US20040245682A1 - Method for refining molten iron containing chromium - Google Patents

Method for refining molten iron containing chromium Download PDF

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Publication number
US20040245682A1
US20040245682A1 US10/490,459 US49045904A US2004245682A1 US 20040245682 A1 US20040245682 A1 US 20040245682A1 US 49045904 A US49045904 A US 49045904A US 2004245682 A1 US2004245682 A1 US 2004245682A1
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United States
Prior art keywords
refining
vacuum
gas
chromium
vessel
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Abandoned
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US10/490,459
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English (en)
Inventor
Kosuke Yamashita
Ryuji Nakao
Tomoaki Tanaka
Masao Igarashi
Koichiro Yoshino
Makoto Sumi
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Nippon Steel Corp
Nippon Steel Plant Designing Corp
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Individual
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Publication date
Priority claimed from JP2001286695A external-priority patent/JP2003096515A/ja
Priority claimed from JP2001286694A external-priority patent/JP4895446B2/ja
Priority claimed from JP2001339046A external-priority patent/JP4262428B2/ja
Priority claimed from JP2001391274A external-priority patent/JP3922923B2/ja
Priority claimed from JP2002235726A external-priority patent/JP3973512B2/ja
Application filed by Individual filed Critical Individual
Assigned to NITTETSU PLANT DESIGNING CORPORATION, NIPPON STEEL COROPORATION reassignment NITTETSU PLANT DESIGNING CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IGARASHI, MASAO, NAKAO, RYUJI, SUMI, MAKOTO, TANAKA, TOMOAKI, YAMASHITA, KOSUKE, YOSHINO, KOICHIRO
Publication of US20040245682A1 publication Critical patent/US20040245682A1/en
Priority to US11/712,778 priority Critical patent/US7497987B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/068—Decarburising
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/16—Introducing a fluid jet or current into the charge
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/005—Manufacture of stainless steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/30—Regulating or controlling the blowing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C21C5/30—Regulating or controlling the blowing
    • C21C5/35—Blowing from above and through the bath
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/068—Decarburising
    • C21C7/0685—Decarburising of stainless steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/10—Handling in a vacuum
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/0025—Charging or loading melting furnaces with material in the solid state
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/0025—Charging or loading melting furnaces with material in the solid state
    • F27D3/0032—Charging or loading melting furnaces with material in the solid state using an air-lock
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/001—Extraction of waste gases, collection of fumes and hoods used therefor
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/004—Systems for reclaiming waste heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/16—Introducing a fluid jet or current into the charge
    • F27D2003/162—Introducing a fluid jet or current into the charge the fluid being an oxidant or a fuel
    • F27D2003/163—Introducing a fluid jet or current into the charge the fluid being an oxidant or a fuel the fluid being an oxidant
    • F27D2003/164—Oxygen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/16—Introducing a fluid jet or current into the charge
    • F27D2003/166—Introducing a fluid jet or current into the charge the fluid being a treatment gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/16—Introducing a fluid jet or current into the charge
    • F27D2003/168—Introducing a fluid jet or current into the charge through a lance

Definitions

  • the present invention relates to a refining method and refining apparatus for chromium-contained molten steel which refine chromium-contained molten steel in a refining vessel while blowing a gas containing oxygen gas.
  • Japanese Unexamined Patent Publication (Kokai) No. 6-287629 discloses the method of supplying oxygen gas or a mixed gas of oxygen gas and inert gas as the blown gas, decarburizing the melt until the concentration of carbon in the melt falls to 0.5 wt %, evacuating in the vessel to not more than 200 Torr (26 kPa), and continuing to decarburize the melt after the concentration of carbon falls below this value.
  • the pressure inside the vessel in the vacuum treatment is made not more than 200 Torr (26 kPa) because it is considered that the oxygen efficiency for decarburization falls at a pressure higher than that.
  • Japanese Unexamined Patent Publication (Kokai) No. 9-71809 discloses a refining method comprising decarburizing a melt by blowing a gas containing oxygen gas in the atmosphere, then switching from atmospheric treatment to vacuum treatment at the stage when the concentration of carbon drops to 0.7 to 0.05 wt % and blowing a gas containing oxygen gas under a vacuum of 200 (26 kPa) to 15 Torr (2 kPa).
  • the vacuum condition is made not more than 200 Torr (26 kPa) because it is considered the vacuum treatment cannot be effectively performed under a pressure higher than this.
  • Japanese Unexamined Patent Publication (Kokai) No. 51-142410 discloses the method of oxygen refining in a converter, then decarburizing the melt in a vacuum decarburization ladle to make the concentration of carbon after vacuum treatment 0.008%.
  • Japanese Examined Patent Publication (Kokoku) No. 60-10087 discloses the method of refining chromium steel by first refining by oxygen gas at the initial ordinary temperature until the carbon falls to about 0.2 to 0.4 wt %, then stopping the supply of oxygen gas while continuing to agitate the melt by the inert gas in the same vessel, continuously lowering the pressure inside the vessel to about 10 Torr (1.3 kPa), and lowering the concentration of carbon after vacuum treatment to 0.13 wt %.
  • 6-287629 discloses a decarburization refining method for chromium-contained molten steel comprising supply a mixed gas of oxygen gas and inert gas as the blown gas, performing decarburization refining under atmospheric pressure until the concentration of carbon in the melt falls to 0.5 wt %, then, after the concentration of carbon falls below this value, evacuating the inside of the vessel to not more than 200 Torr (26 kPa) and continuing to decarburize the melt.
  • gas including oxygen gas is supplied even in the vacuum refining.
  • the oxygen efficiency for decarburization is improved, so an improvement in the decarburization rate is achieved and the refining time can be shortened, so it is possible to achieve a large reduction in the refining costs and improvement in the productivity and refining down to the ultra-low carbon region of a concentration of carbon of not more than 0.01 wt % becomes easy.
  • the total amount of the blown gas during the vacuum annealing is made 0.3 Nm 3 /min ⁇ T.
  • vacuum refining furnaces comes in various types such as VOD, AOD, RH, and REDA, but vacuum exhaust equipment is required for evacuating the inside of the furnace.
  • the vacuum exhaust equipment for industrially evacuating the inside of a vacuum refining furnace generally achieves a predetermined degree of vacuum inside the furnace by combining a large number of ejectors.
  • the degree of vacuum is controlled in accordance with the progress in refining in the vacuum refining furnace, but normally one or more ejectors with capacities commensurate with the targeted degree of vacuum are operated among a large number of ejectors to secure the predetermined degree of vacuum.
  • one type of vacuum exhaust unit used industrially is a water-sealed vacuum pump.
  • the attainable degree of vacuum is about 61 Torr (8 kPa).
  • vacuum oxygen decarburization of a carbon melt is an operation which requires extreme care.
  • the point is to control the degree of vacuum and the oxygen blow rate in accordance with the concentration of carbon in the melt.
  • the oxygen blow rate can be controlled to a certain extent by the flow adjustment valve of the oxygen gas, but no sufficient control method has been established for the degree of vacuum.
  • the exhaust gas sucked in contains a high concentration of CO gas, so when mixing in air containing a combustion-assisting gas constituted by oxygen, there is the danger of combustion and explosion. Employment for actual machinery is extremely dangerous. Further, if allowing gas to leak in from the outside, the load on the exhaust unit increases. For example, the power used by the vacuum pump increases. Therefore, this is not preferable from the viewpoint of energy conservation. Further, the method of controlling the amount of supply of steam to an ejector used in this patent relies on the fact that the optimum steam flow rate of an ejector is distinctive, so changing this remarkably reduces the exhaust performance of the ejector itself. Further, at the same time, a slight fluctuation in the amount of steam is overly sensitively reflected in the ejector performance, so extremely fine control of the pressure inside the refining vessel becomes difficult.
  • alloy or secondary materials are added to the melt in the middle of refining or at the end stage of refining. Normally, these are charged into the vessel and added to the melt by allowing them to naturally drop from an alloy hopper provided at the top of the refining vessel through a chute.
  • the means has been adopted of providing the alloy and secondary material addition port with side walls resistant to the effects of the metal and slag or, in the case of a refining vessel with a high tank height, providing a top cover. Further, the means has also been adopted of using the alloy and secondary material addition port jointly as the insertion port of the top blowing lance. If considering continuous long term operation of a vacuum refining vessel, however, neither means is sufficient in practice.
  • vacuum exhaust equipment for industrially evacuating a vacuum refining vessel generally achieves a predetermined degree of vacuum in the furnace by combining a large number of ejectors or using a vacuum pump.
  • Vacuum ejectors utilize the so-called “mist-blowing principle” and suck in and exhaust the exhaust gas in the vacuum refining vessel and the ducts and other parts of the vacuum path by the ejected media.
  • steam is used industrially. Steam is condensed by the cooling water at a condenser after the ejectors to become water again and therefore only the exhaust gas is exhausted to the next stage.
  • the cooling water of the condenser and the condensed water of the steam are temporarily collected and stored at a water storage tank near the ground and are pumped to the cooling tower by a pump.
  • a water storage tank near the ground and are pumped to the cooling tower by a pump.
  • the vacuum pump industrially a water-sealed pump is used and a large amount of water is used.
  • the water used by the vacuum pump is collected and stored in a water storage tank in the same way as the condenser water.
  • Exhaust gas contains a large amount of CO gas.
  • the condenser water is accompanied by large numbers of bubbles of exhaust gas containing CO which flow into the water storage tank along with it. Therefore, the inside of the water storage tank becomes an atmospheric gas containing CO gas in composition. In the sense of preventing the gas inside the tank from leaking outside the tank, closeability and sealability are very important as functions required for a water storage tank.
  • Water storage tanks come in generally two types: steel seal pots and concrete (the top cover part made of steel) hot wells.
  • Steel seal pots have a good closeability, but suffer from the problems of corrosion and swelling capital costs.
  • concrete hot wells are free from corrosion and relatively inexpensive in terms of capital costs as well, but suffer from problems in the sealability with the top steel covers.
  • the invention will be explained taking as an example mainly the latter concrete hot wells, but the invention may similarly be applied to steel seal pots.
  • the method of forcibly evacuating the inside of the hot well by a suction fan is widely employed. Due to this, the inside of the hot well becomes a constantly negative pressure and the danger of leakage of the inside gas is remarkably reduced. However, the inside of a hot well being made negative pressure due to suction of gas means suction of air from the seal parts. The clearance of the seal parts therefore gradually expands. If the suction fan were to stop in this state for some reason or another, a large amount of CO-containing gas would leak from the expanded clearance of the seal parts.
  • the present invention has as its object the provision of a refining method for a chromium-contained molten steel comprising refining by blowing a gas containing oxygen gas into a chromium-contained molten steel in a refining vessel and enabling a reduction of the amount of use of inert gas or oxygen gas and shortening of the refining time.
  • the present invention has as its object the provision of a refining method able to shorten the time required for refining and reduce the refining cost in decarburization refining of an ultra-low carbon melt.
  • the present invention provides a vacuum control method and apparatus in vacuum exhaust equipment able to control the degree of vacuum in a vessel or ducts at the time of refining a melt by oxygen decarburization in a vacuum refining vessel.
  • the present invention has as its object the provision of a seal unit and seal method able to avoid blocking of an alloy and secondary material addition port even under refining conditions where the metal and slag are remarkably violently splashed.
  • the present invention has as its object to detect with a high precision water leakage in an exhaust gas treatment apparatus in a metallurgical furnace or vessel of an atmospheric refining or vacuum refining apparatus, in particular a water-cooled duct, exhaust gas cooling unit, or other unit using cooling water and provides a detection unit able to detect even a slight amount of water leakage during treatment, easily to manage and maintain, and superior in durability.
  • the present invention has as its object the provision of an apparatus for simply solving the problems in the hot well, that is, suppressing leakage of CO-containing gas from the hot well and damage to equipment at the time of overflow of the cooling water in the hot well.
  • the present invention was made to solve the above problems and has as its gist the following:
  • a refining method refining by blowing a mixed gas including oxygen gas into a chromium-contained molten steel in a refining vessel said refining method for a chromium-contained molten steel characterized by having a first step of blowing in said mixed gas while making the inside of the vessel a pressure of a range of 400 Torr (53 kPa) to atmospheric pressure, a second step of blowing said mixed gas while evacuating said vessel to 250 to 400 Torr (33 to 53 kPa), and a third step of blowing said mixed gas while further evacuating the inside of the vessel to not more than 250 Torr (33 kPa) and by refining step by step while switching from the first step to the second step at a concentration of carbon in the melt of 0.8 to 0.3% and switching from the second step to the third step at a concentration of carbon in the melt of 0.4 to 0.1%.
  • a refining method for a chromium-contained molten steel as set forth in (1) characterized by refining while making the mixed gas blow rate at said second step at least 0.4 Nm 3 /min per ton melt.
  • a refining method for a chromium-contained molten steel as set forth in (1) or (2) characterized by, in said first step, performing refining comprising refining the entire amount under atmospheric pressure, refining the entire amount under a vacuum, or refining first at atmospheric pressure, then under a vacuum.
  • a refining method for a chromium-contained molten steel as set forth in (1) characterized by, in said third step, refining by further evacuating step by step the inside of the vessel along with the decrease in concentration of carbon in the melt.
  • a refining method for a chromium-contained molten steel as set forth in (1) characterized by, in said third step, refining by any means of supplying only inert gas for the blowing of said mixed gas, gradually reducing the ratio of supply of oxygen gas in said mixed gas along with the decrease in concentration of carbon in the melt, or supplying inert gas after the ratio of oxygen gas in said mixed gas decreases.
  • a refining method for a chromium-contained molten steel as set forth in (1) characterized by starting evacuating the inside of said refining vessel, then blowing inert gas, nitrogen, or another non-oxidizing gas or a mixed gas of the same to reduce the concentration of oxygen in the exhaust gas to not more than 7 vol %, then blowing said mixed gas into said evacuated refining vessel and starting refining.
  • a refining method for a chromium-contained molten steel as set forth in (1) characterized by, in said third step, reducing the concentration of carbon in the melt to not more than 0.08%, then restoring the pressure in the vessel to at least 400 Torr (53 kPa), then bottom blowing mixed gas and vacuum refining at a mixed gas blow rate of at least 0.4 Nm 3 /min per ton melt so as to reduce the carbon to an ultra-low level.
  • a refining apparatus for a chromium-contained molten steel said refining apparatus for a chromium-contained molten steel characterized by comprising a vacuum refining vessel, an alloy and sub-material addition unit provided above the vacuum refining vessel, exhaust gas cooler, vacuum valve, one-stage or multiple-stage ejector type vacuum exhaust unit, and water-sealed type vacuum pump arranged successively and by having a pressure control valve under a vacuum for returning part of the exhaust gas from down stream side of said water-sealed type vacuum pump to the upstream side of said water-sealed type vacuum pump.
  • FIG. 1 are views of a refining vessel of the present invention, wherein (a) shows the state at the time of vacuum refining and (b) shows the state at the time of atmospheric pressure refining.
  • FIG. 2 is a view of the relationship between the pressure inside a refining vessel and oxygen efficiency for decarburization.
  • FIG. 3 is a view of the relationship between the pressure inside a refining vessel and a dust generation index.
  • FIG. 4 is a view schematically showing an exhaust gas treatment unit of a vacuum refining facility.
  • FIG. 5 is a view of the trends in the vacuum treatment time and the change in degree of vacuum in a vacuum refining furnace and a vacuum exhaust unit.
  • FIG. 6 is a view schematically showing a seal unit in a conventional vacuum refining unit.
  • FIG. 7 is a view of an embodiment of a seal unit according to the present invention.
  • FIG. 8 is a view schematically showing the area around a hot well.
  • FIG. 9 is a view of a side view of a hot well water-sealed cover.
  • a refining vessel 1 shown in FIG. 1( b ) is used. Refining gas is blown into the chromium-contained molten steel in the refining vessel through a bottom blowing tuyere 2 . Further, the refining vessel 1 has a detachable exhaust hood 3 . At the time of vacuum refining, as shown in FIG. 1( a ), an exhaust hood 3 is attached to the refining vessel 1 and gas is sucked out to evacuate the refining vessel.
  • the exhaust hood 3 is not attached, so as the blown gas, it is also possible to blow gas while using not only the bottom blowing tuyere 2 , but also a top blowing lance 12 .
  • the present invention has as its biggest feature having a step of blowing a gas containing oxygen gas while evacuating the inside of the vessel to 250 to 400 Torr (33 to 53 kPa) in the refining process.
  • This step is called the “second step”.
  • this step hereinafter generally referred to as the “second step” in the medium carbon region around a concentration of carbon of 0.4 wt % and vigorously stirring the melt simultaneously, it is possible to maintain the oxygen efficiency for decarburization in the medium carbon region at a high value and further possible to suppress the generation of dust.
  • FIG. 2 shows the relationship between the pressure inside the refining vessel and the oxygen efficiency for decarburization when making the bottom blowing gas blow rate 0.4 to 0.9 Nm 3 /min per ton melt. It is learned that up until the region above a pressure inside the vessel of 400 Torr (53 kPa), a high oxygen efficiency for decarburization can be maintained. Note that at under 100 Torr (13 kPa), the amount of generation of dust is large and operation not possible.
  • FIG. 3 is a view of the relationship between the pressure inside the refining vessel and dust generation index when making the bottom blowing gas blow rate 0.4 to 0.9 Nm 3 /min per ton melt.
  • the dust generation index is a value indexed to the average value of the dust generation at a pressure inside the vessel of 400 Torr (53 kPa). It is learned that by making the pressure inside the refining vessel at least 250 Torr (33 kPa), it is possible to greatly reduce the dust generation.
  • the bottom blowing gas blow rate is preferably made at least 0.4 Nm 3 /min per ton melt.
  • the type of the blown gas of the bottom blown gas at the second step it may be made a mixed gas of oxygen and an inert gas from the start of the second step, but it is also possible to use a pattern of first blowing oxygen gas alone and then successively increasing the ratio of the inert gas in the second step.
  • the pressure in the refining vessel at the second step can be held at a certain pressure in the range of 250 to 400 Torr (33 to 53 kPa), but if adopting a pattern of successively changing from a high pressure to a low pressure, it is possible to decarburize the melt while maintaining a substantially constant high oxygen efficiency for decarburization without mixing in inert gas, so more preferable results can be obtained.
  • the reason for making the pressure at least 400 Torr (53 kPa) is that if in the region of concentration of carbon of the first step, the content of carbon becomes high, so it is possible to obtain a sufficiently excellent oxygen efficiency for decarburization even under high pressure. Further, in the carbon region, it is important to secure the amount of blown gas and secure a high refining efficiency, but if using the same vacuum suction unit, the higher the pressure, the greater the exhaust gas suction capacity and the greater the amount of blown gas that can be obtained. Together with this, a high pressure enables generation of dust and splashing of the fine particles of metal produced from the melt surface in the vacuum refining vessel to be suppressed even with the same gas blow rate.
  • the inside of the vessel is evacuated to 250 Torr (33 kPa) and gas blown in.
  • the concentration of carbon the greater the effect of melt agitation on the decarburization reaction.
  • the pressure is preferably made lower than the second step.
  • the third step it is preferable to successively evacuate in the vessel step by step along with the decline in the concentration of carbon in the melt. It is further preferable to successively evacuate the inside the vessel to a pressure inside the vessel at the final stage of the decarburization refining of not more than 50 Torr (7 kPa).
  • the P CO at equilibrium with the chromium in the melt rapidly falls. For example, at a carbon of 0.2%, the equilibrium P CO is about 0.3 atm, but at a carbon of 0.1%, it becomes not more than 0.1 atm. If evacuating the vessel step by step corresponding to this, it is possible to stably hold the oxygen efficiency for decarburization at a high level.
  • the concentration of carbon sufficiently falls, so the blown gas may be made a mixed gas not containing oxygen gas or only an inert gas. Further, when supplying a mixed gas of oxygen gas and an inert gas as the blown gas, it is preferable to gradually reduce the ratio of the oxygen gas in the mixed gas along with the decline in concentration of carbon in the melt. Compared with when the blown gas is just an inert gas, when suitably mixing in oxygen gas, efficient decarburization can be performed after securing the rate of supply of oxygen, so it is possible to shorten the refining time.
  • the P CO at equilibrium with the chromium in the melt rapidly falls, so if reducing the ratio of oxygen gas of the blown gas, efficient decarburization becomes possible. Further, there are cases where the refining is performed while making the blown gas only inert gas in the final stage of the third stage. Further, it is possible to charge ferrosilicon immediately before or after making the blown gas an inert gas so as to reduce the chromic acid in the slag on the melt and improve the yield of chromium (chromium) or other valuable metals.
  • the third step evacuates the vessel more than the second step, but the rate of the blown gas is preferably made at least 0.4 Nm 3 /min per ton melt as well. Note that if the rate of blown gas becomes too large, a large amount of splash will be generated and will hinder operation, so it is preferable to make the rate not more than 1.0 Nm 3 /min per ton melt.
  • the refining gas is passed through an inner tube and the cooling gas through an outer tube.
  • the outer tube is supplied with a small amount of a cooling gas such as nitrogen or argon or propane or another hydrocarbon gas or a mixed gas of the same.
  • the gas mixed with the oxygen (O 2 ) may be argon or another inert gas, N 2 , CO, or CO 2 alone or in a mixture.
  • the amount of blown gas is increased, so it becomes necessary to consider a vacuum exhaust unit for evacuating the inside the refining vessel.
  • An increase in the amount of heat generation due to the increase in the amount of exhaust gas can be dealt with by increasing number of the gas coolers 8 installed in the exhaust pipe 7 between the exhaust hood 3 and the vacuum exhaust unit (steam ejector 10 or water pump 11 ) shown in FIG. 1( a ) or the cooling capacity per unit.
  • an increase in the amount of dust generation due to the increase in the amount of exhaust gas can be dealt with by increasing number of the bag filters 9 installed in the exhaust pipe between the exhaust hood 3 and the vacuum exhaust unit or the dust treatment capacity per unit.
  • the amount of dust generation is reduced, so even when increasing the bag filters, the minimum increase is enough.
  • the pressure in the vessel is restored to at least 400 Torr (53 kPa) after the first vacuum refining up to the third step.
  • ultra-low carbon chromium steel with a concentration of carbon of not more than 0.01% in the first-stage vacuum refining as in the past it is necessary to continue the vacuum refining for at least 20 minutes, while if restoring the pressure in the middle of the vacuum refining for two-stage evacuation as in the present invention, it becomes possible to shorten the total time of the vacuum refining by about 10 minutes and produce similar ultra-low carbon steel.
  • the effect of the present invention can be obtained.
  • the amount of natural decarburization occurring when evacuating the vessel is about 0.05%. It is sufficient to decarburize the melt to the concentration of carbon at the time of restoration of pressure minus this amount in the second vacuum refining. If the concentration of carbon at the time of restoration of pressure exceeds 0.12%, the amount of decarburization at the second vacuum refining increases and a sufficient effect can no longer be obtained.
  • the gas blow rate in the second vacuum refining is made at least 0.4 Nm 3 /min per ton melt.
  • the vacuum refining time for producing the ultra-low carbon steel can only be shortened by about 1 to 3 minutes compared with the conventional one-stage vacuum refining.
  • More preferable results can be obtained if making the gas blow rate in the second vacuum refining at least 0.5 Nm 3 /min per ton melt.
  • the concentration of carbon after natural decarburization in the second vacuum refining is not more than 0.05%.
  • the decarburization reaction becomes completely regulated by the diffusion of carbon.
  • the gas blow rate becomes an important factor.
  • the rate is at least 0.4 Nm 3 /min per ton melt.
  • the pressure inside the vessel at the second vacuum refining is preferably made not more than 100 Torr (13 kPA). This is because the lower the pressure in the vessel, the lower the concentration of oxygen dissolving in the melt and because with the same gas supply rate, the agitation force due to expansion of the gas becomes larger and therefore the decarburization rate becomes higher. To enjoy these effects, it is effective to make the pressure not more than 100 Torr (13 kPa). More preferably the pressure inside the vessel in the second vacuum refining is made not more than 50 Torr (7 kPa).
  • the gas blown in the second vacuum refining may be made a mixed gas of oxygen gas and an inert gas.
  • the concentration of carbon falls, so to suppress oxidation of chromium and obtain a high oxygen efficiency for decarburization, it is not possible to make the ratio of the oxygen gas that high.
  • the ratio of the oxygen gas in gas blown in the second vacuum refining is preferably made not more than 30%. If the ratio of the oxygen gas exceeds 30%, the amount of oxygen used for the oxidation of the chromium in the melt rapidly increases. Over half of the oxygen gas blown in is used for oxidation of the chromium, so the ratio is preferably made not more than 30%. More preferably, the ratio of the oxygen gas may be made about 10%.
  • FIG. 4 A conceptual view of the exhaust gas treatment equipment of the present invention is shown in FIG. 4.
  • the exhaust gas 15 produced in the vacuum refining furnace 1 passes through the water-cooled duct 13 and is cooled by an exhaust gas cooler 16 connected there. Next, it passes through the duct 14 , is cleaned of dust by the dust collector 9 , passes through the multiple-stage ejector-type vacuum exhaust unit 10 , is further sucked in by the water-sealed type vacuum pump 11 , and is discharged into the atmosphere.
  • the degree of vacuum of any of the vacuum meter 17 in the furnace, the vacuum meter 18 after the exhaust gas cooler, the vacuum meter 19 after the dust collector, and the vacuum meter 20 after the multiple-stage ejector type vacuum exhaust unit is measured and the pressure signal input to the control unit 21 .
  • Part of the exhaust gas is returned to the front of the vacuum pump 11 while adjusting the opening degree of the vacuum control use pressure adjustment valve 22 . Due to this, it becomes possible to control the inside of the vacuum refining vessel or the inside of the ducts to a predetermined target degree of vacuum. In controlling the degree of vacuum, it is possible to freely select which signal of the vacuum meters to use according to the stage of refining.
  • the level of degree of vacuum controlled to depends on the amount of splashing of metal from the vacuum refining vessel and the amount of oxidation of chromium in the melt. In general, if the degree of vacuum becomes better (the pressure value becomes lower), the carbon in the melt will be preferentially oxidized and the amount of oxidation of the chromium will be reduced. However, the amount of metal and slag splashed from the vacuum refining vessel will increase. That is, from the region of low chromium oxidation loss, it is better to increase the degree of vacuum, but from the region of low metal and slag, it is better to reduce the degree of vacuum. Therefore, considering the two, there is an optimal range of the degree of vacuum controlled to. Further, the amount of oxidation of the chromium in the melt and the amount of splash of the metal and slag also depend on the amount of carbon in the melt.
  • a vacuum valve 23 at the front of the vacuum exhaust unit is closed and the vacuum exhaust equipment side, including the ejectors and the water-sealed type vacuum pump, and the vacuum refining vessel side, including the exhaust gas cooler or the dust collector, are separated by the vacuum valve 23 .
  • the inside of the vacuum equipment side is controlled in degree of vacuum to a target 98 Torr (13 kPa) based on the signal of the vacuum meter 20 . (This is called “operation prevacuum treatment”.)
  • the vacuum pump 11 controls the degree of vacuum while setting the above degree of vacuum since when the degree of vacuum becomes 51 to 61 Torr (7 to 8 kPa), the water rapidly evaporates and cavitation is caused.
  • a cavitation prevention valve was used to relieve the pressure and adjust the degree of vacuum, but the increase in the frequency of operation of the prevention valve caused the problem of leaks of the valve body.
  • the frequency of operation of the prevention valve is sharply reduced and there is no longer any leakage from the valve body. Accordingly, the degree of vacuum is controlled to a range of 61 Torr (8 kPa) or more.
  • the degree of vacuum of the prevacuum treatment be as high a degree of vacuum as possible to suppress a drop in the degree of vacuum. Accordingly, the range of control of the degree of vacuum of the prevacuum treatment was made 61 to 205 Torr (8 to 27 kPa) in consideration of the controllability of the vacuum control use pressure adjustment valve 22 .
  • the inside of the furnace starts to be evacuated.
  • the vacuum valve 14 is opened, the vacuum exhaust equipment side and the vacuum refining vessel side are made the same degree of vacuum, then the passage as a whole is quickly made a high vacuum by the vacuum exhaust unit.
  • the concentration of oxygen in the exhaust gas becoming the explosion limit of CO was found as a result of experiments by the inventors to be from over 7 vol % to not more than 9 vol %. Accordingly, the concentration of oxygen in the exhaust gas is made not more than 7 vol %.
  • the opening degree of the vacuum control use pressure adjustment valve 22 to at least 80% simultaneously with the signal for the start of blowing oxygen and increasing the return of the exhaust gas after the vacuum pump to the upper limit of the capacity of the adjustment valve, it becomes possible to quickly lower the degree of vacuum. If making the opening degree at least 80% from the general valve characteristics of a pressure adjustment valve, a flow rate of close to the fully open state flows, so here the opening degree was made at least 80%.
  • the time for fixing the vacuum control use pressure adjustment valve 22 to at least 80% after the start of blowing oxygen is determined by the degree of vacuum to be controlled to and the internal volume to be made a vacuum from the vacuum refining vessel to the vacuum exhaust unit.
  • the degree of vacuum to be controlled to and the internal volume to be made a vacuum from the vacuum refining vessel to the vacuum exhaust unit was determined by the degree of vacuum to be controlled to and the internal volume to be made a vacuum from the vacuum refining vessel to the vacuum exhaust unit.
  • 30 seconds to 120 seconds was the optimal range. Accordingly, by fixing the opening degree of the vacuum control use pressure adjustment valve 22 to at least 80% for a predetermined time after the start of blowing oxygen to the inside of the refining vessel, it is possible to quickly control the degree of vacuum to a degree of vacuum of 60 to 403 Torr (8 to 53 kPa).
  • the degree of vacuum is controlled so that when the carbon concentration of the melt is high, the degree of vacuum is lowered, while when the carbon concentration becomes low, the degree of vacuum is relatively raised.
  • control was performed by a degree of vacuum of 300 Torr (40 kPa) for a carbon concentration in the melt, by weight percent, of 0.60 to 0.40%, by a degree of vacuum of 205 Torr (27 kPa) for a carbon concentration in the melt of 0.40 to 0.25%, and by a degree of vacuum of 100 Torr (13 kPa) for a carbon concentration in the melt of 0.25 to 0.20%.
  • levels of degree of vacuum differ depending on the type of the steel being refined, the oxygen blow rate, the type and condition of the refining vessel, and other operating conditions and have to be determined so as to meet with local conditions.
  • successively reducing the oxygen blow rate like the degree of vacuum controlled to, in accordance with the reduction in the carbon concentration in the melt is also effective operationally and metallurgically.
  • the present invention has control of the degree of vacuum based on this as its scope. It is founded on successively controlling the degree of vacuum to the high vacuum side by the fall in the carbon concentration in the melt.
  • 0% means completely closing the pressure control valve 22 .
  • the opening degree becomes less than 20%, the valve becomes close to fully closed and has the characteristic of shutting off the fluid. Therefore, the opening degree was made not more than 20%.
  • the time for fixing the opening degree of the vacuum control use pressure adjustment valve 22 to not more than 20% is determined by degree of vacuum to be controlled to and the inside volume etc. to be made a vacuum from the vacuum refining vessel to the vacuum exhaust unit. It is learned from experience that 30 seconds to 120 seconds is the optimum range.
  • the secondary materials, alloy iron, etc. are sometimes added to the vacuum refining vessel during control of the degree of vacuum.
  • the secondary material, alloy iron, etc. to be added are stocked in advance in an intermediate hopper and are added to the vessel after making the intermediate hopper a degree of vacuum substantially the same as the inside of the furnace. Therefore, there should be almost effect on the flow rate of the exhaust gas at the time of addition.
  • the secondary materials to be added include quicklime, gas components are produced such as the residual CO 2 in the quicklime or a sharp gas producing reaction is caused in the vessel due to the other alloys, secondary materials, etc.
  • the gas produced here causes the flow rate of the exhaust gas to rapidly increase, so the opening degree of the pressure adjustment valve can no longer keep up and a rapid deterioration in the degree of vacuum (rise in pressure) is caused. Therefore, for 40 seconds after addition of the alloy, secondary materials, etc. inside the vessel, the opening degree of the pressure adjustment valve is fixed to 0% to positively suck in the exhaust gas. Due to this, the deterioration in the degree of vacuum due to the rapid increase in the flow rate of exhaust gas can be suppressed as shown in (e) of FIG. 5. However, here, “0%” means completely closing the pressure control valve.
  • the pressure adjustment valve 22 is adjusted to return up to 10% of the flow of the exhaust gas to the upstream side of the water-sealed type vacuum pump 11 so as to improve the degree of vacuum inside the vacuum refining vessel quickly. If the flow rate of the returned exhaust gas exceeds 10%, however, the degree of vacuum will not be quickly improved, so this is made not more than 10%.
  • the time for adjusting the opening degree of the pressure adjustment valve 22 for control of the degree of vacuum after addition of the alloy, secondary materials, etc. in the vessel and returning 10% of the flow rate of the exhaust gas is determined by the degree of vacuum to be controlled to, the capacity of the alloy addition hopper, the degree of vacuum inside the hopper, and the inside volume to be made a vacuum from the vacuum refining vessel to the vacuum exhaust unit. It is learned from experience that 30 seconds to 90 seconds is the optimum range.
  • the secondary materials, alloy iron, etc. added to the vacuum refining vessel normally have a cooling effect on the melt, so the melt temperature falls. Further, since addition is intermittent, the amounts of addition become certain considerable sizes and the melt temperature is temporarily greatly cooled. When the melt temperature falls, the oxygen efficiency for decarburization deteriorates metallurgically and the oxidation loss of the iron, chrome, etc. becomes larger. To suppress this, it is effective to raise the degree of vacuum and raise the oxygen efficiency for decarburization at the timing when the temperature temporarily drops. Therefore, even after the temporary increase in the flow rate of the exhaust gas quiets down after the addition of the secondary materials, alloy iron, etc.
  • the opening degree of the pressure adjustment valve 22 continues to be fixed at 0% for 120 seconds so as to hold the degree of vacuum at a higher vacuum. Due to this, it becomes possible to suppress a drop in the decarburization reaction efficiency due to the drop in the melt temperature caused by the addition of the secondary materials and alloy.
  • 0% means completely closing the pressure control valve. From the general valve characteristics of the pressure adjustment valve 22 , when the opening degree becomes less than 20%, the valve becomes close to fully closed and has the characteristic of shutting off the fluid. Therefore, the opening degree of the pressure adjustment valve 22 for control of the degree of vacuum is made 0 to 20%.
  • the time for making the opening degree of the pressure adjustment valve 22 for control of the degree of vacuum after addition of the alloy, secondary materials, etc. to the vessel less than 20% is determined by the degree of vacuum to be controlled to, the amount of addition of alloy, the carbon concentration in the melt, the concentrations of copper, nickel, and other alloy components in the melt, and the inside volume to be made a vacuum from the vacuum refining vessel to the vacuum exhaust unit. It is learned that 90 seconds to 240 seconds is the optimum range.
  • FIG. 6 and FIG. 7 schematically show one embodiment of a seal unit of the present invention.
  • a vacuum cover 30 When vacuum decarburizing a melt in the vacuum refining vessel 1 , the top of the furnace 1 is covered by a vacuum cover 30 , while a middle cover 31 is arranged for preventing splashing of the metal and slag at the top of the space below the vacuum cover 30 .
  • the center of the middle cover 31 is formed with a large opening for adding the alloy and secondary materials. Normally, the upwardly blown metal directly reaches the alloy and secondary material addition port provided at the vacuum cover 30 .
  • a dummy lance 33 is provided as an integral structure with the valve body at the bottom of the bottom seal valve 34 .
  • the inner walls of the alloy and secondary material addition port 40 are provided with a seal hole 37 for blowing seal gas (nitrogen) to the side walls of the dummy lance 33 .
  • seal gas nitrogen
  • the narrower the clearance between the side walls of the dummy lance 33 and the inner walls of the alloy and secondary material addition port 40 the greater the seal effect, but it is necessary to set the extent of the clearance while considering the lateral shaking at the time of elevation or descent of the bottom seal valve 34 and dummy lance 33 and unavoidable deposition of some metal. For example, it is preferable to set a clearance of 10 to 20 mm.
  • the bottom seal valve 34 and the dummy lance 33 normally are connected to an elevator unit arranged at the top (not shown in FIG. 6 and FIG. 7) and are raised or lowered through pneumatic pressure, oil pressure, or a winch through a sieve. If it were possible to keep the lateral shaking at the time of elevation or descent by the elevator unit smaller, it would be possible to further narrow the clearance between the side walls of the dummy lance 33 and the inside walls of the alloy and secondary material addition port 40 and enhance the seal effect.
  • the elevation stroke has to be made longer. That is, it is necessary to make it longer than the conventional elevation stroke by the amount of the height of the dummy lance 33 .
  • the space above the vacuum refining vessel 1 normally has a conveyor, hopper, or other equipment and apparatuses for conveying, charging, and storing the alloy, secondary materials, etc., a vacuum cover or vacuum duct for evacuating the vacuum refining vessel, and an elevator unit, ancillary units, etc. for the same arranged in it, so forms an extremely crowded space. Therefore, it is difficult to arrange an elevator unit with a long stroke there.
  • a pair of elevator units 36 (for example, air cylinders or hydraulic cylinders) are arranged at the two sides of the alloy and secondary material charging chute, a rod linked with the bottom seal valve is connected with the top of the connection bar of the elevator units, and this is pushed upward by the pair of elevator units 36 so as to raise or lower the valve body (bottom seal valve and dummy lance). Due to this means, it becomes possible to effectively use the crowded space above the vacuum refining vessel 1 and extend the elevation stroke of the bottom seal valve 34 with the dummy lance 33 . In the present invention, the dummy lance 33 will not interfere with the alloy and secondary materials at the time of charging the alloy and secondary materials.
  • the seal hole 37 for blowing seal gas (mainly nitrogen) to the dummy lance 33 is provided at the inside walls of the alloy and secondary material addition port 40 .
  • the flow rate of the seal gas can be suitably controlled by a flow adjustment valve (not shown) in accordance with the refining conditions.
  • a flow adjustment valve (not shown) in accordance with the refining conditions.
  • the flow rate of the seal gas is made larger.
  • the flow rate of the seal gas is reduced.
  • the low flow rate region of the seal gas at the end phase of the decarburization also contributes to improvement of the degree of vacuum in the furnace, so this advantageously promotes the metallurgical reaction and simultaneously is effective for reduction of the concentration of nitrogen in the melt.
  • the method of blowing seal gas includes, in addition to the above method, the method of introducing the gas from the outside through a dummy lance and rod of the bottom seal valve and blowing it out from a plurality of holes provided around the dummy lance to the inside walls of the alloy addition port 40 .
  • the middle cover 31 is arranged to prevent splashing of the metal and slag, but the middle cover 31 is cooled by the inert gas (mainly nitrogen).
  • the present invention it is possible to utilize the above inert gas as the seal gas to be blown from the seal hole 37 toward the dummy lance 33 .
  • the gas cooling the metal core of the middle cover 31 is sent in the opposite direction as the supply route and discharged into the atmosphere, but the gas is high in temperature and the noise at the time of discharge of gas becomes a problem, so this has to be handled by complicated equipment and in the end the capital costs are slashed.
  • the gas (nitrogen) used for cooling the metal core of the middle cover 31 becomes high in gas temperature, so even if using the same amount as seal gas, the flow rate of the gas when discharged from the nozzle of the seal hole and passing through the clearance between the inside walls of the alloy and secondary material addition port 40 and the dummy lance 33 will become larger. As a result, entry of the metal and slag can be prevented more and the seal effect becomes larger.
  • the seal gas is blown directly into the alloy addition port 40 , but the method of laying a pipe to the inside of the high temperature exhaust gas duct for heat exchange, raising the seal gas temperature, and blowing the gas to the alloy addition port 40 so as to obtain the effect of a higher gas temperature and higher flow rate is also included in the present invention.
  • the seal gas mainly nitrogen is used, but the gas need only be inert. In addition to nitrogen, it is possible to use argon, CO 2 , steam etc. alone. Further, it is possible to use a mixture of these gases.
  • the dummy lance is exposed to a high temperature, so it is preferable to make part of it out of refractories. Further, it may be cooled by water cooling, air cooling, etc. These methods are also included in the present invention.
  • the exhaust gas 15 produced in the vacuum refining furnace 1 passes through the water cooling duct 13 , is sent to the gas cooler 16 connected to it, and is cooled there. After this, it passes from the gas cooler 16 through the duct 14 , is sent to a dry type dust collector 9 , then is further sent through the duct 14 to the vacuum exhaust unit 10 , then is discharged to the atmosphere.
  • the exhaust gas suction conduit 24 for the humidity meter and analysis meter branching the exhaust gas suction conduit 24 for the humidity meter and analysis meter from a stage after the dust collector 9 , part of the exhaust gas is branched off and introduced to the humidity meter 25 . As a result, the humidity of the exhaust gas is measured at the humidity meter 25 , but the exhaust gas analysis meter is also arranged at that position.
  • the exhaust gas analysis meter is provided after the dust collector 9 , but may also be provided after the gas cooler 16 . Further, the analysis meter provided jointly here may be located at the same location in some cases, but may also be located separately from the humidity meter after the vacuum exhaust unit 10 or after the dust collector 9 in other cases.
  • the analysis meter is provided jointly so as to simultaneously measure at least one of the concentration or partial pressure of the CO, CO 2 , O 2 , H 2 , or other gas when measuring the humidity of the exhaust gas.
  • These analysis values are used to obtain a grasp of the state of progress of the reaction in the vacuum refining vessel or metallurgical furnace and used as operation guidance for blowing gas into the metallurgical furnace, charging the secondary materials and cooling material, etc. or used as information for judgment of the end of the metallurgical operation.
  • the measured value of the humidity meter may be utilized not only as information for judgment of water leakage, but also as information for judgment of the state of the reaction inside the vessel or inside the furnace.
  • the high temperature exhaust gas produced is cooled by providing a gas cooler 16 in the middle of the ducts or water-cooling the middle part of the ducts.
  • the relative humidity of the exhaust gas is continually measured and monitored after the dust collector. For example, assume that during vacuum refining, the water pipes of the gas cooler 16 crack and cooling water sprays out into the exhaust gas. In this case, the water leakage is evaporated by the high temperature exhaust gas and the steam partial pressure of the exhaust gas rises, so the humidity meter 25 provided after later can detect the rise of the relative humidity.
  • the case where there is no water leakage inside the exhaust gas passage and a high humidity continues for a certain time with respect to the relative humidity of the exhaust gas in the normal state is judged as meaning the occurrence of water leakage and action is taken for the equipment and operation.
  • the invention is not limited to detection of just humidity. It is also possible to detect the steam partial pressure.
  • the necessary action for the repair work of the water leakage location is taken immediately after detection of water leakage.
  • Quick repair work for a water leakage location is important. Early detection of water leakage will enable the repair locations to be kept minor in most cases and enable the repair to be finished easily in a short time. Further, in some cases, it is possible to only issue a warning and suitably stop the operation of the equipment.
  • the absolute flow rate of the suction exhaust gas will become considerably small at the time of a high vacuum compared with the time of low vacuum. Accordingly, when using the same suction pump, the flow rate of gas supplied to the humidity meter or gas analysis and measurement will fluctuate greatly depending on the degree of vacuum. On the other hand, to maintain the measurement precision of the humidity measuring unit or gas analyzer, the fluctuation in the flow rate of gas supplied to these meters must be avoided. As a means for this, two suction pumps are provided.
  • the steam partial pressure of the exhaust gas during vacuum refining rises due to reasons other than water leakage of the equipment in some cases.
  • the vacuum refining vessel is charged with the alloy iron, cooling material, quicklime, and other secondary materials during operation. These secondary materials contain some moisture, so after charging, the steam partial pressure in the exhaust gas temporarily rises.
  • the quicklime and other secondary materials easily absorb moisture and have large moisture contents, so the amount of generation of steam after charging remarkably rises. Accordingly, if hastily judging a rise in relative humidity to mean water leakage, the result will be erroneous detection. Therefore, the inventors investigated in detail the behavior of the relative humidity and as a result found the rise in humidity due to water leakage becomes continuous.
  • the gas fuel, solid fuel, etc. containing hydrocarbons is burned for the purpose of providing the heat source at the time of refining in the refining vessel.
  • the gas fuel, solid fuel, etc. containing hydrocarbons is burned for the purpose of providing the heat source at the time of refining in the refining vessel.
  • LNG, LPG, kerosine, or another hydrocarbon-based fuel in the vessel a large amount of steam enters the exhaust gas.
  • the timing of supply and the amount of supply become clear and the amount of entry of steam into the exhaust gas can be estimated with relatively good precision. Therefore, it is sufficiently possible to separate these effects from the results of measurement of the partial pressure of steam in the exhaust gas.
  • the exhaust gas produced in the vacuum refining vessel 1 is cooled by the exhaust gas cooler 16 , cleaned by the dust collector 9 , and introduced into the multiple-stage ejector type vacuum exhaust unit.
  • the multiple-stage vacuum exhaust unit performs first suction by the No. 1 ejector, condenses the steam at the later No. 1 condenser and repeats the suction and steam condensation at the No. 2 ejector and No. 2 condenser. Finally, the gas is sucked in by the water-sealed type vacuum pump 11 , then passes through the separator tank and is discharged into the atmosphere.
  • the condenser water from the nos. 1 and 2 condensers, the sealing water from the water-sealed type vacuum pump, and the cooling water from the separator tank pass through the pipe 26 and are collected at the water storage tank constituted by the hot well 27 .
  • the cooling water of the hot well 27 is managed in level in the tank by a water level meter.
  • the return pump 28 When rising a certain water level or more, the return pump 28 is started up and the water is returned from the hot well 27 to the cooling tower 29 through the return pipe.
  • the cooling water cooled at the cooling tower passes through the feed pipe from the feed pump 30 and is sent to the condensers, water-sealed pump, etc.
  • the feed pump belongs to a different power source system than the return pump of the hot well.
  • the hot well 27 is a concrete structure for storing condenser water and sealing water of the water-sealed pump etc.
  • the top is clad by iron plate 52 at several locations other than the concrete 50 .
  • the condenser water and the cooling water flowing in from the water-sealed pump sealing water pipe 26 are temporarily stored in water 53 stored in the hot well.
  • a supply pump is started up in accordance with the level of the stored water at the left side of the figure to send the water through the feed pipe 54 to the cooling tower 29 .
  • the practice is to provide an exhaust duct 55 and ventilate the inside of the hot well by an exhaust blower 56 from the exhaust outlet port.
  • the inside of the hot well will become a negative pressure, the above-mentioned seal parts will break, the clearance will expand, and air will be sucked in. Normally, this is not a problem, but when the exhaust blower stops due to a breakdown or blackout, CO will leak out from the seal parts with the large clearance of the hot well resulting in a dangerous situation.
  • the inventors discovered that by evacuating gas from the exhaust duct connected to the top of the hot well using a suction means and guiding the ventilation gas from the suction duct of the ventilation gas connected to the top of the hot well to the inside of the return water storage tank, it is possible to reduce the negative pressure inside the hot well and possible to almost completely eliminate damage to seal parts between the concrete and iron plate part.
  • a ventilating flow occurs in the tank as shown by the flow 58 of the ventilation gas.
  • the inside of the hot well becomes an air atmosphere while the Co-containing gas is sucked out. Further, the negative pressure inside the hot well becomes smaller than the air flowing in from the duct. It becomes possible to almost completely eliminate damage to the seals between the rear concrete and the iron plate part.
  • the inventors conducted a detailed survey on the inner pressure inside a hot well in relation to vacuum refining operations and as a result found that, as explained above, the inside of a hot well not only becomes a negative pressure, but also becomes a positive pressure or a negative pressure.
  • a hot well not only becomes a negative pressure, but also becomes a positive pressure or a negative pressure.
  • the degree of vacuum of the prevacuum treatment side rapidly deteriorates (for example, falls from 1.33 ⁇ 10 4 Pa to 6.67 ⁇ 10 4 Pa), so the condenser water rapidly flows into the hot well and, while for a short time, the gas inside the hot well is compressed resulting in a large positive pressure.
  • a survey by the applicant revealed that 1.96 ⁇ 10 3 Pa or more was reached in many heats. Accordingly, even if sucking out gas by an exhaust blower, at this timing, the inside of the hot well cannot be held at a negative pressure. However, with the method of the present invention, damage to the seal parts is small, so the amount of leakage of the gas can be kept small. Further, the inside of the hot well is positively replaced with air, so even if the inside of the hot well becomes a positive pressure and a small amount of gas leaks out, the CO gas contained can be kept to a level not causing any health problems.
  • FIG. 9 illustrates the case of providing two water-sealed covers 51 (side view).
  • the water-sealed cover 51 provided at the top of the hot well is comprised of a double tube shaped cylindrical vessel having an outer tube 59 and an inner tube 60 on an iron plate 52 of the top of the hot well and a partition plate 61 able to be inserted in between the inner and outer tubes.
  • a weight 62 is used for increasing the weight of the partition cover.
  • the weight of the partition cover alone is usually not enough to withstand the gas pressure in the hot well, the weight is normally preferably usually used.
  • the inner tube 59 is lower than the outer tube 60 .
  • the water-sealed cover sealing water is supplied from the outside of the outer tube 60 . Water is continuously supplied so that the sealing water enters the inner tube side from the outer tube side of the partition cover and overflows from the top end of the inner tube, travels along the inside walls of the inner tube, and flows into the hot well.
  • the sealing water height is designed so that at the time of a normal vacuum refining operation, due to the sealing water, the gas inside the hot well will not leak to the outside and the sealing water will not be cut off even with pressure fluctuations of positive pressure and negative pressure of the gas in the hot well. If however the water inside the hot well overflows and is filled to the inside of the water-sealed cover due to some reason or another as explained above, the rise in the water level will cause the partition cover 61 to be lifted up and water to leak to the outside from the clearance between the inner and outer tubes. Due to this, it is possible to greatly ease the force acting on the connecting parts of the iron plate and concrete at the top of the hot well and damage to the seal parts can be kept extremely minor.
  • the size and number of the water-sealed covers placed in the hot well may be suitably set in accordance with the total amount of water of the condenser water supplied, the sealing water for the water sealed pump, etc. For example, if the total amount of water is 600 t/h or so, provision of two water-sealed covers of cylindrical shapes of diameters of 500 mm for allowing the overflowing water to escape to the outside may be mentioned as a common sense embodiment.
  • W 1 +W 2 is the total weight of the movable partition cover 61 and the weight 62
  • P is the maximum gas pressure in the hot well
  • S is the horizontal projected area of the partition cover 61 .
  • the height H of the outer tube 59 at the outside of the partition cover side walls has to be over (200+L) mm considering the sealing water passage height Lmm connecting the inside and outside of the partition cover.
  • the water-sealing height of the water-sealed cover if generalized, must satisfy the following formula (2):
  • the present invention was applied when producing SUS304 stainless steel (8 wt % nickel and 18 wt % chromium) in a 60 ton melt AOD furnace as shown in FIG. 1.
  • bottom blowing is performed in the state shown in FIG. 1( b ) and, in accordance with need, top blowing is jointly used.
  • vacuum refining bottom blowing is performed after reducing the pressure inside the refining vessel in the state shown in FIG. 1( a ).
  • the concentration of carbon in the melt at the time of start of production is about 1.6%.
  • Decarburization refining is performed until a carbon concentration of 0.04%, then the pressure inside the vessel is returned to atmospheric pressure while adding Fe—Si alloy iron as a reducing agent for reducing the chromium oxidized during the decarburization and only argon gas is blown in for reduction.
  • the steel was taken out to a ladle.
  • the pattern shown in Table 1 was used for refining.
  • the first step was made atmospheric pressure refining with top and bottom blowing and use of oxygen gas alone as the bottom blown gas.
  • a concentration of carbon of 0.5% to 0.15% was made the second step.
  • the pressure inside the vessel in the second step was made a two-stage pressure of 350 Torr (46 kPa) and 250 Torr ( 33 kPa), the blow rates of the bottom blown gas were made 0.9 and 0.5 Nm 3 /min, and the blown gas was made oxygen gas alone.
  • the third step was made decarburization refining until a concentration of carbon of 0.04% at a pressure inside the vessel of a two-stage pressure of 100 Torr (13 kPa) and 40 Torr (5 kPa) and a blow rate of bottom blown gas held at 0.5 Nm 3 /min.
  • the oxygen gas is blown in alone until the concentration of carbon reaches 0.5%, so while the oxygen efficiency for decarburization falls somewhat and the oxidation of chromium increases, it was possible to slash the amount of use of the expensive argon gas. Note that in the region of the concentration of carbon of 0.7 to 0.5% of the first step, if making the ratio of the bottom blown gas O 2 /argon not 1/0, but 4/1, while the amount of use of the expensive argon gas increases, the oxygen efficiency for decarburization at the carbon region can be improved.
  • the blow rate of the bottom blown gas was raised to 0.9 to 0.5 Nm 3 /min so as to make the pressure inside the vessel rise to 350 (46 kPa) to 250 Torr (33 kPa) while maintaining the oxygen efficiency for decarburization. As a result, it was possible to realize a reduction in the dust generation and a shorter refining time.
  • the pressure inside the vessel was made 100 Torr (13 kPa) and the blow rate of bottom blown gas was maintained at 0.5 Nm 3 /min under conditions of 40 Torr (5 kPa), whereby it was possible to maintain the high oxygen efficiency for decarburization and contribute to a shorter refining time.
  • the pattern shown in Table 2 was employed for refining. Atmospheric pressure refining was performed for a concentration of carbon of 1.6 to 0.4% and vacuum refining was performed for a concentration of carbon of 0.4% and less.
  • the refining conditions at the atmospheric pressure refining were similar to those of the first step of Example 1.
  • the blow rate of the bottom blown gas in the vacuum refining was made 0.3 Nm 3 /min like the conventional level. Since the blow rate of the bottom blown gas was low, from the viewpoint of preventing a drop in the oxygen efficiency for decarburization and preventing an increase in the dust generation, the pressure inside the vessel was made a maximum of 150 Torr (20 kPa).
  • Atmospheric Reduction Class pressure Vacuum phase Pressure 760 150 150 100 40 760 (Torr) (100 kPa) (20 kPa) (20 kPa) (13 kPa) (5 kPa) (100 kPa) Blow rate of 1.4 1.2 0.3 0.3 0.3 0.3 0.5 bottom blown gas (Nm 3 /min/t) O 2 /argon 1/0 1/0 1/0 1/0 1/5 0/1 0/1 ratio of bottom blown gas Blow rate of 1.4 1.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 top blown gas (Nm 3 /min/t) Carbon 1.6 0.7 0.4 0.25 0.15 0.08 0.04 concentration (%)
  • the present invention enables forcible agitation of melt in the medium carbon region, in particular in the region of a carbon concentration of 0.2 to 0.5%, in vacuum refining of chromium-contained molten steel so as to enable vacuum refining of a high oxygen efficiency for decarburization at a pressure of 250 to 400 Torr (33 to 53 kPa).
  • a pressure of 250 to 400 Torr 33 to 53 kPa.
  • the present invention further enables selection of a higher pressure as the atmosphere in the refining vessel even in the carbon region higher than the carbon region where the vacuum operation of 250 to 400 Torr (33 to 53 kPa) is performed so as to enable use of a vacuum operation rather than an atmospheric pressure operation and thereby enable the amount of use of the expensive inert gas to be slashed and the productivity to be improved.
  • the present invention further enables adoption of two-stage vacuum treatment comprising performing decarburization refining of ultra-low carbon chromium-contained molten steel in an AOD vacuum refining furnace where the pressure inside the vessel is made to rise once in a state where the decarburization has progressed to a certain extent in the refining under a vacuum, then again lowering the pressure and resuming the refining under a vacuum and a great increase in the blow rate of the bottom blown gas compared with the past so as to realize a great improvement in the decarburization rate in the low carbon region and a great reduction in the overall decarburization refining time.
  • the present invention establishes a vacuum exhaust unit and control method enabling control of the degree of vacuum inside a vacuum refining furnace or its ducts for oxygen decarburization refining of a melt under a vacuum.
  • the effects in equipment and operation obtained due to this are as follows:
  • the present invention enables sufficient sealing at an alloy and secondary material addition port in the refining process without trouble caused by splashing of the metal and slag, so it is possible to greatly slash the prime units of the materials and secondary materials, possible to shorten the operating time, and possible to greatly reduce the operating costs.
  • the present invention can measure and monitor the humidity of exhaust gas so as to detect a small amount of water leakage inside the exhaust gas passage and thereby detect water leakage early and simultaneously strikingly improve the reliability of detection of water leakage.
  • the present invention enables the provision of a method and apparatus simply dealing with the issues in hot wells, that is, the leakage of CO-containing gas from the hot well and suppression of damage to equipment at the time of occurrence of overflow of cooling water in the hot well.

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)
US10/490,459 2001-09-20 2002-09-20 Method for refining molten iron containing chromium Abandoned US20040245682A1 (en)

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JP2001-286694 2001-09-20
JP2001-286695 2001-09-20
JP2001286695A JP2003096515A (ja) 2001-09-20 2001-09-20 極低炭含クロム溶鋼の精錬方法
JP2001286694A JP4895446B2 (ja) 2001-09-20 2001-09-20 含クロム溶鋼の精錬方法
JP2001339046A JP4262428B2 (ja) 2001-11-05 2001-11-05 冶金炉における水漏れ検知方法
JP2001-339046 2001-11-05
JP2001-391274 2001-12-25
JP2001391274A JP3922923B2 (ja) 2001-12-25 2001-12-25 真空排気設備における真空度制御方法及び装置
JP2002235726A JP3973512B2 (ja) 2002-08-13 2002-08-13 真空排気装置の戻水貯水槽内ガスの換気方法及び戻水貯水槽の水封蓋
JP2002-235726 2002-08-13
PCT/JP2002/009701 WO2003027335A1 (fr) 2001-09-20 2002-09-20 Procede d'affinage de fer en fusion contenant du chrome

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CN113106187A (zh) * 2021-03-22 2021-07-13 张家港宏昌钢板有限公司 一种改善if钢水口堵塞的精炼双联生产方法
CN113430336A (zh) * 2021-06-18 2021-09-24 首钢集团有限公司 一种利用co2进行rh高效精炼的操作方法

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CN113106187A (zh) * 2021-03-22 2021-07-13 张家港宏昌钢板有限公司 一种改善if钢水口堵塞的精炼双联生产方法
CN113430336A (zh) * 2021-06-18 2021-09-24 首钢集团有限公司 一种利用co2进行rh高效精炼的操作方法
CN113430336B (zh) * 2021-06-18 2022-11-18 首钢集团有限公司 一种利用co2进行rh高效精炼的操作方法

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BRPI0216050B1 (pt) 2015-12-29
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US7497987B2 (en) 2009-03-03
KR100662895B1 (ko) 2007-01-02
BR0212732A (pt) 2004-10-05
WO2003027335A1 (fr) 2003-04-03
KR20040029487A (ko) 2004-04-06
US20070152386A1 (en) 2007-07-05
TW564262B (en) 2003-12-01
BR0212732B1 (pt) 2013-07-02
EP1431404A1 (de) 2004-06-23
CN1556865A (zh) 2004-12-22
EP1431404A4 (de) 2008-06-25

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