CN102888492B - 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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- CN102888492B CN102888492B CN 201210381847 CN201210381847A CN102888492B CN 102888492 B CN102888492 B CN 102888492B CN 201210381847 CN201210381847 CN 201210381847 CN 201210381847 A CN201210381847 A CN 201210381847A CN 102888492 B CN102888492 B CN 102888492B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 43
- 239000010959 steel Substances 0.000 claims abstract description 43
- 239000000956 alloy Substances 0.000 claims abstract description 37
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 32
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000003723 Smelting Methods 0.000 claims abstract description 12
- 229910008455 Si—Ca Inorganic materials 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000011777 magnesium Substances 0.000 claims description 30
- 239000011575 calcium Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000012423 maintenance Methods 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 241001062472 Stokellia anisodon Species 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 16
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- 238000007670 refining Methods 0.000 abstract description 9
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- 238000009847 ladle furnace Methods 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
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- 230000001681 protective effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002679 ablation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000013459 approach Methods 0.000 description 1
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- 238000009749 continuous casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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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
Along with development of 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 develops to the direction of pureization, 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 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 improve the purity of molten steel greatly.
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, the efficient height.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 come-up, 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.Though obtaining very big 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, improves the utilization ratio of alloy, 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 charges into shielding gas;
2) furnace temperature is heated to 400~500 ℃, adds the master alloy Si-Ca of preheating and Al, Si, Fe in proportion, and furnace temperature is slowly heated up, and rises to 1400~1600 ℃;
3) treat furnace charge fusing after, add the rare-earth magnesium intermediate alloy of preheating in proportion, add the pure rare earth element at last in proportion, 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 alloy liquid 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, charge into 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 is raw material with master alloy silico-calcium, rare earth magnesium and aluminium, silicon, iron, rare earth element, 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 for use, and the purity of lanthanum and cerium is greater than 99wt%.
The preparation method of described Si-Ca-Al-Mg-RE composite deoxidant, treat that furnace charge melts back 5~15min 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 the pure rare earth element at last, 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, significantly reduced the burn out rate of Volatile Elements such as Ca, Mg, improved the utilization ratio of alloy, successfully prepare composite deoxidant, thereby improved the ability of deoxidation effect and the removal inclusion of such alloy greatly.
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 technology, and flow process is simple, and is safe, workable, and industry realizes easily.
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, 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 room temperature and high-temperature mechanical property improved.
Description of drawings
Fig. 1 is the reductor synoptic diagram of embodiment 1.
Fig. 2 is the reductor synoptic diagram of embodiment 2.
Fig. 3 is the reductor synoptic 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 made up 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 charges into argon shield.
2) furnace temperature is heated to 400~500 ℃, adds master alloy Si-Ca and Al, Si, the Fe etc. of 100~200 ℃ of preheatings in proportion, and raw material is of a size of 10~100mm bulk, and furnace temperature is slowly heated up by 30~50 ℃/min, rises to 1400~1600 ℃.
3) treat to add in proportion after the furnace charge fusing 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 the pure rare earth element at last in proportion, 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 alloy liquid 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 charges into argon shield, argon pressure 0.05MPa.Furnace temperature is heated to 400 ℃, and adding Si-Ca, Al, Si, Fe etc. are respectively: 2300g, 171g, 916g and 163g, and 100 ℃ of preheatings simultaneously, raw material is of a size of 20mm, is block, and furnace temperature is slowly heated up by 30 ℃/min, rises to 1450 ℃.After treating the furnace charge fusing, add 942g rare-earth magnesium intermediate alloy, 100 ℃ of preheatings simultaneously, 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 alloy liquid 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.Present embodiment adds in the refining process for No. 45 steel of alloy designations, thereby improves the ability of deoxidation effect and the removal inclusion of such alloy greatly.
Embodiment 2
The agent of cast 10kg rare earth composite deoxidation.Smelting furnace is evacuated to 15Pa, behind the maintenance 10min, and charges into argon shield, argon pressure 0.02MPa.Furnace temperature is heated to 450 ℃, and adding Si-Ca, Al, Si, Fe etc. are respectively: 4600g, 342g, 1832g and 326g, and 150 ℃ of preheatings simultaneously, raw material is of a size of 40mm, is block, and furnace temperature is slowly heated up by 40 ℃/min, rises to 1500 ℃.After treating the furnace charge fusing, add 1884g rare-earth magnesium intermediate alloy, 150 ℃ of preheatings simultaneously, 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 alloy liquid 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.Present embodiment is used for No. 45 steel of alloy designations, adds in the refining process, thereby improve the deoxidation effect of such alloy greatly and remove the ability of inclusion.
Embodiment 3
The agent of cast 20kg rare earth composite deoxidation.Smelting furnace is evacuated to 20Pa, behind the maintenance 15min, and charges into argon shield, argon pressure 0.06MPa.Furnace temperature is heated to 500 ℃, and adding Si-Ca, Al, Si, Fe etc. are respectively: 9200g, 684g, 3664g and 652g, and 200 ℃ of preheatings simultaneously, raw material is of a size of 50mm, is block, and furnace temperature is slowly heated up by 50 ℃/min, rises to 1550 ℃.After treating the furnace charge fusing, add 3768g rare-earth magnesium intermediate alloy, 200 ℃ of preheatings simultaneously, 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 alloy liquid 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.Present embodiment is used for No. 45 steel of alloy designations, adds in the refining process, thereby improve the deoxidation effect of such alloy greatly and remove the ability of inclusion.
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, significantly reduce the burn out rate of Volatile Elements such as Ca, Mg, improve the utilization ratio of alloy.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 alloy burn out rate is low, reductor density is little, and fusing point is low, be conducive to and molten steel between react, can reduce the total oxygen content in the steel greatly, provide a kind of valid approach for producing ultra-clean steel.
Claims (5)
1. the preparation method of a Si-Ca-Al-Mg-RE composite deoxidant, it is characterized in that, by weight percentage, reductor 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;
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, behind maintenance 5~15min, charge into argon gas and carry out melting protection, pressure 0.02~0.06MPa;
2) furnace temperature is heated to 400~500 ℃, adds the master alloy Si-Ca of preheating and Al, Si, Fe in proportion, and furnace temperature is slowly heated up by 30~50 ℃/min, rises to 1400~1600 ℃;
3) treat that furnace charge melts back 5~15min 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 the pure rare earth element at last in proportion, 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 alloy liquid is down to 1400~1500 ℃, pour into a mould, finish preparation.
2. according to the preparation method of the described Si-Ca-Al-Mg-RE composite deoxidant of claim 1, it is characterized in that, be raw material with master alloy silico-calcium, rare earth magnesium and aluminium, silicon, iron, rare earth element, add the stokehold and want 100~200 ℃ of preheatings, and it is broken into the bulk of 10~100mm.
3. according to the preparation method of the described Si-Ca-Al-Mg-RE composite deoxidant of claim 1, it is characterized in that rare earth elements RE is selected the mixture of lanthanum and cerium ratio 1:2 for use, the purity of lanthanum and cerium is greater than 99wt%.
4. according to the preparation method of the described Si-Ca-Al-Mg-RE composite deoxidant of claim 1, it is characterized in that, pour into after the steel ingot, pound into bulk or be prepared into thread.
5. according to the preparation method of the described Si-Ca-Al-Mg-RE composite deoxidant of claim 1, it is characterized in that by weight percentage, in the composite deoxidant component, rare earth elements RE is 15~18%.
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