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05- New and Future Steel Technologies Using Mn - K Ichikawa Nippon Steel Corp

05- New and Future Steel Technologies Using Mn - K Ichikawa Nippon Steel Corp

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Development of Japan’s Refining Technologies in the Past and Future

2004.6.2 By Kaoru Ichikawa Nippon Steel Corporation

1. Introduction 2. Behavior of Mn in the Steel-making process 3. History of Process Improvement and Influence on Manganese

    (1) Top-and-Bottom blowing converter
      (2) Hot metal pretreatment       (3) LD-type hot metal pretreatment       (4) MURC process

4. Steel product needs
  (1) Automobile sheet steel   (2) Plate products

5. Future Development

Crude steel production
220

Crude steel production (millon tons/year)

200 180 160 140 120 100 80 60 40 20 0
1950 60 70 80 82 84 86 88
Japanese peak 120 million tons/1973

1000 800 China U.S.A.   Japan 600 400 Germany Korea 200 0
Total production (millon tons/year)

Total

90 92 94 96  98  00  02 03

Changes in the consumption of steel products in Chahges in the consumption of 日本の鋼材消費量の推移    JAPAN
steel products in JAPAN
The per-capita consumption of steel products (kg per person)
口 当 り 鋼 材 見 掛 け 消 費 量 (㎏ / 人 ) 人 1,000

800 600 400 200 0 1960
鋼材消費量は経済的な成長を示す尺度となる。 The average consumption in the advanced 先進工業社会では、年間500~600㎏/人 industrial nations is approx. 500 to 600 kg per person. 程度の鋼材消費となる。

65

70

75

80

85

90

(年)

95

2000
5

NIPPON STEEL CORPORATION

000 GDP (US dollar per person) .Consumption of steel product in the world (2001) The per-capita consumption of steel products (kg per person) 1000 Korea      Japan  575kg Germany U.000           10.000           100. 100                    Russia 173kg  Thailand  121kg Average  China 135kg   132kg                                                        India  27kg                    10 100           1.S.A.

Trend in steel demand in the world The steel demand 900 700 million tons Crude steel (2001) Total  846 million ton Asia   363 million ton( 42%)  Others ed 13% ta l inc reas to The wor ld 4% Asia   24% ) ( 500 300 100 Japan  Korea   China 103 44       152 496 362       422      449 ( million tons) tons) Japan Korea China Consumption of steel product (million tons) tons) 174 38      44 44 211  232 255 73     72      72 2001 2002 2003       2001 2002 2003        2001 2002 2003 2004 .

Economic development in China 6 5 4 3 The outputs of automobiles   The output of electric appliances million 30 20 10 million Forecast Air conditioners 2334 1827 1157 690 1338 727 3135 1 0 48 50 57 216 420 600 110  112 127 146 164 Bus・ Truck 1997 98 99 2000 01 02 03 05 ( Automobile 2 70 61 109 Forecast ) ( ) 961 683 965 786 974 823 China Japan 718 602 732 0 Refrigerators 1210 919 980 1044 1060 1279 1351 1599 16 12 8 4 0 China Japan 388 332 501 516 537 485 454 422 1995 96 97 98 99 2000 01 02 .

000 900 800 700 600 500 400 300 200 1960 Forecast after China.Crude steel production and the long-term trend in the world. 1.100 Crude steel production million tons /year 1.a new growing market. is taken into account ) ( Crude steel production Forcast made at the end of the 20th century 70 80 90 2000 2010 2020 .

5 1 Asia          Oceania     North  America South  America Europe      Africa 0.5 2 .9 t h is n grow latio e po p u unt h Only t to acco in taken The economic growth of each region is also taken into account 1.95 (billion people)                 (billion tons) 1.35  1.Forecast for increased steel demand Forecast for the world population   Forecasts for the crude steel production population   2002 2010 2020 2030 2040 2050 0 20 40 60 80 100   0 0.

S.A.   Japan Total production (millon tons/year) Total 600 400 Germany Korea 200 0 90 92 94 96  98  00  02 03 .Crude steel production 220 Crude steel production (millon tons/year) 200 180 160 140 120 100 80 60 40 20 0 1950 60 70 80 82 84 86 88 Japanese peak 120 million tons/1973 1000 800 China U.

1) 1st phase (1957~1970) 2nd phase (1971~1980) 3rd phase (1981~2000) Present de S de Si de P de Si de S Hot metal Pretreatment de S de S de Si de Si de P de S Separation of de-S Top Blow converter Top Blow converter de S de Si de P de C Top-bottom comvined converter TPC-type → LD-type Ladle-type Top-bottom comvined converter de P de Si de P de C de Si de P de C de C degassing Top-bottom comvined converter BOF de C de C degassing de C de S degassing Inclusion control de C degassing de S degassing Inclusion control degassing Secondary refining process .Progress in the division of refining function at Nippon steel.

LC Si-Mn M.Consumption of Fe-Mn alloy in Japan & Mnequivalent consumption in Japanese steel 2). 5 4 Mn alloy unit (kg/t) 3 2 1 0 1974 1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998 2000 2002 Mn unit (kg/t) HC-FeMn MC. M.Mn.Mn Fe-Si 7 6 5 4 3 2 1 0 1974 1976 1978 1980 1982 1984 1986 1988 Total HC-FeMn MC.LC Fe-Mn. Si-Mn 1990 1992 1994 1996 1998 2000 2002 .

Steel product needs   (1) Automobile sheet steel   (2) Plate products 5.1. Future Development . Introduction 2. Behavior of Mn in the Steel-making process 3. History of Process Improvement and Influence on Manganese     (1) Top-and-Bottom blowing converter       (2) Hot metal pretreatment       (3) LD-type hot metal pretreatment       (4) MURC process 4.

001 tr 0.02 [Mn] Temp.3 Reaction Condition Basicity PO 2 High High High High High Low Low Temp.15 1650 0.4 0.03 1.005 0.15~ ~0.005 0.02 0.An example of the steel making method & acceleration conditions for respective reactions.1 0. (℃) 1530 0.005 0.02 0.2 1350 Dephosphorization Desulfurization Reduction of MnO 0.001 0.5 ~0. Low High High Decarburization 4 tr 0.5 -  C + 1/2O2 = CO  P + 5/4O2 + 3/2CaO = 1/2Ca3(PO4)2   S + CaO = CaS + 1/2O2     Mn + 1/2O2 = MnO .5 0.05 tr 0.3 ~0.03 ~0. Process Flux & oxygen % content in Fe [C] [Si] [P] [S] BF (dS) CaO、 Hot Metal   Mg or Na2CO3 Pretreatment (dP) CaO、 Fe-Ore、O 2 BOF  CaO、MgO  Mn-Ore   Fe-Ore、O2 Secondary  Refining  Alloy Product 4.

2 0 [Mn] 0.0 0 0 .5 0 1.40 [C] 0 .09 0 . 1 2 72 0 52 37 kg/heat HCFeMn LCFeMn Si-Mn Set 1 2 72 0 52 37 0 23 8 5 36 1 5 kg/heat HCFeMn LCFeMn Si-Mn Yield 95 95 95 % 0 23 8 5 36 1 5 0 2 38 5 3 61 5 kg/heat 95 95 95 % 0 2 38 5 3 61 5 95 95 95 % Chemical content (%) C 6.20 Si 0.86 2.08 0 .25 0 .00 0.12 0 .70 HCFeMn LCFeMn Si-Mn .2 0 [Mn] 0 .6 0 1.1 2 0.05 0 .6 0 1 .1 5 0.15 1 .1 5 1 .50 Mn 74.3 0 0.50 81.60 1 .00 60.4 0 Alloy HCFeMn LCFeMn Si-Mn Caic .00 0 .07 [Si] 0 .06 [Si] 0 .3 0 0 .4 0 [C] 0 .5 0 1 .50 1 .1 5 1. End poin t Ladle aim Uppe r limit Lower limit [C] 0.0 5 0.85 0.11 0 .2 5 0.0 0 0.20 [Mn] 0 .05 0 .30 0 .1 0 [Si] 0.2 5 0 .Example of calculation results of ferroalloys 3).00 14.

048×log (%CaO/%SiO2) [%Mn] T Mn yield (%) = 1 55 1 (%MnO) 1+ × × × Slag volume 71 1000 [%Mn] × 100 .79 + 1.07×log (%T.980× 1 -0.Manganese yield Mn + 1/2O 2 = MnO log (%MnO) = -1.Fe) + 3.

1. History of Process Improvement and Influence on Manganese     (1) Top-and-Bottom blowing converter       (2) Hot metal pretreatment       (3) LD-type hot metal pretreatment       (4) MURC process 4. Future Development . Introduction 2. Steel product needs   (1) Automobile sheet steel   (2) Plate products 5. Behavior of Mn in the Steel-making process 3.

10 to 0.10 O2 CO2 N2 LPG Fig.N2.CO2.60 0. Relation between turndown free oxygen and turndown carbon in top-blown.N2.01 to 0. bottom-blown. .Outline of combined-blown processes 4) Process LD-OB LD-CB Bottom tuyere construction Double-pipe tuyere Small-diameter pipe assembly plug Bottom gas type O 2. and combined-blown converter 4).LPG CO 2.Ar.(O2) Bottom gas flow rate(Nm3/t/min) 0.

Changes in reaction using the top-and-bottom blowing method 5). O2 CO2 N2 LPG .

1. Steel product needs   (1) Automobile sheet steel   (2) Plate products 5. History of Process Improvement and Influence on Manganese     (1) Top-and-Bottom blowing converter       (2) Hot metal pretreatment       (3) LD-type hot metal pretreatment       (4) MURC process 4. Behavior of Mn in the Steel-making process 3. Introduction 2. Future Development .

Recent advances of hot metal pretreatment in Japan 6). 82 Nipponn Steel Kimitsu Yawata Oita Nagoya Muroran Chiba Mizushima Keihin Fukuyama ★ ★ ★ ★ ★ ★ ★ ▲ ▲ ● ★ ★ ● ● ● ★ ● ● ▲ ● ● ● 84 86 88 90 92 94 96 98 00 ● ● 02 JFE Sumitomo Kashima ★ Wakayama Kobe Kakogawa Kobe ★:TPC ▲:Ladle ●:Converter .

Example of torpedo car hot metal pretreatment process (Kimitsu. Nippon steel)4). .

Nippon Steel) 4).Example of ladle hot metal pretreatment process (Oita. .

Changes in converter operating with introduction of hot metal pretreatment and LD-OB process (Kimitsu) 4).1 39.6 54.000 69 85.2 .2 6. LD process (1981) Monthly crude steel production capacity (t/furnace/month) Hot metal pretreatment ratio (%) Availability (%) Tap-to-tap time (min) Furnace life (heats) Molten steel yield (%) Total CaO consumption (kg/t) Ferromanganese consumption (kg/t) 200.5 28 5.795 93.4 Hot metal pretreatment and LD-OB process (1989) 407.340 95.2 34 1.3 4.000 0 55.

Effect of slag volume on dephosphorizing degree and manganese yield (Oita) 4). 100 90 80 70 60 50 40 30 20 10 0 0 20 40 60 80 Slag Volume (kg/t) 100 120       26 ( P:24 → 18)  ×10 -3 De phosphorization degree (% ) & Manganese yield (%) L e ss slag blo win g wit h de ph o sph o r ize d h o t me t al ar e a D ephos phori za ti on deg ree 65 Mn-y i el d 85 ( P : 120 → 18 )  ×10 -3 % 25 Co n ve n t io n al LD c o n ve r t e r ar e a % .

8 Input [Mn] (%) .2% 0.8 1.0 2.4 2.6 1.0 [C]<0.4 1.Turn-down [Mn] by mass reduction of Manganese ore 7).6 2. [Mn ] (%) at turn-down 1.

History of Process Improvement and Influence on Manganese     (1) Top-and-Bottom blowing converter       (2) Hot metal pretreatment       (3) LD-type hot metal pretreatment       (4) MURC process 4. Future Development . Behavior of Mn in the Steel-making process 3.1. Introduction 2. Steel product needs   (1) Automobile sheet steel   (2) Plate products 5.

Nippon Steel ) 4). .Example of converter hot metal pretreatment process (Nagoya .

Process Free boad Exhaust gas treatment Simple Stirring energy Oxygen supplying rate Low Oxygen gas ratio Scrap melting Initial investment cost Low Injection Process Small Low Low Impossible Top-and-bottom blowing converter Large OG System High High High Possible High Treatment condition Slag basicity (T.Comparison of hot metal dephosphorization process and treatment conditions 8).Fe) content De-Si before de-P Addition of Slag fluorspar foaming Slag utilization Injection Process 4-8 2-5 Imperative Necessary Small Difficult Top-and-bottom blowing converter 1-2 7-18 Not Not Imperative Necessary Large Easy .

KR desulphurization and LD-type dephosphorization (Kimitsu) 9). .

Manganese use in the LD-type process For manganese use in the LD-type process. . manganese yield improvement due to the decreased slag volume in the converter can be obtained in the same way as using conventional technology.Fe and lowered basicity during dephosphorization. a decrease in Mn during dephosphorization cannot be avoided due to increased %T. However.

Evolution of chemical elements during desiliconization and dephosphorization at LD-type dephosphorization 10). . The [Mn] value goes down.

Future Development .1. History of Process Improvement and Influence on Manganese     (1) Top-and-Bottom blowing converter       (2) Hot metal pretreatment       (3) LD-type hot metal pretreatment       (4) MURC process 4. Introduction 2. Steel product needs   (1) Automobile sheet steel   (2) Plate products 5. Behavior of Mn in the Steel-making process 3.

Low HMR Operation ・Slag Hot Recycle→Reduction of Slag . High (T.Fe). Charging Carging De[Si]/[P] m De[Si]/[P] ( Blow 1 ) a Deslagging De[C] (Blow 2) Tap So lidific at in Con firmation Co n Slag Solidification Next ch Charging Carging De[Si]/[P] ( Blow 1) Speciality of MURC Process ・Low Basicity.Fe)≧8%,(~1350℃) ・High Gaseous Oxygen Ratio.The Outline of MURC process(Oita)11). Low Temperature →High Efficiency De[P]   (CaO/SiO2≦2),(T.

42%  Low C Steel 100 80 60 40 20 0 Conventional MURC No Recycle MURC .Reductionof lime consumption by MURC process 11). 120 Total CaO Consumption (Conventional Blow=100%) Hot Metal [Si]=0.

42% Low C Steel  (Exclude Metal .Water) 90 80 BOF Slag (kg/t) 70 60 50 40 30 20 Conventional MURC No Recycle MURC .Reduction of Slag Discharge by MURC process 11). Hot Metal[Si]=0.

with dephosphorization and decarburization being operated continuously. Since the smelting reduction of manganese ore becomes difficult with increased manganese loss. the turn-down [Mn] is consequently reduced compared to that in the conventional pretreatment process. In addition. .Manganese loss in the MURC process Manganese loss in the MURC process increases as a result of low basicity and high %T.Fe during the dephosphorization process. the carry-over of phosphorus into the decarburization process increases. requiring light dephosphorization treatment in the decarburization process.

・On the other hand. .  So there is little or no reduction compared to the conventional pretreatment. ・Neither technology emphasizes  reducing the volume of the Mn alloy used.Manganese alloy in the LD-type pretreatment & MURC process ・In the LD-type pretreatment method.  priority is given to using scrap and reusing or reducing slag.  which is demanded by today’s society.  the MURC process focuses on improving heat loss  and shortening the process time.

Introduction 2. Behavior of Mn in the Steel-making process 3. Future Development . History of Process Improvement and Influence on Manganese     (1) Top-and-Bottom blowing converter       (2) Hot metal pretreatment       (3) LD-type hot metal pretreatment       (4) MURC process 4. Steel product needs   (1) Automobile sheet steel   (2) Plate products 5.1.

Steel product needs • Market demands related to steel products are becoming increasingly strict. →We shall examine the changes in improved and upgraded steel products using automobile sheet steel and heavy plate products as example. . • There has been continuous cost reduction in the refining process and cost increase due to improved and upgraded quality of steel products.

Behavior of Mn in the Steel-making process 3. Steel product needs   (1) Automobile sheet steel   (2) Plate products 5. History of Process Improvement and Influence on Manganese     (1) Top-and-Bottom blowing converter       (2) Hot metal pretreatment       (3) LD-type hot metal pretreatment       (4) MURC process 4. Future Development .1. Introduction 2.

.Trend of car weight and HSS ratio 12). Application of TS 590 Mpa or higher steel to automobile 13).

TRIP steel) Conventional high strength sheet steel for automobiles used to be solid solution-hardened steel or precipitation-hardened steel with alloy added. high strength steel products whose microstructure is reinforced for greater strength have been used. . Currently. (DP steel.Relation between tensile strength and elongation of HSS 14).

25 D Precipitation 0.89 1.08 0.99 - .46 hardened steel C DP steel 0.15 1.05 0.09 0.48 0.01 0. Yield Tensile Elonstrength strength gation (Mpa) (Mpa) (%) 241 370 432 539 510 384 487 618 636 644 43 30 27 22 37 Type of steel A Mild steel C Si Mn Ti - 0.24 B Solid solution 0.80 0.05 0.02 1.01 0.07 hardened steel E TRIP steel 0.Chemical compositions (mass%) and mechanical properties of the steels 15).

Future Development . Introduction 2. Behavior of Mn in the Steel-making process 3. Steel product needs   (1) Automobile sheet steel   (2) Plate products 5.1. History of Process Improvement and Influence on Manganese     (1) Top-and-Bottom blowing converter       (2) Hot metal pretreatment       (3) LD-type hot metal pretreatment       (4) MURC process 4.

Re u sin g an d re c yc lin g waste .CaO (au xiliary mate rial) .Improve me n t in iron yie ld .Adju stability for h igh .su lfu r f u e l) .Re du c tion in T.grade ste e l sc rap and du st .Re u sin g slag an d du st .P ste el man u fac tu rin g En e rgy savin g .P ste e l man u fac tu rin g proc e ss 1 98 2 ~ ・ Mass produ c tion proc e ss ・ TPC type.Min imize d e mission from th e syste m: slag an d du st . Ladle type Ne e ds of th e re f in in g proc e ss in e ac h pe riod Improve me n t in ste e l qu ality .qu an tity ・ Low.ph osphoru s ore an d h igh .Tire s.Re du c tion in Mn alloys Ration alization →Expan sion of produc tivity Re du c tion in slag volu me an d re usin g of slag 1 99 9 ~ ・ Mass produ c tion proc e ss ・ LD type Proc ess in fu tu re En viron me ntally c on sc iou s produ c t te c h nology .Needs of the refining process and transition of the hot metal pretreatment process Evolu tion of th e h ot me tal pre tre atme n t proc e ss ~1 9 8 2 ・ Small. an d an e c onomical sou rce of h e at) .Re du c in g an d re c yc lin g slag an d du st .su lfu r hot metal (h igh . automobiles and glass Proc e ss fe atu rin g h igh de gre e of fre edom of mate rial (High e ffic ie n c y de ph osph orization an d de su lph u rization .ph osph oru s an d h igh .Low e n viron me n tal load  .Utilization of low.Low.

namely dephosphorization.Conclusion  As for manganese use in the process in view of the above prospects.  we can assume that the smelting reduction of manganese ore  in the converter will not be actively employed in the future  since it decreases the scrap usage rate.  As long as the main technological concern in the refining process  focuses on improving the main reaction.  this is on the condition that the Fe-Mn price remains very economical. .  the supply of manganese that has different reactive characteristics  will take the form that adds alloys. increases slag generation  and results in a low yield level of manganese.

strength.   . higher quality.  will be in much greater demand from now.    For the above sheet steel and plate products. price. toughness and versatility. especially low carbon alloys.    Fe-Mn alloys. The advantages of steel materials over other materials  include volume. higher quality steel products  will be the addition of alloys to steel materials.  the need for higher grade.    The base for developing higher grade.  and meeting strict requirements will grow in the steel market.

The iron and steel Institute of Japan.4 (2001). 9)Tomita.6 (1999).:Nippon steel technical report No. Vol. p.3 (Dec. 12) Kuriyama.: 7th International Ferroalloy Conference.p59. and Masuda.21 17) Advanced Technology of Plate Production in Japan. 1987.10.M. Oct.81 (2000). 10) Shima. & Tech.Y.2002) P. 13) Yukihisa Komiya: Kobe steel engineering reports Vol. of Iron and Steel Program. Italy. Vol.:Bulletin of the iron and steel Institute of Japan.p57. 11) Kumakura.T.K.51.:127th Seikou-bukai . 8)Kitamura.367. The iron and steel Institute of Japan . Report of Proceedings.References 1)Kohtani.:Nippon steel technical report No. S675. et al. p. The Iron and steel Institute of Japan. 15) Uenishi.K.p3 2)Ferroalloy Handbook.p. (1997).K.61 (1994). (1995) 4)Endoh. 14) Itoh. 65(1979). 5)Tada.(1984) p116. 6)Handbook of Iron and Steel 4th edition (2002).: Tetsu-to-Hagane. Nov.52 No.2. 3)Nakamura. 16) Amano. :IISI 21 Annual Meeting & Conference.M.S.K.No. Nov.A.(2000).(2002). Vol. No. on Sci.H. et al: 9th China-Japan Symp. et al:Bulletin of the iron and steel Institute of Japan. et al:3rdEuropean Oxygen Steelmaking Conference.S.(2001).p.1. .p.4.S. et al:Journal of Society of Automotive Engineers of Japan.8(2003)No.18. et al:2nd European Oxygen Steelmaking Congress. Japan Ferro alloy association.S et al:Proceedings of the 6th International Iron and Steel Congress (1990). 7)Tabuchi.55.

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