CN102010934B - RH refining desulphurization process of non-oriented electrical steel - Google Patents
RH refining desulphurization process of non-oriented electrical steel Download PDFInfo
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- CN102010934B CN102010934B CN201010595509.7A CN201010595509A CN102010934B CN 102010934 B CN102010934 B CN 102010934B CN 201010595509 A CN201010595509 A CN 201010595509A CN 102010934 B CN102010934 B CN 102010934B
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910000565 Non-oriented electrical steel Inorganic materials 0.000 title claims abstract description 19
- 238000007670 refining Methods 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 title claims abstract description 12
- 239000002893 slag Substances 0.000 claims abstract description 44
- 238000005261 decarburization Methods 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims abstract description 6
- 238000005275 alloying Methods 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229910000629 Rh alloy Inorganic materials 0.000 claims abstract description 5
- 235000003599 food sweetener Nutrition 0.000 claims description 52
- 239000003765 sweetening agent Substances 0.000 claims description 52
- 238000006477 desulfuration reaction Methods 0.000 claims description 46
- 230000023556 desulfurization Effects 0.000 claims description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 238000009749 continuous casting Methods 0.000 claims description 6
- 238000010079 rubber tapping Methods 0.000 claims description 6
- 238000005304 joining Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 230000001351 cycling effect Effects 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000009628 steelmaking Methods 0.000 abstract description 2
- 238000007664 blowing Methods 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 150000001485 argon Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
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- Treatment Of Steel In Its Molten State (AREA)
Abstract
The invention discloses an RH refining desulphurization process of non-oriented electrical steel, belonging to the technical field of steel making. The process comprises the following steps: setting the lift gas flowrate to 1200 NL/min after the entering of the RH, and enhancing the lift gas flowrate to 1600 NL/min 3 minutes later; blowing oxygen to perform the forced decarburization when the vacuum degree is reduced to 2.0 mba, and when the oxygen blowing is finished and the vacuum degree is lower than 2.0 mba, performing the natural decarburization for 20 minutes; adding the aluminum for deoxidation when the vacuum decarburization is finished; and performing the silicon alloying by using the low carbon ferrosilicon, and adding the desulfurizing agent into the vacuum chamber in two times through the RH alloy bin. The circulation time of the test furnace batch is from 10 minutes to 15 minutes. The process provided by the invention has the advantages that the RH device needs no reconstruction, and the operation is simple. The average RH desulphurization degree is 36.7%, and the desulphurization effect is better. The contents of the FeO and the MnO of the ladle slag have significant influence on the desulphurization effect, and the enhancing of the alkalinity of the ladle slag can increase the RH desulphurization efficiency as well as reduce the corrosion of the RH device.
Description
Technical field
The invention belongs to steelmaking technical field, particularly relate to a kind of RH refining desulfuration technique for non-oriented electrical steel, it is the processing method of non-oriented electrical steel desulfurization first-selection.
Background technology
Along with the gradually raising that the user requires steel product quality, the contour trade mark Ultra-low carbon of non-oriented electrical steel, super low sulfur steel grade smelting technology are anxious to be developed.Tradition non-oriented electrical steel production process only relies on Deep Desulphurization of Hot Metal, reduction converter to return sulphur and control sulphur content.Yet only return sulphur by hot metal pretreatment and converter control and realize the more production of the non-oriented electrical steel of low sulfur content, not only can cause great converter smelting pressure, and can't satisfy the higher category non-oriented electrical steel for the requirement of sulphur content.Therefore the exploitation of RH Vacuum Desulfurization technology comes into one's own gradually.
The present present situation of Technology: Baosteel has obtained a kind of average desulfurization degree in the RH desulfurization test be 42.9% the dark sulfur removal technology of RH.Wuhan Iron and Steel Plant, steel company and Nippon Steel have all obtained the RH average desulfurization degree more than 50% in the Taiwan in production practice, and have all obtained sulphur content at the ultralow-sulfur steel below 0.002%.Yet sweetening agent CaF in the above process of the test
2Content causes Eroded all more than 15% to RH equipment, has affected rhythm of production.The people such as Yu Xuebin, Shi Qilong utilizes the CaO after the improvement
2-Al
2O
3-SiO
2Slag system hangs down the fluorine sweetening agent, when processing, the RH desulfurization that the weak deoxidized steels such as non-oriented electrical steel are carried out obtained 31.6% average desulfurization degree, obviously improved the sweetening effectiveness of low fluorine class sweetening agent, but the desulfurization degree of low fluorine class sweetening agent is still lower generally, and the corrosion to equipment is still more serious in the RH treating processes.Therefore need to seek aborning the process control condition that is fit to and improve the RH desulfuration efficiency, further reduce in the RH desulfurization treating processes corrosion to equipment.
Summary of the invention
The objective of the invention is: a kind of RH refining desulfuration technique for non-oriented electrical steel is provided.The present invention has drawn the RH control condition of suitable non-oriented electrical steel desulfurization by the analysis to factors such as equipment corrosion, top slag composition, basicity, desulfurization times, has determined the related process parameter control of suitable RH desulfurization.So that the RH desulfurization degree on average reaches 36.7%, has preferably sweetening effectiveness.Can be widely used in the RH refining desulfuration technique of non-oriented electrical steel.
The technical scheme that the present invention is used for the RH refining desulfuration technique of non-oriented electrical steel is: it is characterized in that:
(1) technological process of production is: molten iron pretreatment desulfurizing → LD (ladle) → pushing off the slag tapping → LF (electric furnace refining) → RH (vacuum refinement) decarburization, desulfurization → continuous casting;
(2) after RH enters the station, be 1200NL/min with the lift gas flow set, behind the 3min lift gas flow be increased to 1600NL/min;
(3) decarburization is forced in oxygen blast after vacuum tightness is reduced to 2.0mba, and oxygen blast below 2.0mba, enters the nature decarburization with vacuum degree control after finishing, and guarantees that the nature decarburization time is at 20min;
(4) after vacuum decarburization finishes, aluminum deoxidation, and by FeO+MnO content in the add-on control top slag of aluminium, at first adopt low-carbon ferrosilicon to carry out alloying with silicon, then drop into the low fluorine sweetening agent of fritting by RH alloy feed bin to vacuum chamber, sweetening agent adds in batches, and first sweetening agent added 60% of sweetening agent gross weight before alloy adds, behind the vacuum cycle 2min, the second batch sweetening agent adds together with alloy.It is 15min less than RH cycling time of 2.0mba that sweetening agent adds rear assurance vacuum tightness.
The adding mode of sweetening agent of the present invention adopts alloy feed bin directly joining method, adopts the low fluorine sweetening agent of fritting, and the sweetening agent particle diameter is controlled at 3～5mm, and add-on is 3～5Kg/t.
The present invention is by adding the content that aluminum shot is regulated top slag FeO+MnO to ladle top slag, the content that FeO+MnO in the ladle top slag that enters the station is processed in the RH desulfurization is controlled at below 12%, the top basicity of slag need to be controlled at more than 6, after finishing, RH desulfurization processing in ladle, adds silicon carbide to the ladle top slag modification, improve ladle top slag basicity, reduce the ladle top slag oxidisability, return sulphur to prevent subsequent handling.
The RH desulphurization circulating time of the present invention will guarantee preferably can reach 15min more than 10min, and it is 15min less than vacuum cycle time of 2.0mba that sweetening agent adds rear assurance vacuum tightness.
The RH of the present invention top basicity of slag that enters the station reaches 6, guarantees in the slag of top that the content of MgO is 8%～10%.
Beneficial effect of the present invention is: 1, RH significant desulfurization effect, average desulfurization degree can reach 36.7%, specifically sees Table 2.Can satisfy the requirement of the dark desulfurization of non-oriented electrical steel.
2, can regulate FeO+MnO content by adding aluminum shot to ladle top slag.The RH desulfurization is processed in the ladle top slag that enters the station FeO+MnO content and need to be controlled at below 12% and can obtain preferably sweetening effectiveness, and the lower sweetening effectiveness of FeO+MnO content is better, and the top basicity of slag need to be controlled at more than 6.RH desulfurization processing finishes and need to prevent that subsequent handling from returning sulphur to the ladle top slag modification, thereby guarantees the RH sweetening effectiveness.
3, in order to guarantee the RH sweetening effectiveness, the RH desulphurization circulating time will guarantee preferably can reach 15min more than 10min.
4, the RH station top basicity of slag that enters the station reaches 6, and the loss of the anti-material of equipment when 8～10% can obviously reduce the RH desulfurization and process of the assurance MgO content in the slag of top improves RH equipment life, specifically sees Table 3.Table 1 is that RH sweetening agent of the present invention forms, and table 2 is RH sweetening effectiveness of the present invention, and table 3 improves RH effect equipment life for the present invention.
Embodiment
The production technique that the present invention adopts is: molten iron pretreatment desulfurizing → LD → pushing off the slag tapping → LF → RH decarburization, desulfurization → continuous casting.
Determine processing parameter lift gas flow: increase within the specific limits the lift gas flow and can increase the RH circulation, thereby accelerate desulfurization rate, but after the saturated Argon amount of Argon amount greater than equipment, circulation no longer increases with the increase of Argon amount.Excessive Argon amount can make the serious splash of molten steel in the vacuum chamber on the contrary, thereby produces a large amount of cold steel.Therefore needing rule of thumb, formula F=(0.75～1.0) * S determines rational Argon amount.In the formula: F is the Argon amount, and unit is NL/min; S is tubular stinger internal diameter sectional area, and unit is cm
2
On-the-spot tubular stinger internal diameter is 45cm, thereby determines that the lift gas flow is:
F＝(0.75～1.0)×(22.5)
2×π＝1190～1590NL/min
Determine the sweetening agent processing parameter: because RH desulfurization processing requirements sweetening agent has lower fusing point and higher basicity, therefore adopt the low fluorine CaO-Al that fusing point is low, basicity is high
2O
3The slag system sweetening agent.Simultaneously in sweetening agent, add BaO, thus improved sweetening agent sweetening power, reduced the sweetening agent fusing point, reduced CaF
2Consumption.Sweetening agent sees Table 1 concrete the composition.Pre-melted desulfurizing agent is adopted in test, and the sweetening agent particle diameter is controlled at 3～5mm.Add-on is 3～5Kg/t.The adding mode of sweetening agent adopts alloy feed bin directly joining method.In order to realize continuing desulfurization, with in two batches time adding of sweetening agent, first sweetening agent added 60% of sweetening agent gross weight before alloy adds, and behind the vacuum cycle 2min, the second batch sweetening agent adds together with alloy.The vacuum cycle time that sweetening agent adds the little 2.0mba of rear assurance vacuum tightness is 15min.
Embodiment 1:
Technique of the present invention is: after RH enters the station, be 1200NL/min with the lift gas flow set, behind the 3min lift gas flow be increased to 1600NL/min.Decarburization is forced in oxygen blast after vacuum tightness is reduced to 2.0mba, and oxygen blast below 2.0mba, enters the nature decarburization with vacuum degree control after finishing, and guarantees that the nature decarburization time is at 20min.After vacuum decarburization finishes, aluminum deoxidation.At first adopt low-carbon ferrosilicon to carry out alloying with silicon, then drop into sweetening agent by RH alloy feed bin to vacuum chamber, sweetening agent is inferior adding in two batches.Test heat cycling time is 10min to 15min.
Carry out at the slab production line RH of certain iron and steel enterprise refining furnace, the test steel grade is non-oriented electrical steel.The employing production technique is: molten iron pretreatment desulfurizing → LD → pushing off the slag tapping → LF → RH decarburization, desulfurization → continuous casting.Then rule of thumb formula is determined rational Argon amount, to determine rational lift gas flow.After RH enters the station, be 1200NL/min with the lift gas flow set, behind the 3min lift gas flow be increased to 1600NL/min.After vacuum decarburization finished, aluminum deoxidation was controlled at FeO+MnO content in the slag of top below 12%.Adopt the low fluorine sweetening agent of fritting, the adding mode is alloy feed bin directly joining method, and the sweetening agent particle diameter is controlled at 3～5mm, and add-on is 3～5Kg/t.With in two batches time adding of sweetening agent.Drop into the sweetening agent circulation 2min that first accounts for 60% total add-on by RH alloy feed bin to vacuum chamber after the deoxidation, then adopt low-carbon ferrosilicon to carry out alloying with silicon and add simultaneously second batch of sweetening agent.It is 15min less than vacuum cycle time of 2.0mba that sweetening agent adds rear assurance vacuum tightness.Add 200Kg silicon carbide in the RH departures ladle top slag.The finished product sulphur content can be controlled at below the 40ppm, and RH operation mean efficiency of desulfurization reaches more than 36%.The RH tubular stinger life-span can reach 68 stoves.
Contrast case 1:
Carry out at the slab production line RH of iron and steel enterprise of same steel mill refining furnace, the test steel grade is non-oriented electrical steel.Adopt molten iron pretreatment desulfurizing → LD → pushing off the slag tapping → LF → RH decarburization → continuous casting production process.After RH enters the station, be 1200NL/min with the lift gas flow set, behind the 3min lift gas flow be increased to 1600NL/min.Decarburization is forced in oxygen blast after vacuum tightness is reduced to 2.0mba, and oxygen blast below 2.0mba, enters the nature decarburization with vacuum degree control after finishing, and guarantees that the nature decarburization time is at 20min.Do not carry out desulfurization and process, ladle RH departures ladle top slag does not carry out modification.The finished product sulphur content is more than 65ppm, and the RH operation is without sweetening power.The RH tubular stinger life-span is 75 stoves.
Contrast case 2:
Carry out at the slab production line RH of iron and steel enterprise of same steel mill refining furnace, the test steel grade is non-oriented electrical steel.Adopt molten iron pretreatment desulfurizing → LD → pushing off the slag tapping → LF → RH decarburization, desulfurization → continuous casting production process.After RH enters the station, be 1200NL/min with the lift gas flow set, behind the 3min lift gas flow be increased to 1600NL/min.After vacuum decarburization finished, aluminum deoxidation was not controlled FeO+MnO in the slag of top.Adopt fritting tradition sweetening agent, the adding mode is alloy feed bin directly joining method, and the sweetening agent particle diameter is controlled at 3～5mm, and add-on is 3～5Kg/t.Carrying out alloying with silicon at the employing low-carbon ferrosilicon once adds sweetening agent simultaneously.It is 15min less than vacuum cycle time of 2.0mba that sweetening agent adds rear assurance vacuum tightness.The not plus silicon carbide modification of RH departures ladle top slag.The finished product sulphur content can be controlled at below the 55ppm, and RH operation mean efficiency of desulfurization reaches more than 33%.The RH tubular stinger life-span is 46 stoves.
The invention has the advantages that: RH equipment need not to transform, and is simple to operate.The RH desulfurization degree on average reaches 36.7%, has preferably sweetening effectiveness.The content of finding the FeO+MnO of ladle top slag has material impact for sweetening effectiveness.Improving ladle top slag basicity not only can improve the RH desulfuration efficiency but also can alleviate corrosion to RH equipment.
Table 1 RH sweetening agent forms
| SiO 2 | Al 2O 3 | CaO | MgO | BaO | CaF 2 |
| 3 | 25～30 | 50～55 | 3～5 | 7～12 | 3 |
Table 2 RH sweetening effectiveness
| The heat numbering | The RH sulphur content (%) that enters the station at the station | RH station departures sulphur content (%) | Desulfurization degree (%) |
| 1 | 0.0059 | 0.0036 | 39.0 |
| 2 | 0.0043 | 0.0025 | 41.9 |
| 3 | 0.0056 | 0.0039 | 30.4 |
| 4 | 0.0062 | 0.0042 | 32.3 |
| 5 | 0.0050 | 0.0028 | 44.0 |
| 6 | 0.0058 | 0.0039 | 32.8 |
Table 3 improves RH effect equipment life
Claims (4)
1. RH refining desulfuration technique that is used for non-oriented electrical steel is characterized in that:
(1) technological process of production is: molten iron pretreatment desulfurizing → LD (ladle) → pushing off the slag tapping → LF (electric furnace refining) → RH (vacuum refinement) decarburization, desulfurization → continuous casting;
(2) after the RH desulfurization is processed and entered the station, be 1200NL/min with the lift gas flow set, behind the 3min lift gas flow be increased to 1600NL/min;
(3) decarburization is forced in oxygen blast after vacuum tightness is reduced to 2.0mba, and oxygen blast below 2.0mba, enters the nature decarburization with vacuum degree control after finishing, and guarantees that the nature decarburization time is at 20min;
(4) after vacuum decarburization finishes, aluminum deoxidation, and by FeO+MnO content in the add-on control top slag of aluminium, at first adopt low-carbon ferrosilicon to carry out alloying with silicon, then drop into the low fluorine sweetening agent of fritting by RH alloy feed bin to vacuum chamber, sweetening agent adds in batches, first sweetening agent added 60% of sweetening agent gross weight before alloy adds, behind the vacuum cycle 2min, the second batch sweetening agent adds together with alloy, and it is 15min less than RH cycling time of 2.0mba that sweetening agent adds rear assurance vacuum tightness;
By adding the content that aluminum shot is regulated top slag FeO+MnO to ladle top slag, the content that FeO+MnO in the ladle top slag that enters the station is processed in the RH desulfurization is controlled at below 12%, the top basicity of slag need to be controlled at more than 6, after finishing, RH desulfurization processing in ladle, adds silicon carbide to the ladle top slag modification, improve ladle top slag basicity, reduce the ladle top slag oxidisability, return sulphur to prevent subsequent handling;
Described RH desulfurization is processed the top basicity of slag that enters the station and is reached more than 6, guarantees in the slag of top that the content of MgO is 8%～10%.
2. technique according to claim 1, it is characterized in that: the adding mode of sweetening agent adopts alloy feed bin directly joining method, adopts the low fluorine sweetening agent of fritting, and the sweetening agent particle diameter is controlled at 3～5mm, and add-on is 3～5Kg/t.
3. technique according to claim 1, it is characterized in that: the RH desulphurization circulating time will guarantee more than 10min, it is 15min less than vacuum cycle time of 2.0mba that sweetening agent adds rear assurance vacuum tightness.
4. technique according to claim 1, it is characterized in that: the RH desulphurization circulating time will guarantee that the best can reach 15min.
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| CN102199687A (en) * | 2011-04-26 | 2011-09-28 | 攀钢集团钢铁钒钛股份有限公司 | RH vacuum treatment desulfurizing agent used for non-oriented electrical steel, preparation method thereof, and desulfurizing method using same |
| CN102417951A (en) * | 2011-10-17 | 2012-04-18 | 南京钢铁股份有限公司 | Vacuum refining process |
| CN102634642A (en) * | 2012-04-10 | 2012-08-15 | 河北省首钢迁安钢铁有限责任公司 | Deep desulfuration method for non-oriented electrical steel |
| CN103484600B (en) * | 2013-09-10 | 2015-05-27 | 首钢总公司 | Anti-RH (Relative Humidity) resulfurization technology for ultralow-sulfur moderate-thickness plate steel in high-sulfur molten steel smelting |
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| CN104073599A (en) * | 2014-07-21 | 2014-10-01 | 攀钢集团西昌钢钒有限公司 | Deep decarbonization method for mild steel and steel prepared according to method |
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