CN1071205A - The technology of preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O, C and Ce - Google Patents
The technology of preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O, C and Ce Download PDFInfo
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- CN1071205A CN1071205A CN 92109998 CN92109998A CN1071205A CN 1071205 A CN1071205 A CN 1071205A CN 92109998 CN92109998 CN 92109998 CN 92109998 A CN92109998 A CN 92109998A CN 1071205 A CN1071205 A CN 1071205A
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Abstract
The present invention relates to a kind of processing method of preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O, C and Ce, its main processes be with fluoro-carbon-cerium ore concentrate 550-750 ℃ of roastings, under excessive carbonaceous reducing agent condition, make ball then; Prepare batch of material with rare earth pelletizing, silica, charcoal, coke by following principle, the ratio of its rare earth metal and silicon is 0.3-0.6, the amount of carbonaceous reducing agent is 0.9-1.0 times of theoretical value, evenly go into the hot stove in ore deposit, the blow-on initial stage is justified power density 1400-2000A/M with silica fraud furnace lining and at the stove utmost point heart in pan feeding
2, secondary current and secondary voltage be than smelting down greater than 300 condition of power supply.It realizes that no slag, furnace bottom do not have obvious rise, good, the excellent effect that reduces cost of product of alloy matter, is suitable for the hot stove in ore deposit and produces rare earth ferrosilicon alloy.
Description
The present invention relates to a kind of technology of preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O, C and Ce, belong to smelting technology, be particularly suitable in the hot stove in ore deposit, containing the rare earth ferrosilicon alloy of 25-45% rare earth metal (REM) with the production of carbothermic reduction bastnaesite concentrate.
Well-known rare earth metal and rare earth ferrosilicon alloy, be widely used in the production of steel and iron, and can improve the mechanical property and the processing performance of steel, but because rare earth metal costs an arm and a leg and be difficult for adding in the steel, so use cheap rare earth ferrosilicon alloy to the processing of steel, yet its production method mainly contains two kinds of electric silicon pyrogen method and carbothermic methods.The silicothermic process in electric arc furnace of the whole employings of China is in the past smelted, make reductive agent with FeSi75, with the rich slag of fluoro-carbon-cerium ore concentrate, rare earth ore concentrate or in the rich rare earth slag of poor iron ore blast furnace deferrization dephosphorization be rare earths material, the high bed drain purge of power consumption of the rare earth ferrosilicon alloy per ton (containing 30%REM) that this method is smelted is big, rare earth yield is low, calcium impurities content height in the alloy; Domestic in 1975 once had a rich slag of human refined re ore slag and rare earth, in the hot stove in 1800KW ore deposit, carried out the test work of carbothermic reduction, but owing to adopt conventional carbo-thermal process, cause the serious dross of furnace bottom, smelting cycle weak point, alloy pulverization, a series of problems such as the rare earth yield is low, the big alloy grade of bed drain purge is low, bottom temperature reduction not to be resolved, and ended test work.However, producing the test of rare earth ferrosilicon alloy domestic early stage in the hot stove in ore deposit also is a kind of good try.Recent two decades has also carried out the research of this respect in the U.S., the Soviet Union, and certain progress arranged, begin one's study from the initial stage in the sixties as U.S. Ford mineral company and to produce the possibility of rare earth alloy with the direct reduction of rare earth concentrate of carbon, and applied for a patent U.S.Patent 4018597 in 1977, the said firm uses higher-grade bastnaesite concentrate, barium carbonate, Strontium carbonate powder, iron and silica to make raw material, and the rare earth ferrosilicon alloy that contains calcium, strontium and barium is produced in carbon reduction in the hot stove in ore deposit.Because the carbon that batching adopts in its technology also agent is crossed 50% of theoretical requirement.Must cause dry slag to be discharged from stove and the rise of furnace bottom dross, the working of a furnace worsens and shortens the continuous production cycle and the alloy pulverization thereof of stove; The Soviet Union adopts purer rare earth oxide to carry out pilot scale in the hot stove in 1600KW ore deposit, really do not carry out suitability for industrialized production, carry out the production of rare earth ferrosilicon alloy simultaneously with the pure rare earth compound, consider there is not vitality from economic angle, the smelting process of rare earth ferrosilicon alloy has further improved necessity for these reasons.
The hot stove in the ore deposit that the object of the present invention is to provide a kind of utilization to handle a little, cheap raw material, its alloying constituent evenly, not slag inclusion, not efflorescence, rare earth yield height, prevent that the furnace bottom carbide from generating and assemble, reach furnace condition anterograde, furnace bottom does not have the effect of obvious rise, no slag melting, and can reduce the processing method of the preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O, C and Ce of alloy power consumption per ton.
Invention thought of the present invention is: silicon-dioxide is silicon, silicon monoxide by carbon reduction: the rare earth compound carbonization generates the rare earth carbide, and then is reduced to rare earth metal by silicon monoxide, further combines with the silicon that restores to generate the RE-Si alloy again.By the carbonization process of preferential reinforcement through the hamartite middle-weight rare earths of roasting; Improve the insulating property of false furnace lining; Use lower operating voltage and higher utmost point heart circle power density; Lose main processes such as carbon operation in the smelting process and realize goal of the invention.
Processing step of the present invention is:
1, the fluorine carbon cerium mischmetal concentrate (REFCO) that will contain 55-65%REO was done the ore deposit burn decrement rate at 12-15% at 550-750 ℃ of roasting temperature 1-1.5 hour, promptly met the briquetting requirement;
2, rare earth ore concentrate after roasting and carbonaceous reducing agent, binding agent are made ball in the pair roller pelletizer of pressure greater than 17Mpa, its add-on is that rare earth all changes REC into
2The 1-3 of required theoretical carbon amount times, sphere diameter 30-50mm;
3, batching:
Rare earth pelletizing, silica, carbonaceous reducing agent by following principle preparation batch of material, are evenly gone into stove, and the ratio of its rare earth metal and silicon is 0.3-0.6, and the amount of allocating into of carbonaceous reducing agent is reduction of rare earth and the theoretical requirement of silicon 0.9-1.0 a times;
4, the batch of material for preparing is evenly gone into the hot stove in ore deposit and smelt, the blow-on initial stage piles up the thick false furnace lining of 150-200mm with silica, and carries out under following power supply system along with reinforced the time in the inboard, furnace wall, and stove utmost point heart circle power density is 1400-2000A/M
2, secondary current should be emitted alloy every two hours and once go into tundish greater than 300 with the secondary voltage ratio, through leaving standstill 5 minutes, poured in the cast iron mold.
Described carbonaceous reducing agent is charcoal (wooden unit), coke, and the ratio of charcoal and coke is 0.2-0.4, also can only use coke.
Described coke is metallurgical coke, gas coke and refinery coke.
The technology contents that the invention is further illustrated by the following examples:
Example 1: with main chemical compositions is that the fluorine carbon cerium type rare earth ore concentrate of ∑ REO55-65%, BaO＜8%, F=5-7% is in reverberatory furnace or tunnel furnace or rotary kiln, carry out roasting under 550-750 ℃, 1-1.5 hour, do that REO content reaches 65-70% in the rare earth ore concentrate of igloss amount in ore deposit after 12-15%, roasting, with roasted ore by the briquetting of preparing burden of following three kinds of schemes:
I) 200 kilograms of roasted ores, 20 kilograms of wood charcoal powders, 30 kilograms of coal gas coke powders, (40%) 40 kilogram of water glass, through mixing, then in the pair roller type pelletizer to make ball greater than 17MPa pressure, its sphere diameter is about 50mm, seasoning or dry for standby;
II) 200 kilograms of roasted ores, 60 kilograms of wood charcoal powders, 70 kilograms of coal gas coke powders, (40%) 33 kilogram of water glass use the same sampling technology with (I) to carry out mixed pelletizing, and it joins carbon is 2 times of theoretical value, about the about 30mm of sphere diameter;
III) 200 kilograms of roasted ores, 29 kilograms of metallurgical cokes, 23 kilograms of wood charcoal powders, 32 kilograms of spent pulping liquors (proportion 1.8), by above-mentioned with quadrat method mix, make ball, sphere diameter is about 40mm.
Get 137 kilograms of batch proportioning rare earth pelletizings (II), silica (SiO2＞98%) lumpiness be 25-80mm wherein 40-50mm should account for about 50% 200 kilograms, gas coke (fixed carbon 〉=80%) granularity is at the 3-8mm65 kilogram, charcoal (fixed carbon 〉=70%) lumpiness 3-50mm, be not more than 20% less than 10mm, 20 kilograms, mix into the hot stove in the ore deposit of 3000KW, the electrode circle diameter φ 1520mm of this hot stove in ore deposit, self baking electrode diameter phi 630mm, at the smelting initial stage, when above-mentioned furnace charge is evenly gone into stove, pile up the thick false furnace lining of 150-200mm in cupola well wall inboard with silica, the ratio of batching middle-weight rare earths metal and silicon is 0.46,84 volts of operating voltages, primary side current 200-210A, 10000 volts of primary side voltages, electrode insert furnace charge degree of depth 900-1100mm, and charge level in order, do not lump, burn with anger evenly, material collapses, smash material easily, the interval emitted alloy once in two hours, flowed into tundish, left standstill to pour in the cast iron mold in 5 minutes.Every two hours feeding quantity is 4 batches.
Hot stove in ore deposit and operating procedure that example 2 usefulness and example 1 are identical adopt the rare earth pelletizing of (I) in the example 1, smelt by following batch of material proportioning:
107 kilograms in rare earth ball (I), 86 kilograms of gas cokes, 19 kilograms in charcoal, 200 kilograms in silica.
Example 3: with the hot stove in the ore deposit of 4150KW, same when furnace charge is evenly gone into stove with silica pile up false furnace lining, electrode circle diameter is φ 1750mm, self baking electrode diameter 4630mm, the rare earth pelletizing of getting (III) in the example 1 is mixed into stove by following batch of material proportioning and smelts.
200 kilograms in silica
Metallurgical coke (fixed carbon 〉=84%) granularity 3-8mm medium size should account for 50%) 73 kilograms
19 kilograms in charcoal
95 kilograms of rare earth group'ss (III)
The ratio of batching middle-weight rare earths metal and silicon is 0.43.
At 85 volts of primary side current 200-210A of operating voltage, smelt under the primary side voltage 10000 laid shoot spares, electrode depth of penetration 900-1100mm charge level good air permeability, collapse material evenly.Emitted alloy once in 1.5 hours at interval, alloy flows into tundish, pours into cast iron mold after leaving standstill, and can add an amount of steel scrap from the electrode root near iron notch half an hour before coming out of the stove in case of necessity.
The rare earth ferrosilicon alloy of smelting with the inventive method is REM25-45%, Si45-65%, Ca＜1.5%, Fe5-10%, Ti＜0.2%, Al＜1.5% through chemico-analytic chemical ingredients.
The present invention compared with prior art, by the carbonisation that has adopted preferential reinforcement through the bastnaesite middle rare earth of roasting, improve the insulating properties of false furnace lining, use lower operating voltage and higher utmost point heart circle power density that bottom temperature is concentrated and reach a series of technical measures such as losing the carbon operation in the smelting process, and there is cost of material cheap by one month evidence, alloying component is even, no slag inclusion, not efflorescence, the rare earth reduction enters the yield of alloy greater than 95%, every benchmark ton (containing 30%REM) rare earth ferrosilicon alloy power consumption is lower than 10000KWh, no slag melting, furnace bottom does not have obvious rise, reach the advantages such as furnace condition anterograde, for further industrial implementation provides reliable process.
Claims (3)
1, a kind of technology of preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O, C and Ce is characterized in that processing step is:
1) will contain the fluorine carbon cerium mischmetal concentrate (REFCO of 55-65%REO
3), 550 ℃-750 ℃ roasting temperature 1-1.5 hour, do the ore deposit burn decrement rate and promptly meet the briquetting requirement at 12-15%;
2) make ball through the rare earth ore concentrate after the roasting and carbonaceous reducing agent, binding agent in the pelletizer of pressure greater than 17Mpa, its add-on is that rare earth all changes REC into
2The 1-3 of required theoretical carbon amount times, sphere diameter 30-50mm;
3) batching:
Rare earth pelletizing, silica, carbonaceous reducing agent by following principle batching, are evenly gone into stove, and the ratio of its rare earth metal and silicon is 0.3-0.6, and the amount of allocating into of carbonaceous reducing agent is reduction of rare earth, the theoretical requirement of silicon 0.9-1.0 a times;
4) batch of material for preparing is evenly gone into the hot stove in ore deposit and smelt, pile up the thick false furnace lining of 150-200mm in the inboard, furnace wall with silica along with reinforced the time before the blow-on, and carry out under following power supply system condition, it is 1400-2000A/M that the stove utmost point heart is justified power density
2, secondary current should be emitted alloy every two hours and once go into tundish greater than 300 with the secondary voltage ratio, through leaving standstill 5 minutes, poured in the cast iron mold.
2, technology according to claim 1 is characterized in that described carbonaceous reducing agent is coke and charcoal (wooden unit), and the ratio of its charcoal and coke is 0.2-0.4, also can only use coke.
3, technology according to claim 1 is characterized in that described coke is metallurgical coke, gas coke and refinery coke.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109998 CN1025052C (en) | 1992-10-27 | 1992-10-27 | Process for preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O,C and Ce |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 92109998 CN1025052C (en) | 1992-10-27 | 1992-10-27 | Process for preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O,C and Ce |
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| CN1071205A true CN1071205A (en) | 1993-04-21 |
| CN1025052C CN1025052C (en) | 1994-06-15 |
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| CN 92109998 Expired - Fee Related CN1025052C (en) | 1992-10-27 | 1992-10-27 | Process for preparation of rareearth ferro-silicon alloy by carbon thermal reduction to ore bearing O,C and Ce |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1084301C (en) * | 1999-04-29 | 2002-05-08 | 清华大学 | Method for recovering rare earth carbonate by bastnaesite decomposition through ammonium chloride baking process |
| CN1093564C (en) * | 1998-12-16 | 2002-10-30 | 东北大学 | Technology for producing rare earth barium silicide alloy by carbon thermal reduction method |
| CN103184332A (en) * | 2013-03-29 | 2013-07-03 | 四川省彭山宇力化工有限公司 | Method for roasting, converting and resolving fluorocarbon cerium rare earth mine by adding covering agent to calcium compound |
| CN104878289A (en) * | 2015-06-29 | 2015-09-02 | 理县岷江稀土新材料开发有限公司 | Ceric rare earth ferrosilicon alloy and production method thereof |
| CN104962741A (en) * | 2015-07-09 | 2015-10-07 | 平罗县丰华冶金有限公司 | Process for producing rare earth silicon alloy by using rare earth enriched material |
| CN106133157A (en) * | 2014-03-28 | 2016-11-16 | 日立金属株式会社 | The recovery method of rare earth element |
| CN107760869A (en) * | 2017-10-27 | 2018-03-06 | 安吉绿金金属材料有限公司 | A kind of preparation method of rare earth ferrosilicon alloy |
| CN108546835A (en) * | 2018-04-27 | 2018-09-18 | 乌拉特前旗三才第铁合金有限公司 | A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy |
| CN109837385A (en) * | 2019-04-15 | 2019-06-04 | 李洪明 | A kind of method that Rare Earth Mine is decomposed in heating melting conversion |
| WO2021097693A1 (en) | 2019-11-20 | 2021-05-27 | 包头稀土研究院 | Smelting method for bastnaesite and use of carbon powder |
| CN116121582A (en) * | 2023-02-17 | 2023-05-16 | 中冶东方工程技术有限公司 | Method for producing silicon alloy material by smelting in submerged arc furnace |
| CN116426773A (en) * | 2023-04-28 | 2023-07-14 | 东北大学 | Method for producing rare earth ferrosilicon alloy by using rare earth slag |
-
1992
- 1992-10-27 CN CN 92109998 patent/CN1025052C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093564C (en) * | 1998-12-16 | 2002-10-30 | 东北大学 | Technology for producing rare earth barium silicide alloy by carbon thermal reduction method |
| CN1084301C (en) * | 1999-04-29 | 2002-05-08 | 清华大学 | Method for recovering rare earth carbonate by bastnaesite decomposition through ammonium chloride baking process |
| CN103184332A (en) * | 2013-03-29 | 2013-07-03 | 四川省彭山宇力化工有限公司 | Method for roasting, converting and resolving fluorocarbon cerium rare earth mine by adding covering agent to calcium compound |
| CN103184332B (en) * | 2013-03-29 | 2015-04-22 | 四川省彭山宇力化工有限公司 | Method for roasting, converting and resolving fluorocarbon cerium rare earth mine by adding covering agent to calcium compound |
| CN106133157A (en) * | 2014-03-28 | 2016-11-16 | 日立金属株式会社 | The recovery method of rare earth element |
| US10316393B2 (en) | 2014-03-28 | 2019-06-11 | Hitachi Metals, Ltd. | Method for recovering rare earth element |
| CN104878289A (en) * | 2015-06-29 | 2015-09-02 | 理县岷江稀土新材料开发有限公司 | Ceric rare earth ferrosilicon alloy and production method thereof |
| CN104962741A (en) * | 2015-07-09 | 2015-10-07 | 平罗县丰华冶金有限公司 | Process for producing rare earth silicon alloy by using rare earth enriched material |
| CN107760869A (en) * | 2017-10-27 | 2018-03-06 | 安吉绿金金属材料有限公司 | A kind of preparation method of rare earth ferrosilicon alloy |
| CN108546835A (en) * | 2018-04-27 | 2018-09-18 | 乌拉特前旗三才第铁合金有限公司 | A kind of method of carbothermy technique serialization production high-quality rare earth ferrosilicon alloy |
| CN109837385A (en) * | 2019-04-15 | 2019-06-04 | 李洪明 | A kind of method that Rare Earth Mine is decomposed in heating melting conversion |
| WO2021097693A1 (en) | 2019-11-20 | 2021-05-27 | 包头稀土研究院 | Smelting method for bastnaesite and use of carbon powder |
| CN116121582A (en) * | 2023-02-17 | 2023-05-16 | 中冶东方工程技术有限公司 | Method for producing silicon alloy material by smelting in submerged arc furnace |
| CN116426773A (en) * | 2023-04-28 | 2023-07-14 | 东北大学 | Method for producing rare earth ferrosilicon alloy by using rare earth slag |
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| Publication number | Publication date |
|---|---|
| CN1025052C (en) | 1994-06-15 |
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