CN102888492A - Si-Ca-Al-Mg-RE (rare earth) composite deoxidizer and preparation method thereof - Google Patents
Si-Ca-Al-Mg-RE (rare earth) composite deoxidizer and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of steel smelting deoxidization, and relates to an Si-Ca-Al-Mg-RE (rare earth) composite deoxidizer for molten steel deoxidization and a preparation method thereof. The composite deoxidizer is added to deoxidize molten steel in the converter or electric furnace tapping process or a refining process of an RH, LF (ladle furnace), VD (vacuum degasser) or the like. The alloy comprises the following components in percentage by weight: 40-50% of Si, 10-12% of Ca, 3-4% of Al, 1-1.5% of Mg, 10-20% of RE and the balance of iron. The preparation method comprises the following steps: 1) smelting in a vacuum furnace, vacuumizing the smelting furnace, and charging protective gas; 2) preheating the furnace, and adding preheated interalloy Si-Ca, Al, Si and Fe; 3) after the furnace material is molten, adding preheated RE-Mg interalloy, adding pure RE element, melting, evenly stirring, and standing; and 4) preheating the casting mold, and casting. The volatile elements Ca and Mg are added in the forms of interalloy Si-Ca and RE-Mg, thereby reducing the burnout rate of the Ca and Mg elements, and enhancing the deoxidizing effect and inclusion removal capacity of the alloy.
Description
Technical field
The invention belongs to smelting iron and steel deoxy technology field, is a kind of Si-Ca-Al-Mg-RE composite deoxidant for deoxidation of molten steel and preparation method thereof.In converter, electric furnace steel tapping process or in the refining processs such as RH, LF, VD, add, molten steel is carried out deoxidation.
Background technology
Development along with science and technology, in the industrial and daily life, demand to steel is more and more, specification of quality to steel is also more and more higher, steel quality is to the future development of sublimate, ultra-pure purification, harmful element content in the requirement steel and the control of inclusion are more and more stricter, and this certainly will have higher requirement with the quality of the raw materials such as reductor to iron and steel.Rare earth has the adsorption stronger with oxygen, can play cleaning molten steel and the rotten effect that is mingled with, thereby can greatly improve the purity of molten steel.
At present, metallic aluminium generally uses in converter or electric furnace steel tapping process as a kind of deep deoxidation agent, and it has good deoxy performance and has obtained everybody approval, and deoxidizing capacity is strong, and efficient is high.Present employed reductor has metal aluminium ingot, ferro-aluminum etc., but the Al that produces after its deoxidation
2O
3Solid inclusion can be present in the molten steel in a large number, be difficult for floating, if in smelting technology after this not with its removal, nozzle clogging in the time of not only can causing continuous casting, and can promote the formation of static ingot A segregation, more can reduce mechanical property and the machinability of Finished Steel.
In order to eliminate Al in the molten steel
2O
3The defective that inclusion causes, feeding SiCa cored-wire or calcium line in ladle make Al in the molten steel in recent years
2O
3Solid inclusion becomes 12CaO7Al under the effect of calcium metal
2O
3Float on the liquid phase in the slag of top, or make Al
2O
3Irregular inclusion modification is nodule.But this kind method calcium line utilization ratio is low and cost is higher.
The subsurface defect problem of large-scale steel ingot, foundry goods, blank enjoys researcher and business circles to pay close attention to.Although obtaining very large progress aspect the removal of deoxidation mechanism and deoxidation products, also fundamentally do not eliminating or alleviate.
Summary of the invention
The object of the present invention is to provide a kind of Si-Ca-Al-Mg-RE composite deoxidant and preparation method thereof, effectively preparation contains the composite deoxidant of rare earth, puies forward heavy alloyed utilization ratio, reduce the total oxygen content in the steel, form liquid inclusions, impel inclusion to float rapidly, solve pure property problem in the steel.
Technical scheme of the present invention is:
A kind of Si-Ca-Al-Mg-RE composite deoxidant, by weight percentage, its component and content are as follows: Si40～50%, Ca 10～12%, Al 3～4%, Mg 1～1.5%, rare earth elements RE 10～20%, surplus are iron.
Described Si-Ca-Al-Mg-RE composite deoxidant, by weight percentage, rare earth element FE preferred 15～18%.
The preparation method of described Si-Ca-Al-Mg-RE composite deoxidant comprises the steps:
1) adopts vacuum oven to smelt, smelting furnace is evacuated to 10～20Pa, and is filled with shielding gas;
2) furnace temperature is heated to 400～500 ℃, adds in proportion the master alloy Si-Ca of preheating and Al, Si, Fe, and furnace temperature is slowly heated up, and rises to 1400～1600 ℃;
3) after the furnace charge fusing, add in proportion the rare-earth magnesium intermediate alloy of preheating, add in proportion at last the pure rare earth element, stir after the fusing, left standstill after the stirring 3～5 minutes;
4) with 200～300 ℃ of metallic mould preheatings, when the temperature for the treatment of aluminium alloy is down to 1400～1500 ℃, pour into a mould, finish preparation.
The preparation method of described Si-Ca-Al-Mg-RE composite deoxidant is evacuated to 10～20Pa with smelting furnace, keep 5～15min after, be filled with argon gas and carry out the melting protection, pressure 0.02～0.06MPa, and stove is heated to 400～500 ℃.
The preparation method of described Si-Ca-Al-Mg-RE composite deoxidant take master alloy silico-calcium, rare earth magnesium and aluminium, silicon, iron, rare earth element as raw material, adds the stokehold and wants 100～200 ℃ of preheatings, and it is broken into the bulk of 10～100mm.
The preparation method of described Si-Ca-Al-Mg-RE composite deoxidant, step 2) add after the master alloy, furnace temperature is slowly heated up by 30～50 ℃/min, rise to 1400～1600 ℃.
The preparation method of described Si-Ca-Al-Mg-RE composite deoxidant, rare earth elements RE select the mixture of lanthanum and cerium ratio 1:2, and the purity of lanthanum and cerium is greater than 99wt%.
The preparation method of described Si-Ca-Al-Mg-RE composite deoxidant, 5～15min after furnace charge melts fully, add the rare-earth magnesium intermediate alloy of 100～200 ℃ of preheatings, the composition of rare earth magnesium is RE 3～6%, Si 30～40%, Mg 3～10%, Ca 3～10%, surplus Fe; Add at last the pure rare earth element, stir after the fusing, leave standstill 3～5min after the stirring.
The preparation method of described Si-Ca-Al-Mg-RE composite deoxidant pours into after the steel ingot, pounds into bulk or is prepared into thread.
The present invention has following beneficial effect:
1. technological design of the present invention is reasonable, by adding Si-Ca and rare-earth magnesium intermediate alloy, greatly reduced the burn out rate of the Volatile Elements such as Ca, Mg, improved the utilization ratio of alloy, successfully prepare composite deoxidant, thereby greatly improved the ability of deoxidation effect and the removal of inclusions of such alloy.
2. product alloying element reasonable ratio of the present invention, density is little, is 3.6g/cm
3Fusing point is low, is conducive to the absorption of molten steel alloying element, and deoxidation effect is good.
3. it is reasonable that the present invention designs preparation rare earth composite deoxidation agent technique, and flow process is simple, and is safe, workable, and industry easily realizes.
4. adopt the present invention to contain the composite deoxidant of rare earth, this reductor is the bar composition that is constituted by various metastable master alloys or simple substance, the combined composition of said composition and with steel in oxygen be combined the low melting point, the inclusion of small and dispersed of formation and thoroughly avoided the deficiencies in the prior art.
5. rare earth element of the present invention, calcium, silicon and aluminium is used in conjunction with, can play refining, desulfurization, in and the effect of low melting point detrimental impurity, and can improve the processing characteristics of steel, the physical and chemical performance of alloy be can improve, and Alloy At Room Temperature and high-temperature mechanical property improved.
Description of drawings
Fig. 1 is the reductor schematic diagram of embodiment 1.
Fig. 2 is the reductor schematic diagram of embodiment 2.
Fig. 3 is the reductor schematic diagram of embodiment 3.
Embodiment
Si-Ca-Al-Mg-RE composite deoxidant of the present invention and preparation method thereof, the Si-Ca-Al-Mg-RE composite deoxidant is comprised of the component of following weight per-cent: Si 40～50%, Ca 10～12%, Al 3～4%, Mg1-1.5%, RE 10～20%, surplus is iron, and concrete steps are as follows:
1) adopts vacuum oven to smelt, smelting furnace is evacuated to 10～20Pa, and is filled with argon shield.
2) furnace temperature is heated to 400～500 ℃, adds in proportion master alloy Si-Ca and Al, Si, the Fe etc. of 100～200 ℃ of preheatings, and it is block that raw material is of a size of 10～100mm, and furnace temperature is slowly heated up by 30～50 ℃/min, rises to 1400～1600 ℃.
3) add in proportion the rare-earth magnesium intermediate alloy of 100～200 ℃ of preheatings after furnace charge fusing, the composition of rare earth magnesium is RE 3～6%, Si 30～40%, Mg 3～10%, Ca 3～10%, surplus Fe.Add in proportion at last the pure rare earth element, stir after the fusing, left standstill after the stirring 3～5 minutes.
4) with 200～300 ℃ of metallic mould preheatings, when the temperature for the treatment of aluminium alloy is down to 1400～1500 ℃, pour into a mould, finish preparation.
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment 1
The agent of cast 5kg rare earth composite deoxidation.Smelting furnace is evacuated to 10Pa, behind the maintenance 5min, and is filled with argon shield, argon pressure 0.05MPa.Furnace temperature is heated to 400 ℃, and adding Si-Ca, Al, Si, Fe philosophy are: 2300g, 171g, 916g and 163g, and 100 ℃ of simultaneously preheatings, raw material is of a size of 20mm, is block, and furnace temperature is slowly heated up by 30 ℃/min, rises to 1450 ℃.After the furnace charge fusing, add 942g rare-earth magnesium intermediate alloy, 100 ℃ of simultaneously preheatings, the composition of rare earth magnesium is RE 4%, Si 40%, Mg 8%, Ca3%, surplus Fe.Add at last in the pure rare earth element 959g(rare earth elements RE, the part by weight of lanthanum and cerium is 1:2), stir after the fusing, left standstill after the stirring 3 minutes.With 200 ℃ of metallic mould preheatings, when the temperature for the treatment of aluminium alloy is down to 1480 ℃, pour into a mould, finish preparation.Through check, the composition of rare earth composite deoxidation agent is: Si:45.5%, Ca:11.8%, Al:3.2%, Mg:1.2%, RE:16.2%, Fe:17.9%.
In the present embodiment, composite deoxidant density is 3.6g/cm
3, be 1200 ℃-1400 ℃ between ablation zone.Composite deoxidant pours into after the steel ingot, pounds into the block (see figure 1) of 20～30mm, adds in converter, electric furnace steel tapping process or in the refining processs such as RH, LF, VD, and molten steel is carried out deoxidation.The present embodiment adds in the refining process for No. 45 steel of alloy designations, thereby greatly improves the ability of deoxidation effect and the removal of inclusions of such alloy.
Embodiment 2
The agent of cast 10kg rare earth composite deoxidation.Smelting furnace is evacuated to 15Pa, behind the maintenance 10min, and is filled with argon shield, argon pressure 0.02MPa.Furnace temperature is heated to 450 ℃, and adding Si-Ca, Al, Si, Fe philosophy are: 4600g, 342g, 1832g and 326g, and 150 ℃ of simultaneously preheatings, raw material is of a size of 40mm, is block, and furnace temperature is slowly heated up by 40 ℃/min, rises to 1500 ℃.After the furnace charge fusing, add 1884g rare-earth magnesium intermediate alloy, 150 ℃ of simultaneously preheatings, the composition of rare earth magnesium is RE 5%, Si 35%, Mg 6%, Ca 4%, surplus Fe.Add at last in the pure rare earth element 1918g(rare earth elements RE, the part by weight of lanthanum and cerium is 1:2), stir after the fusing, left standstill after the stirring 4 minutes.With 250 ℃ of metallic mould preheatings, when the temperature for the treatment of aluminium alloy is down to 1450 ℃, pour into a mould, finish preparation.Through check, the composition of rare earth composite deoxidation agent is: Si:49.5%, Ca:11.7%, Al:3.3%, Mg:1.4%, RE:15.6%, Fe:16.7%.
In the present embodiment, composite deoxidant density is 3.6g/cm
3, be 1200 ℃-1400 ℃ between ablation zone.Composite deoxidant pours into after the steel ingot, pounds into the block (see figure 2) of 60～80mm, adds in converter, electric furnace steel tapping process or in the refining processs such as RH, LF, VD, and molten steel is carried out deoxidation.The present embodiment is used for No. 45 steel of alloy designations, adds in the refining process, thereby greatly improve the ability of deoxidation effect and the removal of inclusions of such alloy.
Embodiment 3
The agent of cast 20kg rare earth composite deoxidation.Smelting furnace is evacuated to 20Pa, behind the maintenance 15min, and is filled with argon shield, argon pressure 0.06MPa.Furnace temperature is heated to 500 ℃, and adding Si-Ca, Al, Si, Fe philosophy are: 9200g, 684g, 3664g and 652g, and 200 ℃ of simultaneously preheatings, raw material is of a size of 50mm, is block, and furnace temperature is slowly heated up by 50 ℃/min, rises to 1550 ℃.After the furnace charge fusing, add 3768g rare-earth magnesium intermediate alloy, 200 ℃ of simultaneously preheatings, the composition of rare earth magnesium is RE 6%, Si 38%, Mg 9%, Ca 5%, surplus Fe.Add at last in the pure rare earth element 3836g(rare earth elements RE, the part by weight of lanthanum and cerium is 1:2), stir after the fusing, left standstill after the stirring 5 minutes.With 300 ℃ of metallic mould preheatings, when the temperature for the treatment of aluminium alloy is down to 1450 ℃, pour into a mould, finish preparation.Through check, the composition of rare earth composite deoxidation agent is: Si:44.2%, Ca:11.3%, Al:3.4%, Mg:1.9%, RE:16.6%, Fe:15.9%.
In the present embodiment, composite deoxidant density is 3.6g/cm
3, be 1200 ℃-1400 ℃ between ablation zone.Composite deoxidant pours into after the steel ingot, pounds into the block (see figure 3) of 30～50mm, adds in converter, electric furnace steel tapping process or in the refining processs such as RH, LF, VD, and molten steel is carried out deoxidation.The present embodiment is used for No. 45 steel of alloy designations, adds in the refining process, thereby greatly improve the ability of deoxidation effect and the removal of inclusions of such alloy.
Working process of the present invention and result are as follows:
The invention provides effective method for preparing the rare earth composite deoxidation agent, by adding Si-Ca and rare-earth magnesium intermediate alloy, greatly reduce the burn out rate of the Volatile Elements such as Ca, Mg, put forward heavy alloyed utilization ratio.By the rational proportion alloying element, reductor has little, the low-melting characteristics of density, is conducive to the absorption of molten steel alloying element, and deoxidation effect is good.
The result of embodiment shows, the rare earth composite deoxidation agent of the present invention's preparation, Volatile Elements all satisfies the composition requirement, the burning loss of alloy rate is low, reductor density is little, and fusing point is low, be conducive to and molten steel between react, can greatly reduce the total oxygen content in the steel, provide a kind of effective approach for producing ultra-clean steel.
Claims (9)
1. a Si-Ca-Al-Mg-RE composite deoxidant is characterized in that, by weight percentage, its component and content are as follows: Si 40～50%, Ca 10～12%, Al 3～4%, Mg 1～1.5%, rare earth elements RE 10～20%, surplus are iron.
2. according to Si-Ca-Al-Mg-RE composite deoxidant claimed in claim 1, it is characterized in that, by weight percentage, rare earth elements RE preferred 15～18%.
3. according to the preparation method of Si-Ca-Al-Mg-RE composite deoxidant claimed in claim 1, it is characterized in that, comprise the steps:
1) adopts vacuum oven to smelt, smelting furnace is evacuated to 10～20Pa, and is filled with shielding gas;
2) furnace temperature is heated to 400～500 ℃, adds in proportion the master alloy Si-Ca of preheating and Al, Si, Fe, and furnace temperature is slowly heated up, and rises to 1400～1600 ℃;
3) after the furnace charge fusing, add in proportion the rare-earth magnesium intermediate alloy of preheating, add in proportion at last the pure rare earth element, stir after the fusing, left standstill after the stirring 3～5 minutes;
4) with 200～300 ℃ of metallic mould preheatings, when the temperature for the treatment of aluminium alloy is down to 1400～1500 ℃, pour into a mould, finish preparation.
4. according to the preparation method of Si-Ca-Al-Mg-RE composite deoxidant claimed in claim 3, it is characterized in that, smelting furnace is evacuated to 10～20Pa; after keeping 5～15min; be filled with argon gas and carry out melting protection, pressure 0.02～0.06MPa, and stove is heated to 400～500 ℃.
5. according to the preparation method of Si-Ca-Al-Mg-RE composite deoxidant claimed in claim 3, it is characterized in that, take master alloy silico-calcium, rare earth magnesium and aluminium, silicon, iron, rare earth element as raw material, add the stokehold and want 100～200 ℃ of preheatings, and it is broken into the bulk of 10～100mm.
6. according to the preparation method of Si-Ca-Al-Mg-RE composite deoxidant claimed in claim 3, it is characterized in that step 2) add after the master alloy, furnace temperature is slowly heated up by 30～50 ℃/min, rise to 1400～1600 ℃.
7. according to the preparation method of Si-Ca-Al-Mg-RE composite deoxidant claimed in claim 3, it is characterized in that, rare earth elements RE is selected the mixture of lanthanum and cerium ratio 1:2, and the purity of lanthanum and cerium is greater than 99wt%.
8. according to the preparation method of Si-Ca-Al-Mg-RE composite deoxidant claimed in claim 3, it is characterized in that, 5～15min after furnace charge melts fully, add the rare-earth magnesium intermediate alloy of 100～200 ℃ of preheatings, the composition of rare earth magnesium is RE 3～6%, Si 30～40%, Mg 3～10%, Ca 3～10%, surplus Fe; Add at last the pure rare earth element, stir after the fusing, leave standstill 3～5min after the stirring.
9. according to the preparation method of Si-Ca-Al-Mg-RE composite deoxidant claimed in claim 3, it is characterized in that, pour into after the steel ingot, pound into bulk or be prepared into thread.
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| CN103243196A (en) * | 2013-05-15 | 2013-08-14 | 中国科学院金属研究所 | Purified smelting method of adding rare earth in intermediate frequency furnace |
| CN103924030A (en) * | 2014-04-09 | 2014-07-16 | 中国科学院金属研究所 | Smelting method of ultra-low oxygen pure steel |
| CN106834602A (en) * | 2016-12-16 | 2017-06-13 | 包头稀土研究院 | Steel-making rare-earth aluminum-calcium ferrosilicon composite alloy and preparation method thereof |
| CN109762959A (en) * | 2019-03-27 | 2019-05-17 | 中国科学院金属研究所 | A kind of smelting process and special steel of special steel |
| CN110004270A (en) * | 2019-05-24 | 2019-07-12 | 中国科学院包头稀土研发中心 | A kind of commercialization efficiency refining high deoxidier and preparation method thereof |
| CN110016580A (en) * | 2019-05-09 | 2019-07-16 | 珠海国合融创科技有限公司 | A kind of degasser and its preparation method and application and application method |
| CN113073173A (en) * | 2021-03-29 | 2021-07-06 | 福建三宝钢铁有限公司 | Low-cost slab Q235B steel-making process |
| CN113502373A (en) * | 2021-07-07 | 2021-10-15 | 芜湖县天海耐火炉料有限公司 | Multi-element composite deoxidizer for steel processing and preparation method thereof |
| CN114107601A (en) * | 2021-11-15 | 2022-03-01 | 东北大学 | Method for refining rare earth inclusions in steel by magnesium pretreatment |
| CN114807491A (en) * | 2021-01-28 | 2022-07-29 | 上海梅山钢铁股份有限公司 | Production method of ultralow-oxygen and sulfide high-spheroidization-rate medium-low-carbon steel molten steel |
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| CN103243196B (en) * | 2013-05-15 | 2015-10-07 | 中国科学院金属研究所 | A kind of intermediate frequency furnace adds the method that rare earth sublimate is smelted |
| CN103243196A (en) * | 2013-05-15 | 2013-08-14 | 中国科学院金属研究所 | Purified smelting method of adding rare earth in intermediate frequency furnace |
| CN103924030A (en) * | 2014-04-09 | 2014-07-16 | 中国科学院金属研究所 | Smelting method of ultra-low oxygen pure steel |
| CN103924030B (en) * | 2014-04-09 | 2015-05-06 | 中国科学院金属研究所 | Smelting method of ultra-low oxygen pure steel |
| CN106834602A (en) * | 2016-12-16 | 2017-06-13 | 包头稀土研究院 | Steel-making rare-earth aluminum-calcium ferrosilicon composite alloy and preparation method thereof |
| CN109762959A (en) * | 2019-03-27 | 2019-05-17 | 中国科学院金属研究所 | A kind of smelting process and special steel of special steel |
| CN110016580A (en) * | 2019-05-09 | 2019-07-16 | 珠海国合融创科技有限公司 | A kind of degasser and its preparation method and application and application method |
| CN110004270A (en) * | 2019-05-24 | 2019-07-12 | 中国科学院包头稀土研发中心 | A kind of commercialization efficiency refining high deoxidier and preparation method thereof |
| CN114807491A (en) * | 2021-01-28 | 2022-07-29 | 上海梅山钢铁股份有限公司 | Production method of ultralow-oxygen and sulfide high-spheroidization-rate medium-low-carbon steel molten steel |
| CN114807491B (en) * | 2021-01-28 | 2024-01-05 | 上海梅山钢铁股份有限公司 | Production method of ultra-low oxygen and sulfide high spheroidization rate medium and low carbon steel molten steel |
| CN113073173A (en) * | 2021-03-29 | 2021-07-06 | 福建三宝钢铁有限公司 | Low-cost slab Q235B steel-making process |
| CN113502373A (en) * | 2021-07-07 | 2021-10-15 | 芜湖县天海耐火炉料有限公司 | Multi-element composite deoxidizer for steel processing and preparation method thereof |
| CN114107601A (en) * | 2021-11-15 | 2022-03-01 | 东北大学 | Method for refining rare earth inclusions in steel by magnesium pretreatment |
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