary smelting, and secondary smelting is produced rare earth calcium alloy, and the separation of slag iron, alloy cast and the finishing procedure of secondary smelting are identical with primary smelting.Primary smelting produces that rare earth, silicon, iron respectively account for 1/3rd rare-earth low titanium alloy and the secondary slag of rare earth calcium alloy is a waste residue.
Embodiment: add 2400 kilograms of the refined re ore slags of REO33% in 5 tons of electric arc furnace, 2000 kilograms in lime send electrofusion, send electric system to be: 127～220 volts of voltages, electric current 5000～7000 is pacified.Furnace charge melted 85% o'clock, added 530 kilograms of 75 ferrosilicon again, and after ferrosilicon was molten, furnace temperature rose to more than 1400 ℃, and the dense smoke of emerging stops to send electricity, logical 2～5 kilograms per centimeter
2Pressurized air stirred sampling analysis alloy ingredient: RE41.80% 3～5 minutes.Check analysis: RE44.55% after coming out of the stove, Si31.76%, Ca1.80%, Ti0.74%, Mn1.0%.With 3300 kilograms of this stove secondary slags, 1650 kilograms in lime, 700 kilograms of 75 ferrosilicon, reducing and smelting in 5 tons of electric arc furnace, reduction was stirred 5～7 minutes, produced RE20.20%, Si44.85%, Ca7.20%, Ti0.62%, the rare earth calcium alloy of Mn0.78%.
Claims (2)
1, smelts the method for the rare earth intermediate alloy that is used as steel additive agent, it is characterized in that the refined re ore slag to contain 30～60% rare earth oxides is a raw material, produce three kinds of rare earth intermediate alloys;
(1) be 1.0～2.1 with slag agent ratio, free basicity is that 4.7～6.2 mode is prepared burden to produce in electric arc furnace and contained rare earth 30～46%, and silicon 30～40%, titanium are less than 1.0%, and surplus is the low titanium alloy of high rare earth of iron,
(2) be 1.0～1.3 with slag agent ratio, free basicity is 5.5～6.3, and iron silicon ratio is that 0.1～0.2 mode is prepared burden to produce in electric arc furnace and contained rare earth 30～35%, and silicon 30～35%, iron 27～35%, titanium is less than 0.5% rare-earth low titanium alloy,
(3) be 0.2～0.8 with slag agent ratio, free basicity is that 3.0～5.0 mode is prepared burden to produce in electric arc furnace and contained rare earth 10～25%, calcium 7～15%, and silicon 40～60%, surplus is the rare earth calcium alloy of iron.
2, smelt method, it is characterized in that adopting and produce that to contain the secondary slag that low titanium alloy of high rare earth obtains be raw material, be with ratio of components as the rare earth intermediate alloy of steel additive agent:
75 ferrosilicon/secondary slag=0.1～0.4
The wrong slag of lime/two=0.3～0.6
In electric arc furnace, produce and contain rare earth 10～25%, calcium 7～15%, silicon 40～60%, surplus is the rare earth calcium alloy of iron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103958 CN1006810B (en) | 1985-05-23 | 1985-05-23 | Refined re ore slag electric arc furnace smelting rare earth intermediate alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103958 CN1006810B (en) | 1985-05-23 | 1985-05-23 | Refined re ore slag electric arc furnace smelting rare earth intermediate alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85103958A CN85103958A (en) | 1986-09-03 |
| CN1006810B true CN1006810B (en) | 1990-02-14 |
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ID=4793550
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85103958 Expired CN1006810B (en) | 1985-05-23 | 1985-05-23 | Refined re ore slag electric arc furnace smelting rare earth intermediate alloy |
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| Country | Link |
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| CN (1) | CN1006810B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105316484A (en) * | 2014-08-04 | 2016-02-10 | 陆丰市东煊实业有限公司 | Method for preparing rare earth silicon-calcium alloy through waste residues obtained after rare earth separation |
| CN108456773B (en) * | 2018-05-03 | 2019-06-28 | 包头市华商稀土合金有限公司 | A method of producing rare earth ferrosilicon alloy |
| CN108611543B (en) * | 2018-05-12 | 2019-11-12 | 包头市华商稀土合金有限公司 | A method of rare earth magnesium ferrosilicon alloy is produced based on comprehensive utilization of resources means |
| CN111041332A (en) * | 2019-12-23 | 2020-04-21 | 包头稀土研究院 | Rare earth niobium-titanium-iron alloy and production method and use method thereof |
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1985
- 1985-05-23 CN CN 85103958 patent/CN1006810B/en not_active Expired
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