WO2013172042A1 - Method for loading raw material into blast furnace - Google Patents
Method for loading raw material into blast furnace Download PDFInfo
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- WO2013172042A1 WO2013172042A1 PCT/JP2013/003165 JP2013003165W WO2013172042A1 WO 2013172042 A1 WO2013172042 A1 WO 2013172042A1 JP 2013003165 W JP2013003165 W JP 2013003165W WO 2013172042 A1 WO2013172042 A1 WO 2013172042A1
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- charging
- coke
- raw material
- blast furnace
- turn
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/006—Automatically controlling the process
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B7/00—Blast furnaces
- C21B7/002—Evacuating and treating of exhaust gases
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/008—Composition or distribution of the charge
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B1/00—Shaft or like vertical or substantially vertical furnaces
- F27B1/10—Details, accessories, or equipment peculiar to furnaces of these types
- F27B1/20—Arrangements of devices for charging
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B7/00—Blast furnaces
- C21B7/18—Bell-and-hopper arrangements
- C21B7/20—Bell-and-hopper arrangements with appliances for distributing the burden
Definitions
- the present invention relates to a raw material charging method for a blast furnace in which the raw material is charged into the furnace with a turning chute.
- a blast furnace generally charges raw materials such as sintered ore, pellets, and massive ore and coke in layers from the top of the furnace, and flows combustion gas from the tuyere to obtain pig iron.
- the coke and ore raw material which are the charged raw materials for the blast furnace, descend from the top of the furnace to the lower part of the furnace, and ore reduction and raw material temperature rise occur.
- the ore raw material layer is gradually deformed while filling the gaps between the ore raw materials due to the temperature rise and the load from above, and the lower part of the shaft part of the blast furnace has a very high resistance to gas and almost no gas flows. Form a layer.
- raw material charging into a blast furnace is performed by alternately charging ore raw materials and coke, and in the furnace, ore raw material layers and coke layers are alternately layered. Further, in the lower part of the blast furnace, there are an ore raw material layer having a large ventilation resistance in which an ore called softening zone is softened and fused, and a coke slit having a relatively small ventilation resistance derived from coke.
- the air permeability of this cohesive zone has a great influence on the air permeability of the entire blast furnace, and the productivity in the blast furnace is limited.
- the coke slit becomes extremely thin because the amount of coke used is reduced.
- Patent Document 2 ore and coke are separately stored in a bunker at the top of the furnace, and coke and ore are mixed and charged at the same time, so that a normal coke charging batch and a coke central charging batch are used. And three batches for mixing and charging are performed simultaneously.
- Patent Document 3 in order to prevent the instability of the cohesive zone shape in the blast furnace operation and the decrease in the gas utilization rate near the center, and to improve the safe operation and thermal efficiency, the raw material charging method in the blast furnace is In addition, after all ore and all coke are thoroughly mixed, they are charged into the furnace.
- JP-A-3-211210 JP 2004-107794 A Japanese Patent Publication No.59-10402
- the average particle size of typical coke described in Patent Document 3 is about 40 to 50 mm, and the average particle size of ore is about 15 mm. If only mixed, the porosity is greatly reduced, the air permeability is deteriorated in the furnace, and there is a possibility that troubles such as gas blow-out and poor lowering of raw materials may occur. Moreover, even if the ore and coke are cut out from two bunkers simultaneously and mixed and charged, the coke with a large particle size rolls farther due to the inclination of the charging surface, so that the coke is easily separated. .
- a method of forming a coke-only layer in the furnace axis can be considered. According to this method, the passage of gas through the coke layer is secured in the core portion of the furnace, so that air permeability can be improved. Moreover, when ore and coke are cut out and mixed and charged at the same time, it is known that reverse tilt charging in which charging raw materials are stacked from the center is effective in avoiding the above trouble.
- the present invention was developed in view of the above-mentioned present situation, and even if the raw material charging interval is narrow, the mixing property in the mixed layer is ensured to stabilize the blast furnace operation and improve the thermal efficiency.
- the amount of raw material charged per turn or the charging interval can be adjusted to By preventing the charging material from crossing the mountain this time and flowing into the center side, it is possible to secure the mixing in the mixed layer and to stabilize the blast furnace operation and improve the reaction efficiency. It aims at providing the raw material charging method.
- the gist configuration of the present invention is as follows. 1.
- the charge of raw material charging to the blast furnace is divided into 2 or more batches of coke charging and 2 batches of ore charging, and charging using a rotating chute, the coke charging and the ore charging
- V n Raw material volume per turn in the nth turn (m 3 ) [Amount of charge per turn in the nth turn (t) / (Apparent density of coke and ore mixed layer (t / m 3 ))]
- R n fall radius of the charged raw material in the n-th turn (m)
- L av2 (n) V n / [(R n 2 ⁇ R n-1 2 ) ⁇ ] 2
- L av2 (n + 1) V n + 1 / [(R n + 1 2 ⁇ R n 2 ) ⁇ ] 3
- V n the raw material volume per turn in the n-th turn (m 3 )
- R n-1 Falling radius of the charged raw material in the (n-1) th turn (m)
- R n fall radius of the charged raw material in the n-th turn (m)
- V n + 1 The charging raw material volume per turn in the (n + 1) th turn (m 3 )
- R n + 1 Fall radius (m) of the charged raw material in the (n + 1) th turn L av2 (n + 1) ⁇ L av2 (n) 4
- the charged raw material when charging the ore raw material and coke into the blast furnace, the charged raw material is poured into a predetermined position and the mixed coke is not separated, so that the air permeability in the lower part of the furnace is greatly improved.
- the ore reduction speed is greatly improved, even when the raw material charging interval is narrow, and when reverse tilt charging is applied when mixing and mixing coke and ore simultaneously, stable blast furnace operation is performed. be able to.
- FIG. 1 It is a schematic diagram which shows the raw material charging procedure to a blast furnace.
- A is a schematic diagram which shows the conventional raw material charging state according to the present invention and (b) according to the present invention.
- (A) is the conventional, and (b) is a schematic diagram which shows each other raw material charging state according to this invention.
- It is a schematic diagram which contrasts and shows the raw material charging state to the blast furnace by this invention, and the raw material charging state in a normal blast furnace.
- the raw material charging destination of the swirl chute 16 is the inner peripheral part of the furnace wall of the blast furnace, and only the coke is loaded.
- a central coke layer is formed at the center of the blast furnace.
- a peripheral coke layer may be formed on the inner peripheral portion of the furnace wall. That is, in a state where the raw material charging destination of the turning chute 16 faces the furnace wall portion of the blast furnace, the flow rate adjusting gates 13 of the furnace top bunkers 12b and 12c are closed, and the flow rate adjusting gate 13 of only the furnace top bunker 12a is opened.
- a central coke layer is formed at the center of the blast furnace.
- the average layer thickness Lav1 for each turning of the turning chute obtained by the following equation 1 is made smaller than the thickness h of the central coke charged in the shaft center portion of the blast furnace. is important.
- L av1 V n / [(R n 2 ⁇ R n-1 2 ) ⁇ ] 1
- V n charging amount per turn in the n-th turn (t) / (apparent density of coke and ore mixed layer (t / m 3 ))
- R n fall radius of the charged raw material in the n-th turn (m)
- the Lav1 obtained by Equation 1 is made smaller than the thickness h of the central coke charged in the axial center portion of the blast furnace, so Uniformity is eliminated, and as a result, even if the amount of coke is small or a large amount of pulverized coal is injected, the air permeability in the blast furnace can be secured stably. .
- L av1 is preferably in the range of about 0.7 to 0.95 times h. This is because the charged raw material climbs over the pile of raw material that has been sown immediately before and flows to the center side, and the mixed coke is separated to prevent deterioration of the mixing rate controllability and reduction of the coke mixing rate.
- L av1 ⁇ h As specific values, L av1 is about 0.90 to 1.35 (m), and h is 1.20. It is desirable that the range be about ⁇ 1.50 (m).
- the formation of the mixed layer 12e is such that the average layer thickness Lav1 for each turn of the turning chute obtained by the above equation 1 is smaller than the thickness of the central coke: h. Is formed.
- L av2 (1) h can be obtained.
- L av2 (n) V n / [(R n 2 ⁇ R n-1 2 ) ⁇ ] 2
- L av2 (n + 1) V n + 1 / [(R n + 1 2 ⁇ R n 2 ) ⁇ ] 3
- V n the raw material volume per turn in the n-th turn (m 3 )
- R n-1 Falling radius of the charged raw material in the (n-1) th turn (m)
- R n fall radius of the charged raw material in the n-th turn (m)
- V n + 1 The charging raw material volume per turn in the (n + 1) th turn (m 3 )
- R n + 1 Fall radius (m) of the charged raw material in the (n + 1) th turn L av2 (n + 1) ⁇ L av2 (n) 4
- the average layer thickness L av2 (n) of the nth turn obtained by the above equation 2 is changed to the average layer thickness L av2 (n + 1) of the (n + 1) th turn obtained by the above equation 3. ),
- the non-uniformity of the mixed layer is eliminated.
- Air permeability can be secured stably.
- the ratio of L av2 (n) to L av2 (n + 1) (L av2 (n + 1) / L av2 (n)) is preferably in the range of about 0.5 to 0.9. If the above ratio is 0.9 or more, the raw material charged in the (n + 1) th turn is more likely to flow over the peak of the raw material charged in the nth time and flow into the center side. This is because it is difficult to control the raw material deposition shape by increasing the charging interval or reducing the charging raw material. In the present invention, it is important to satisfy the relationship of the above formula 4. As specific values, V n is about 2 to 7 (m 3 ) and R 1 is about 1 to 2 (m). , ⁇ R is preferably in the range of about 0.2 to 0.5 (m).
- the layers composed of the central coke layer and the mixed layer 12e are sequentially formed in the blast furnace 10 from the lower part to the upper part.
- a coke layer and a layer composed of the co-mixed mixed layer 12e are sequentially laminated, so that a coke layer having a low ventilation resistance is formed from the lower portion of the blast furnace to the axial center portion and the furnace wall portion in the blast furnace 10.
- the mixed layer 12e in which the coke and the ore raw material are completely mixed therebetween but also the porosity due to the coke mixing. It is possible to prevent the blast furnace upper air permeability deterioration due to the decrease.
- the mixed layer 12e in which the coke and the ore raw material are completely mixed can be formed between the coke layers, the effect of improving the air permeability in the lower portion of the blast furnace can be obtained.
- the ore raw material in the lower part of the blast furnace 10 is melted, and the coke and the ore raw material charged in the blast furnace 10 descend from the top of the furnace to the lower part of the furnace, and the reduction of the ore raw material and the ore raw material A temperature rise occurs. For this reason, a fusion zone in which the ore material is softened is formed on the upper side of the molten layer, and the ore material is reduced on the upper side of the fusion zone.
- the ore raw material and the coke are completely mixed in the mixed layer 12 e, and the coke enters between the ore raw materials.
- the high-temperature gas passes directly between the ore raw materials, so there is no heat transfer delay and the heat transfer characteristics can be improved.
- the contact area between the ore raw material and the high-temperature gas is expanded, and carburization can be promoted. Further, in the cohesive zone, air permeability and heat transfer can be improved. Furthermore, since the ore raw material and coke are arranged close to each other in the upper part of the blast furnace 10, the coupling is a mutual activation phenomenon between the reduction reaction of the ore raw material and the gasification reaction (carbon solution loss reaction). Good reduction is performed without causing a reduction delay due to the reaction.
- a coke slit is formed on the upper side of the cohesive zone, and heat is conducted to the ore mainly through the coke slit, so that a heat transfer delay occurs and heat transfer becomes insufficient. Furthermore, since the coke layer with good air permeability and the ore layer with poor air permeability are laminated at the upper part of the blast furnace 10, not only the temperature rising rate is lowered, but only the reduction reaction is performed, and the above-described coupling is performed. Since the reaction cannot be expected, there arises a problem that a reduction delay occurs.
- the charging layer formed by the coke layer and the mixed layer 12e in which the coke and the ore raw material are completely mixed is laminated, the coke slit is formed in the mixed layer. Therefore, the gas flow is made uniform, and good heat transfer is ensured, and stable ventilation can be improved, so that the above-mentioned conventional problems can be advantageously solved.
- the amount of coke required for producing hot metal 1 ton (kg), that is, the coke ratio was about 320 to 350 kg / t.
- the coke ratio is 270. It can be reduced to about ⁇ 320 kg / t.
- Example 1 In order to verify the effect of the present invention, the change in the ventilation resistance was investigated by simulating the raw material reduction and temperature raising processes in the blast furnace using the experimental apparatus shown in FIG.
- a furnace core tube 32 is disposed on the inner peripheral surface of a cylindrical furnace body 31, and a cylindrical heating heater 33 is disposed outside the furnace core tube 32.
- a graphite crucible 35 is disposed at the upper end of a cylindrical body 34 made of a refractory inside the furnace core tube 32, and a charging raw material 36 is charged into the crucible 35.
- a load is applied to the charged raw material 36 from above by a load loading device 38 connected via a punch bar 37 so as to be in the same level as the fused layer at the bottom of the blast furnace.
- a drop sampling device 39 is provided below the cylindrical body 34.
- the gas adjusted by the gas mixing device 40 is sent to the crucible 35 through the lower cylindrical body 34. Thereafter, the gas that has passed through the charging material 36 in the crucible 35 is analyzed by the gas analyzer 41.
- the heating heater 33 is provided with a thermocouple 42 for controlling the heating temperature, and the crucible 35 is controlled by controlling the heater 33 with a control device (not shown) while measuring the temperature with the thermocouple 42. Is heated to 1200-1500 ° C.
- the charging raw material 36 charged in the crucible 35 the following materials were used.
- the coke ratio and the pulverized coal ratio are the amount of coke and the amount of pulverized coal (kg) used when producing hot metal 1t.
- the reducing material ratio is the sum of the coke ratio and pulverized coal ratio.
- the gas utilization rate is a ratio of the concentration of CO 2 and CO at the top of the furnace, and is calculated by the following equation.
- Gas utilization rate CO 2 / (CO 2 + CO) ⁇ 100
- CO 2 is the furnace top CO 2 concentration [%]
- CO furnace top CO concentration [%]
- ⁇ P / V is an index obtained by indexing the ventilation resistance in the blast furnace, and is calculated by the following equation.
- ⁇ P / V (BP-TP) / BGV
- BP the blowing pressure [Pa].
- TP the furnace top pressure [Pa]
- BGV Bosch gas amount [m 3 (standard state) / min]
- the coke ratio of Comparative Example 1 was 342 kg / t, but L av1 was in the range of about 0.7 to 0.95 times h, and L av1 was 0.90 to 1.35.
- the coke ratio of Invention Example 1 is 312 kg / t, and Invention Example 2 can be reduced to about 300 kg / t. It was proved that the ventilation resistance can be reduced even at a low reducing material ratio with a low coke ratio.
- the charging amount per turning: V n and the radius increase amount per turning of the falling radius of the charging raw material: ⁇ R are fixed for each example, but the relationship of L av1 ⁇ h is satisfied. if, even by changing the V n and ⁇ R for each pivot, it is possible to obtain the effect of the present invention without any problem.
- the present invention is not limited thereto.
- a dedicated coke chute that feeds coke directly into the blast furnace shaft center is placed at a position where it does not interfere with the swivel chute, and the coke is charged directly into the blast furnace shaft core to form a central coke layer. You may make it do.
- L av1 0.7 to 0.95 times approximately in the range of h
- L av1 is 0.90 ⁇ 1.35 (m) about a range h is about 1.20 ⁇ 1.50 (m)
- Example 2 Furthermore, internal volume: In 4000 mm 3 grade blast furnace actual, conducted material charging tests were compared operating conditions.
- this blast furnace as shown in FIG. 1, it has three independent bunkers in the upper part of the blast furnace, and each is charged with coke or ore raw materials.
- 2 batches of ore raw materials are charged.
- mixed charging 120 kg / t
- the 2nd batch In the first half of the coke cutting, the coke was charged into the center of the furnace to form a central coke layer.
- the ore raw material was cut out simultaneously from the other bunker, and the raw material was charged by reverse tilt charging to form a coke mixed layer.
- Table 2 The test results according to the above procedure are shown in Table 2.
- the coke ratio and pulverized coal ratio are the amount of coke and the amount of pulverized coal (kg) used when producing hot metal 1t.
- the reducing material ratio is the sum of the coke ratio and pulverized coal ratio.
- the gas utilization rate is a ratio of the concentration of CO 2 and CO at the top of the furnace, and is calculated by the following equation.
- Gas utilization rate CO 2 / (CO 2 + CO) ⁇ 100
- CO 2 is the furnace top CO 2 concentration [%]
- CO furnace top CO concentration [%]
- ⁇ P / V is an index obtained by indexing the ventilation resistance in the blast furnace, and is calculated by the following equation.
- ⁇ P / V (BP-TP) / BGV
- BP the blowing pressure [Pa].
- TP the furnace top pressure [Pa]
- BGV Bosch gas amount [m 3 (standard state) / min]
- the charging amount per turning: V n and the radius increase amount per turning of the falling radius of the charging raw material: ⁇ R are fixed for each example, but L av2 (n + 1) ⁇ L av2 If the relationship (n) is satisfied, the effect of the present invention can be obtained without any problems even if V n and ⁇ R for each turn are appropriately changed.
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Abstract
Description
この融着帯の通気性が高炉全体の通気性に大きく影響を及ぼしており、高炉における生産性を律速している。さらに、低コークス操業を行う場合、使用されるコークス量が減少することからコークススリットが限りなく薄くなることが考えられる。 Conventionally, raw material charging into a blast furnace is performed by alternately charging ore raw materials and coke, and in the furnace, ore raw material layers and coke layers are alternately layered. Further, in the lower part of the blast furnace, there are an ore raw material layer having a large ventilation resistance in which an ore called softening zone is softened and fused, and a coke slit having a relatively small ventilation resistance derived from coke.
The air permeability of this cohesive zone has a great influence on the air permeability of the entire blast furnace, and the productivity in the blast furnace is limited. Furthermore, when a low coke operation is performed, it is conceivable that the coke slit becomes extremely thin because the amount of coke used is reduced.
例えば、特許文献1においては、ベルレス高炉において、鉱石ホッパーのうち下流側の鉱石ホッパーにコークスを装入し、コンベア上で鉱石の上にコークスを積層し、炉頂バンカーに装入して、鉱石とコークスとを旋回シュートを介して高炉内に装入するようにしている。 In order to improve the cohesive zone ventilation resistance, it is known that mixing coke into the ore raw material layer is effective, and many studies have been reported to obtain an appropriate mixing state. .
For example, in
しかしながら、特許文献3に記載された代表的なコークスの平均粒径は約40~50mmであって、鉱石の平均粒径は約15mmであり、両者の粒径は大幅に異なることから、単純に混合しただけでは空隙率が大幅に低下して、炉内において通気性が悪化し、ガスの吹き抜けや原料の降下不良といったトラブルを生じる可能性がある。
また、鉱石とコークスとをそれぞれ2つのバンカーから同時に切り出して混合装入したとしても、装入面の傾斜によって、大粒径のコークスがより遠くまで転がるため、コークスが分離し易いといった課題がある。
これらのトラブルを回避するためには、炉軸心部にコークスのみの層を形成する方法が考えられる。この方法によれば、炉軸心部にコークス層によるガスの通り道が確保されるため、通気性の改善が可能となる。また、鉱石とコークスとを同時に切り出して混合装入する際に、装入原料を中心から積み付ける逆傾動装入が、上記トラブル回避に有効であることが知られている。 Incidentally, in order to improve the ventilation resistance of the cohesive zone, it is known that it is effective to mix coke in the ore layer as in the technique described in Patent Document 3 described above.
However, the average particle size of typical coke described in Patent Document 3 is about 40 to 50 mm, and the average particle size of ore is about 15 mm. If only mixed, the porosity is greatly reduced, the air permeability is deteriorated in the furnace, and there is a possibility that troubles such as gas blow-out and poor lowering of raw materials may occur.
Moreover, even if the ore and coke are cut out from two bunkers simultaneously and mixed and charged, the coke with a large particle size rolls farther due to the inclination of the charging surface, so that the coke is easily separated. .
In order to avoid these troubles, a method of forming a coke-only layer in the furnace axis can be considered. According to this method, the passage of gas through the coke layer is secured in the core portion of the furnace, so that air permeability can be improved. Moreover, when ore and coke are cut out and mixed and charged at the same time, it is known that reverse tilt charging in which charging raw materials are stacked from the center is effective in avoiding the above trouble.
1.高炉への原料装入1チャージを、コークス装入2バッチ以上、鉱石装入2バッチ以上に分けて、旋回シュートを用いて装入する多バッチ装入において、該コークス装入と該鉱石装入とを同時切り出しで行うに際し、
以下の式1で求められる上記旋回シュートの旋回ごとの平均層厚:Lav1を、高炉の軸中心部に装入されたコークスの厚み:hよりも小さくする高炉への原料装入方法。
Lav1 = Vn/〔(Rn 2-Rn-1 2)π〕 ・・・ 1
ここに、Vn:n回目の旋回における旋回あたりの装入原料体積(m3)[n回目の旋回における旋回あたりの装入量(t)/(コークスと鉱石混合層の見掛け密度(t/m3))]
Rn:n回目の旋回における装入原料の落下半径(m) That is, the gist configuration of the present invention is as follows.
1. In the multi-batch charging in which the charge of raw material charging to the blast furnace is divided into 2 or more batches of coke charging and 2 batches of ore charging, and charging using a rotating chute, the coke charging and the ore charging When performing simultaneous cut-out,
A raw material charging method for a blast furnace in which an average layer thickness: Lav1 for each turning of the turning chute obtained by the following
L av1 = V n / [(R n 2 −R n-1 2 ) π] 1
Here, V n : Raw material volume per turn in the nth turn (m 3 ) [Amount of charge per turn in the nth turn (t) / (Apparent density of coke and ore mixed layer (t / m 3 ))]
R n : fall radius of the charged raw material in the n-th turn (m)
nを任意の自然数とした時、以下の式2で求められる上記旋回シュートのn旋回目の平均層厚:Lav2(n)と、以下の式3で求められるn+1旋回目の平均層厚:Lav2(n+1)とが、以下の式4を満足する高炉への原料装入方法。
Lav2 (n)= Vn/〔(Rn 2-Rn-1 2)π〕 ・・・ 2
Lav2 (n+1)= Vn+1/〔(Rn+1 2-Rn 2)π〕 ・・・ 3
ここに、Vn:n回目の旋回における旋回あたりの装入原料体積(m3)
Rn-1:n-1回目の旋回における装入原料の落下半径(m)
Rn:n回目の旋回における装入原料の落下半径(m)
Vn+1:n+1回目の旋回における旋回あたりの装入原料体積(m3)
Rn+1:n+1回目の旋回における装入原料の落下半径(m)
Lav2(n+1)< Lav2 (n) ・・・ 4 2. In the multi-batch charging in which the charge of raw material charging to the blast furnace is divided into 2 or more batches of coke charging and 2 batches of ore charging, and charging using a rotating chute, the coke charging and the ore charging When performing simultaneous cut-out,
When n is an arbitrary natural number, the average layer thickness of the n-th turn of the above-mentioned turning chute obtained by the following equation 2: L av2 (n) and the average layer thickness of the n + 1-th turn obtained by the following equation 3: A raw material charging method into a blast furnace in which L av2 (n + 1) satisfies the following formula 4.
L av2 (n) = V n / [(R n 2 −R n-1 2 ) π] 2
L av2 (n + 1) = V n + 1 / [(R n + 1 2 −R n 2 ) π] 3
Here, V n : the raw material volume per turn in the n-th turn (m 3 )
R n-1 : Falling radius of the charged raw material in the (n-1) th turn (m)
R n : fall radius of the charged raw material in the n-th turn (m)
V n + 1 : The charging raw material volume per turn in the (n + 1) th turn (m 3 )
R n + 1 : Fall radius (m) of the charged raw material in the (n + 1) th turn
L av2 (n + 1) <L av2 (n) 4
高炉内に、鉱石類原料およびコークスを装入する具体的な装入要領を、図1に基づいて説明する。
以下の説明では、炉頂バンカー12aにはコークスのみが、また炉頂バンカー12bおよび12cには鉱石類原料が、それぞれ貯留されているものとする。
なお、図中、10は高炉、12a~12cは炉頂バンカー、13は流量調整ゲート、14は集合ホッパー、15はベルレス式装入装置、16は旋回シュートである。また、θは、旋回シュートの垂直方向に対する角度である。 Hereinafter, representative embodiments of the present invention will be described with reference to the drawings.
A specific charging procedure for charging ore raw materials and coke into the blast furnace will be described with reference to FIG.
In the following description, it is assumed that only the coke is stored in the
In the figure, 10 is a blast furnace, 12a to 12c are furnace bunker, 13 is a flow rate adjusting gate, 14 is a collecting hopper, 15 is a bell-less charging device, and 16 is a turning chute. Further, θ is an angle with respect to the vertical direction of the turning chute.
すなわち、旋回シュート16の原料装入先が高炉の炉壁部を向いている状態では、炉頂バンカー12bおよび12cの流量調整ゲート13を閉じ、炉頂バンカー12aのみの流量調整ゲート13を開き、この炉頂バンカー12aに貯留されているコークスのみを旋回シュート16に供給することによって、高炉の中心部に、中心コークス層を形成する。 First, when forming the central coke layer in the center of the blast furnace, the raw material charging destination of the
That is, in a state where the raw material charging destination of the turning
Lav1 = Vn/〔(Rn 2-Rn-1 2)π〕 ・・・ 1
ここに、Vn:n回目の旋回における旋回あたりの装入量(t)/(コークスと鉱石混合層の見掛け密度(t/m3))
Rn:n回目の旋回における装入原料の落下半径(m) Here, in the present invention, the average layer thickness Lav1 for each turning of the turning chute obtained by the
L av1 = V n / [(R n 2 −R n-1 2 ) π] 1
Here, V n : charging amount per turn in the n-th turn (t) / (apparent density of coke and ore mixed layer (t / m 3 ))
R n : fall radius of the charged raw material in the n-th turn (m)
炉頂バンカーまでの搬送設備などに鉱石類原料やコークスが偏析する場合には、鉱石類原料又はコークスのみが装入されることになり、集合ホッパー14で他の炉頂バンカー12a、12bおよび12cから装入されるコークスや鉱石類原料と混合されることにはなるが、鉱石類原料又はコークスの比率が増加して、旋回シュート16によって形成される鉱石類原料およびコークスの混合層の混合率が不均一となる。
そこで、本発明では、図2に示すように、式1で求めたLav1を、高炉の軸中心部に装入された中心コークスの厚み:hよりも小さくすることで、上記混合層の不均一性が解消され、結果的に、コークス量が少なかったり、微粉炭の大量吹込み操業を実施したりする場合であっても、高炉内の通気性を安定的に確保することができるのである。 [L av1 <h]
When the ore raw material and coke are segregated in the transport facility to the furnace top bunker, etc., only the ore raw material or coke is charged, and the
Therefore, in the present invention, as shown in FIG. 2, the Lav1 obtained by
装入原料が直前に撒いた原料の山を乗り越えて中心側に流れ込み、混合コークスが分離して、混合率制御性の悪化や、コークス混合率の低下を防止するためである。
なお、本発明では、上記Lav1<hの関係を満足することが重要であるが、具体的な値としては、Lav1が0.90~1.35(m)程度、hが1.20~1.50(m)程度の範囲とすることがそれぞれ望ましい。 Furthermore, L av1 is preferably in the range of about 0.7 to 0.95 times h.
This is because the charged raw material climbs over the pile of raw material that has been sown immediately before and flows to the center side, and the mixed coke is separated to prevent deterioration of the mixing rate controllability and reduction of the coke mixing rate.
In the present invention, it is important to satisfy the relationship of L av1 <h. As specific values, L av1 is about 0.90 to 1.35 (m), and h is 1.20. It is desirable that the range be about ˜1.50 (m).
Lav2 (n)= Vn/〔(Rn 2-Rn-1 2)π〕 ・・・ 2
Lav2 (n+1)= Vn+1/〔(Rn+1 2-Rn 2)π〕 ・・・ 3
ここに、Vn:n回目の旋回における旋回あたりの装入原料体積(m3)
Rn-1:n-1回目の旋回における装入原料の落下半径(m)
Rn:n回目の旋回における装入原料の落下半径(m)
Vn+1:n+1回目の旋回における旋回あたりの装入原料体積(m3)
Rn+1:n+1回目の旋回における装入原料の落下半径(m)
Lav2(n+1)< Lav2 (n) ・・・ 4 Further, in the present invention, when n is an arbitrary natural number, the average layer thickness Lav2 (n) of the nth turn of the turning chute obtained by the following
L av2 (n) = V n / [(R n 2 −R n-1 2 ) π] 2
L av2 (n + 1) = V n + 1 / [(R n + 1 2 −R n 2 ) π] 3
Here, V n : the raw material volume per turn in the n-th turn (m 3 )
R n-1 : Falling radius of the charged raw material in the (n-1) th turn (m)
R n : fall radius of the charged raw material in the n-th turn (m)
V n + 1 : The charging raw material volume per turn in the (n + 1) th turn (m 3 )
R n + 1 : Fall radius (m) of the charged raw material in the (n + 1) th turn
L av2 (n + 1) <L av2 (n) 4
炉頂バンカー12a、12b若しくは12cから、同時に切り出されるコークスと鉱石類原料は、集合ホッパー14内で合流し、装入シュートを通して装入される。この際、装入シュートn旋回目においてリング状に装入された原料の山より、n+1旋回目においてリング状に装入される原料の山の高さが高い場合、n旋回目の山を超えて装入原料が中心側へ流れこむ可能性がある。この場合、n+1旋回目の原料は斜面を流れる過程でコークスが分離するため、コークス混合率が低下し、通気性改善効果を十分に発揮することが出来なくなる。 [L av2 (n + 1) <L av2 (n)]
The coke and ore raw material cut out simultaneously from the furnace
なお、本発明では、上記式4の関係を満足することが重要であるが、具体的な値としては、Vnが2~7(m3)程度、R1が1~2(m)程度、ΔRが0.2~0.5(m)程度の範囲とすることがそれぞれ望ましい。 Furthermore, the ratio of L av2 (n) to L av2 (n + 1) (L av2 (n + 1) / L av2 (n)) is preferably in the range of about 0.5 to 0.9. If the above ratio is 0.9 or more, the raw material charged in the (n + 1) th turn is more likely to flow over the peak of the raw material charged in the nth time and flow into the center side. This is because it is difficult to control the raw material deposition shape by increasing the charging interval or reducing the charging raw material.
In the present invention, it is important to satisfy the relationship of the above formula 4. As specific values, V n is about 2 to 7 (m 3 ) and R 1 is about 1 to 2 (m). , ΔR is preferably in the range of about 0.2 to 0.5 (m).
これらの方法に従い、コークス層並びに同時切り出しの混合層12eで構成される層を順次積層することによって、高炉10内の軸心部および炉壁部には通気抵抗の小さいコークス層が高炉下部から高炉上部に向かって形成され、たとえ、原料装入間隔が狭い状況下においても、その間にコークスと鉱石類原料とが完全混合された混合層12eを形成することができるだけでなく、コークス混合による空隙率低下に起因する高炉上部通気性悪化を防ぐことが出来る。加えて、コークス層の間にコークスと鉱石類原料とが完全混合された混合層12eを形成することができるため、高炉炉下部における通気性改善効果を最大限得ることが可能となる。 Then, the layers composed of the central coke layer and the
In accordance with these methods, a coke layer and a layer composed of the co-mixed
この際の高炉内におけるガスの流れを図4または5に示す。高炉10の下部に設置された送風管21から羽口を通して高温の空気が送風され、羽口近傍のコークスや微粉炭を燃焼することにより高温のCO2ガスを発生させる。CO2ガスは、高炉下部のコークスと反応しCOとなり、鉱石類原料を還元溶解する。 Therefore, as shown in the right half of FIG. 4 or 5, by passing a high-temperature gas mainly composed of CO from a
The gas flow in the blast furnace at this time is shown in FIG. Hot air from the
このため、溶融層の上部側に鉱石類原料が軟化した融着帯が形成され、この融着帯の上部側で鉱石類原料の還元が行われる。
このとき、図6の右半部に示すように、高炉10の下部では、混合層12eにおいて、鉱石類原料とコークスとが完全混合されて、鉱石類原料間にコークスが入り込んだ状態となり、通気性が改善されるとともに、高温ガスが直接鉱石類原料間を通過するため伝熱遅れがなく伝熱特性を改善することができる。 Thereby, the ore raw material in the lower part of the
For this reason, a fusion zone in which the ore material is softened is formed on the upper side of the molten layer, and the ore material is reduced on the upper side of the fusion zone.
At this time, as shown in the right half of FIG. 6, in the lower part of the
このときの還元反応は、FeO+CO=Fe+CO2で表される。
また、ガス化反応は、C+CO2=2COで表される。 In addition, in the lower part of the cohesive zone of the
The reduction reaction at this time is represented by FeO + CO = Fe + CO 2 .
The gasification reaction is represented by C + CO 2 = 2CO.
しかしながら、本発明では、前述したように、コークス層およびコークスと鉱石類原料とを完全混合した混合層12eとで形成される装入層を積層しているので、混合層でコークススリットが形成されることはなく、ガス流れが均一化すると共に、良好な伝熱性を確保して安定的な通気改善が可能となり、上記従来の問題点を有利に解決することができる。 In addition, a coke slit is formed on the upper side of the cohesive zone, and heat is conducted to the ore mainly through the coke slit, so that a heat transfer delay occurs and heat transfer becomes insufficient. Furthermore, since the coke layer with good air permeability and the ore layer with poor air permeability are laminated at the upper part of the
However, in the present invention, as described above, since the charging layer formed by the coke layer and the
本発明の効果を実証するために、図7に示す実験装置を用いて、高炉内での原料還元、昇温過程を模擬してその通気抵抗の変化を調べた。
この実験装置は、円筒状の炉体31の内周面に炉芯管32を配置し、この炉芯管32の外側に円筒状の加熱用ヒーター33を配置する。炉芯管32の内側には耐火物で構成された円筒体34の上端に黒鉛製るつぼ35を配置し、このるつぼ35内に装入原料36が装入されている。この装入原料36には、高炉下部の融着層と同程度の状態となるように、パンチ棒37を介して連結した荷重負荷装置38により上部から荷重を負荷する。円筒体34の下部には、滴下物サンプリング装置39が設けられている。 [Example 1]
In order to verify the effect of the present invention, the change in the ventilation resistance was investigated by simulating the raw material reduction and temperature raising processes in the blast furnace using the experimental apparatus shown in FIG.
In this experimental apparatus, a
ここで、るつぼ35内に装入された装入原料36としては、以下に示すものを用いた。 The gas adjusted by the
Here, as the charging
さらに、それぞれの場合における操業結果を、表1に比較して併記する。 Further, the charging amount of charging raw material per turn: V n , the initial falling radius of charging raw material: R 1, and the radius increase amount per turning of the falling radius of charging raw material: ΔR are shown in Table 1. It is as follows. Note that R n −R n−1 = ΔR (n is an arbitrary natural number).
Further, the operation results in each case are shown in comparison with Table 1.
還元材比は、コークス比と微粉炭比の総和である。
ガス利用率は、炉頂におけるCO2とCOとの濃度の比であり、次式により算出する。
ガス利用率=CO2/(CO2+CO)×100
ここで、CO2は炉頂CO2濃度[%]
COは炉頂CO濃度[%]
また、ΔP/Vは高炉内での通気抵抗を指数化した指標であり、次式により算出する。
ΔP/V=(BP-TP)/BGV
ここで、BPは送風圧力[Pa]
TPは炉頂圧力[Pa]
BGVはボッシュガス量[m3(標準状態)/min] In Table 1, the coke ratio and the pulverized coal ratio are the amount of coke and the amount of pulverized coal (kg) used when producing hot metal 1t.
The reducing material ratio is the sum of the coke ratio and pulverized coal ratio.
The gas utilization rate is a ratio of the concentration of CO 2 and CO at the top of the furnace, and is calculated by the following equation.
Gas utilization rate = CO 2 / (CO 2 + CO) × 100
Here, CO 2 is the furnace top CO 2 concentration [%]
CO is furnace top CO concentration [%]
ΔP / V is an index obtained by indexing the ventilation resistance in the blast furnace, and is calculated by the following equation.
ΔP / V = (BP-TP) / BGV
Here, BP is the blowing pressure [Pa].
TP is the furnace top pressure [Pa]
BGV is Bosch gas amount [m 3 (standard state) / min]
低コークス比とした低還元材比においても、通気抵抗を低滅できることが実証された。 As is apparent from Table 1, the coke ratio of Comparative Example 1 was 342 kg / t, but L av1 was in the range of about 0.7 to 0.95 times h, and L av1 was 0.90 to 1.35. When the raw material charging is performed according to the present invention, such as about (m) and h in the range of about 1.20 to 1.50 (m), the coke ratio of Invention Example 1 is 312 kg / t, and Invention Example 2 can be reduced to about 300 kg / t.
It was proved that the ventilation resistance can be reduced even at a low reducing material ratio with a low coke ratio.
さらに、内容積:4000mm3級の高炉実機において、原料装入試験を実施し、操業条件を比較した。本高炉においては図1に示すように、高炉上部に3つの独立したバンカーを有し、それぞれにコークスまたは鉱石類原料を装入する。通常装入においては、1チャージごとにコークス2バッチを装入後、鉱石類原料2バッチを装入し、混合装入(120kg/t)においては、コークス1バッチ装入後、2バッチ目のコークス切り出しの前半で炉中心部にコークスを装入し、中心コークス層を形成した。その後、他方のバンカーから鉱石類原料を同時に切り出し、逆傾動装入にて原料を装入しコークス混合層を形成した。
上記手順に従った試験結果を表2に示す。 [Example 2]
Furthermore, internal volume: In 4000 mm 3 grade blast furnace actual, conducted material charging tests were compared operating conditions. In this blast furnace, as shown in FIG. 1, it has three independent bunkers in the upper part of the blast furnace, and each is charged with coke or ore raw materials. In normal charging, after charging 2 batches of coke for each charge, 2 batches of ore raw materials are charged. In mixed charging (120 kg / t), after charging 1 batch of coke, the 2nd batch In the first half of the coke cutting, the coke was charged into the center of the furnace to form a central coke layer. Then, the ore raw material was cut out simultaneously from the other bunker, and the raw material was charged by reverse tilt charging to form a coke mixed layer.
The test results according to the above procedure are shown in Table 2.
還元材比は、コークス比と微粉炭比の総和である。
ガス利用率は、炉頂におけるCO2とCOとの濃度の比であり、次式により算出する。
ガス利用率=CO2/(CO2+CO)×100
ここで、CO2は炉頂CO2濃度[%]
COは炉頂CO濃度[%]
また、ΔP/Vは高炉内での通気抵抗を指数化した指標であり、次式により算出する。
ΔP/V=(BP-TP)/BGV
ここで、BPは送風圧力[Pa]
TPは炉頂圧力[Pa]
BGVはボッシュガス量[m3(標準状態)/min] In Table 2 above, the coke ratio and pulverized coal ratio are the amount of coke and the amount of pulverized coal (kg) used when producing hot metal 1t.
The reducing material ratio is the sum of the coke ratio and pulverized coal ratio.
The gas utilization rate is a ratio of the concentration of CO 2 and CO at the top of the furnace, and is calculated by the following equation.
Gas utilization rate = CO 2 / (CO 2 + CO) × 100
Here, CO 2 is the furnace top CO 2 concentration [%]
CO is furnace top CO concentration [%]
ΔP / V is an index obtained by indexing the ventilation resistance in the blast furnace, and is calculated by the following equation.
ΔP / V = (BP-TP) / BGV
Here, BP is the blowing pressure [Pa].
TP is the furnace top pressure [Pa]
BGV is Bosch gas amount [m 3 (standard state) / min]
以上の結果より、低コークス比とした低還元材比においても、通気抵抗を低滅できることが実証された。 As is apparent from Table 2, Invention Examples 1 and 2 exhibited a lower ΔP / V than Comparative Examples 1 and 2 having a high coke ratio. Moreover, even if it was invention example 3 whose coke ratio is 310 kg / t still lower, (DELTA) P / V same as the comparative example 2 whose coke ratio is 350 kg / t was obtained.
From the above results, it was proved that the airflow resistance can be reduced even at a low reducing material ratio with a low coke ratio.
12a~12c 炉頂バンカー
13 流量調整ゲート
14 集合ホッパー
15 ベルレス式装入装置
16 旋回シュート
31 炉体
32 炉芯管
33 加熱用ヒーター
34 円筒体
35 黒鉛製るつぼ
36 装入原料
37 パンチ棒
38 荷重負荷装置
39 滴下物サンプリング装置
40 ガス混合装置
41 ガス分析装置
42 熱電対 DESCRIPTION OF
Claims (2)
- 高炉への原料装入1チャージを、コークス装入2バッチ以上、鉱石装入2バッチ以上に分けて、旋回シュートを用いて装入する多バッチ装入において、該コークス装入と該鉱石装入とを同時切り出しで行うに際し、
以下の式1で求められる上記旋回シュートの旋回ごとの平均層厚:Lav1を、高炉の軸中心部に装入されたコークスの厚み:hよりも小さくする高炉への原料装入方法。
Lav1 = Vn/〔(Rn 2-Rn-1 2)π〕 ・・・ 1
ここに、Vn:n回目の旋回における旋回あたりの装入量(t)/(コークスと鉱石混合層の見掛け密度(t/m3))
Rn:n回目の旋回における装入原料の落下半径(m) In the multi-batch charging in which the charge of raw material charging to the blast furnace is divided into 2 or more batches of coke charging and 2 batches of ore charging, and charging using a rotating chute, the coke charging and the ore charging When performing simultaneous cut-out,
A raw material charging method for a blast furnace in which an average layer thickness: Lav1 for each turning of the turning chute obtained by the following formula 1 is made smaller than a thickness of a coke charged to the axial center portion of the blast furnace: h.
L av1 = V n / [(R n 2 −R n-1 2 ) π] 1
Here, V n : charging amount per turn in the n-th turn (t) / (apparent density of coke and ore mixed layer (t / m 3 ))
R n : fall radius of the charged raw material in the n-th turn (m) - 高炉への原料装入1チャージを、コークス装入2バッチ以上、鉱石装入2バッチ以上に分けて、旋回シュートを用いて装入する多バッチ装入において、該コークス装入と該鉱石装入とを同時切り出しで行うに際し、
nを任意の自然数とした時、以下の式2で求められる上記旋回シュートのn旋回目の平均層厚:Lav2(n)と、以下の式3で求められるn+1旋回目の平均層厚:Lav2(n+1)とが、以下の式4を満足する高炉への原料装入方法。
Lav2 (n)= Vn/〔(Rn 2-Rn-1 2)π〕 ・・・ 2
Lav2 (n+1)= Vn+1/〔(Rn+1 2-Rn 2)π〕 ・・・ 3
ここに、Vn:n回目の旋回における旋回あたりの装入原料体積(m3)
Rn-1:n-1回目の旋回における装入原料の落下半径(m)
Rn:n回目の旋回における装入原料の落下半径(m)
Vn+1:n+1回目の旋回における旋回あたりの装入原料体積(m3)
Rn+1:n+1回目の旋回における装入原料の落下半径(m)
Lav2(n+1)< Lav2 (n) ・・・ 4
In the multi-batch charging in which the charge of raw material charging to the blast furnace is divided into 2 or more batches of coke charging and 2 batches of ore charging, and charging using a rotating chute, the coke charging and the ore charging When performing simultaneous cut-out,
When n is an arbitrary natural number, the average layer thickness of the n-th turn of the above-mentioned turning chute obtained by the following equation 2: L av2 (n) and the average layer thickness of the n + 1-th turn obtained by the following equation 3: A raw material charging method into a blast furnace in which L av2 (n + 1) satisfies the following formula 4.
L av2 (n) = V n / [(R n 2 −R n-1 2 ) π] 2
L av2 (n + 1) = V n + 1 / [(R n + 1 2 −R n 2 ) π] 3
Here, V n : the raw material volume per turn in the n-th turn (m 3 )
R n-1 : Falling radius of the charged raw material in the (n-1) th turn (m)
R n : fall radius of the charged raw material in the n-th turn (m)
V n + 1 : The charging raw material volume per turn in the (n + 1) th turn (m 3 )
R n + 1 : Fall radius (m) of the charged raw material in the (n + 1) th turn
L av2 (n + 1) <L av2 (n) 4
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Cited By (2)
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CN112410484A (en) * | 2020-11-18 | 2021-02-26 | 山东钢铁集团日照有限公司 | Blast furnace distributing method for interval ore pressing |
JP2021175822A (en) * | 2020-04-22 | 2021-11-04 | Jfeスチール株式会社 | Method for charging center coke |
Families Citing this family (3)
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JP6269549B2 (en) * | 2015-03-26 | 2018-01-31 | Jfeスチール株式会社 | Blast furnace operation method |
JP6260751B2 (en) * | 2015-10-28 | 2018-01-17 | Jfeスチール株式会社 | Raw material charging method to blast furnace |
KR102574567B1 (en) * | 2019-04-03 | 2023-09-04 | 제이에프이 스틸 가부시키가이샤 | Blast furnace fault determination apparatus, method for determining fault in blast furnace, and method for operating blast furnace |
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JPH06271908A (en) * | 1993-03-19 | 1994-09-27 | Kawasaki Steel Corp | Method for charging raw material in multi-batches into bell-less blast furnace |
JP2004107794A (en) | 2002-08-30 | 2004-04-08 | Jfe Steel Kk | Method for charging raw material into bell-less blast furnace |
JP2005060797A (en) * | 2003-08-18 | 2005-03-10 | Jfe Steel Kk | Method for charging material to blast furnace |
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JPS5910402A (en) | 1982-07-10 | 1984-01-19 | Toshiba Corp | Rolling mill and rolling method |
JP3565172B2 (en) * | 2001-02-28 | 2004-09-15 | Jfeスチール株式会社 | How to put blast furnace raw materials inside the furnace |
TWI239355B (en) * | 2002-08-29 | 2005-09-11 | Jfe Steel Corp | Method for charging material into blast furnace with distributing chute instead of bells |
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2013
- 2013-05-17 TR TR2018/16178T patent/TR201816178T4/en unknown
- 2013-05-17 CN CN201380025729.8A patent/CN104302787B/en active Active
- 2013-05-17 JP JP2013556706A patent/JP5574064B2/en active Active
- 2013-05-17 KR KR1020147033494A patent/KR101592955B1/en active IP Right Grant
- 2013-05-17 WO PCT/JP2013/003165 patent/WO2013172042A1/en active Application Filing
- 2013-05-17 EP EP13791416.4A patent/EP2851437B1/en active Active
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JPS5910402B2 (en) | 1978-12-08 | 1984-03-08 | 川崎製鉄株式会社 | How to operate a blast furnace with mixed charges |
JPS61243107A (en) * | 1985-04-19 | 1986-10-29 | Nippon Kokan Kk <Nkk> | Method for charging raw material to blast furnace |
JPH03211210A (en) | 1990-01-16 | 1991-09-17 | Kawasaki Steel Corp | Method for charging raw material in bell-less blast furnace |
JPH06271908A (en) * | 1993-03-19 | 1994-09-27 | Kawasaki Steel Corp | Method for charging raw material in multi-batches into bell-less blast furnace |
JP2004107794A (en) | 2002-08-30 | 2004-04-08 | Jfe Steel Kk | Method for charging raw material into bell-less blast furnace |
JP2005060797A (en) * | 2003-08-18 | 2005-03-10 | Jfe Steel Kk | Method for charging material to blast furnace |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2021175822A (en) * | 2020-04-22 | 2021-11-04 | Jfeスチール株式会社 | Method for charging center coke |
JP7331876B2 (en) | 2020-04-22 | 2023-08-23 | Jfeスチール株式会社 | Injection method of center coke |
CN112410484A (en) * | 2020-11-18 | 2021-02-26 | 山东钢铁集团日照有限公司 | Blast furnace distributing method for interval ore pressing |
CN112410484B (en) * | 2020-11-18 | 2022-03-25 | 山东钢铁集团日照有限公司 | Blast furnace distributing method for interval ore pressing |
Also Published As
Publication number | Publication date |
---|---|
EP2851437A1 (en) | 2015-03-25 |
KR101592955B1 (en) | 2016-02-11 |
KR20150004907A (en) | 2015-01-13 |
TR201816178T4 (en) | 2018-11-21 |
CN104302787A (en) | 2015-01-21 |
EP2851437A4 (en) | 2015-12-16 |
JPWO2013172042A1 (en) | 2016-01-12 |
EP2851437B1 (en) | 2018-10-03 |
CN104302787B (en) | 2016-10-05 |
JP5574064B2 (en) | 2014-08-20 |
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