491 論 文 鉄と鋼 Tetsu-to-Hagané Vol. 100 (2014) No. 4 溶銑脱燐プロセスシミュレーションモデルの開発 Development of Simulation Model for Hot Metal Dephosphorization Proce
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1 491 論 文 溶銑脱燐プロセスシミュレーションモデルの開発 Development of Simulation Model for Hot Metal Dephosphorization Process Shin-ya Kitamura, Kimihisa Ito, Farshid Pahlevani and Masaki Mori Synopsis : The simulation model for hot metal dephosphorization process by multi-phase slag was developed by the ISIJ research group of Process Simulation for Dephosphorization of Pig Iron by Multi-Phases. The model employed a multi-scale model, which was an integration of macro- and meso-scale models. In the macro-scale model, the reactions between the liquid slag and the metal were described by a coupled reaction model. In the meso-scale model, the fraction of solid phase was calculated from the numerated phase diagram data, and the distribution of P 2 O 5 between solid and liquid slag phases was evaluated by thermodynamic data. The dissolution of flux was also considered in the model. The program runs on a normal Windows personal computer (PC) with Microsoft C The pull-down menu is available for selecting jobs. The input and output data files are written in CSV style, which can be handled easily by a spreadsheet processor such as Microsoft Excel. One calculation requires less than a second when a typical PC is used. This program was applied the various experiments carried out by five steelmaking companies in Japan and the reasonable results were obtained. The use of the program is sufficiently easy and enables the user to apply it to processes control as well as process simulation. Key words: hot metal dephosphorization; simulation; kinetic model; mass transfer coefficient; stirring energy. 1. 緒言 CaO-SiO 2 -FeO-P 2 O 5 2CaO SiO 2 C 2 S C 2 S 3CaO P 2 O 5 C 3 P 3 C 2 S-C 3 P 4,5 6, , Received on Apr. 4, 2013 ; Accepted on May 13, Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira Aoba-ku Sendai School of Fundamental Science and Engineering, Waseda University 3 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, now Singapore Institute of Manufacturing Technology 4Student, Graduate School of Fundamental Science and Engineering, Waseda University Corresponding author : kitamura@tagen.tohoku.ac.jp DOI : 59
2 492 MPSR Multi-Phase Slag Refining B モデルの概要 MPSR Fig MPSR Fig.2 Fig.3 1 FeO 1 CaO-SiO 2 -FeO 3 10 C 2 S 10% CaF 2 5% 100 K 1 C 2 S C 2 S C 2 S P 2 O 5 C 2 S P 2 O 5 P 2 O C 2 S C 2 S C 2 S P 2 O 5 Fig. 2. Schematics of the MPSR model (Phases and reactions that considered in the model). Fig. 1. Basic structure of the Multi-Phase Slag Refining (MPRS) Model, which consists of macro-scale model and meso-scale model. Fig. 3. Flow chart of the calculation. 60
3 k m m/s CO G CO mol/ m 2 s k m k s k m /k s k s k m /k s k s CO 10 CO G CO 4 FeO CO CO 10 2/3 CaO MgO 17,18 CaO C 2 S 1/m m CaO MgO SiO 2 FeO CaO 10 CO 2 CO 2 DCR FeO 2 2 PCR CO 2 Table 1 Fe 2 O 3 FeO FeO 2 C Mn Si PFeO C 2 S C 3 P h 2 100% 3. ユーザーインターフェース 12) Windows Microsoft C Fig Fig.5 CSVMicrosoft Table 1. Used values to calculate heat balance. Specific Heat Hot Metal 0.88 kj/kg/deg Slag 1.13 kj/kg/deg Reaction Heat C+1/2O 2 =CO kj/kg-c C+O 2 =CO kj/kg-c Fe+1/2O 2 =FeO 4812 kj/kg-fe Fe+3/4O 2 =1/2Fe 2 O kj/kg-fe Si+O 2 =SiO kj/kg-si Mn+1/2O 2 =MnO 5326 kj/kg-mn P+5/4O 2 =PO kj/kg-p Heat of Formation 2CaO+SiO 2 =2CaO SiO kj/kg-si 3CaO+P 2 O 5 =3CaO P 2 O kj/kg-p 61
4 494 Excel で作成でき 予め作成したインプット条件の数値リ 2 塩基度を合わせるために生石灰粒径を変化させる 酸化 ストをプルダウンメニューの ファイル から開けば 各 鉄も含め 他の添加物も同じ粒径とした 尚 スラグの 数字が読み込まれる プルダウンメニューの 計算 には フリーCaO を分析してある実験結果もあるが その値を このモデルを実行する他に 液相スラグの粘性 固液共存 添加した CaO から差し引くと塩基度が極端に低くなる スラグの熱伝導度を計算するモデルが独立に実行できる ので 実験結果の塩基度を計算する際にはフリーCaO は MPSR モデルの計算時間は 1 s 程度であり 結果は Fig.6 の 考慮しなかった ような表形式で作成される 3 実験結果で 2 次燃焼を考慮しないで酸素収支を計算して 無効酸素量を求め その酸素が 2 次燃焼に費やされたと 4. 各種操業への適用 みなして 2 次燃焼率とする 直接脱炭率は原則的に 50% とした 各種実験に対して このモデルを適用した 全体を通し 4 FeO と P の濃度推移が実験値に合うように GCO と ての計算手順は以下の様なものである km を変化させる メタル側とスラグ側の物質移動係数 1 温度変化を合わせるため熱ロス h を変化させる 誘導 の比 km/ks は 5 で一定とした 尚 スラグ中の Fe2+ 炉の実験の場合は入熱させる場合もある Fe3+ は 実験結果では分離して分析されていない場合が 多いのですべて Fe2+ として扱った 尚 上吹き酸素の直接脱炭率は脱炭速度に影響し FeO 生成比率は T Fe に影響する 一方 GCO はスラグ中の FeO と炭素の反応による CO ガス発生速度を規定するものなの で 脱炭速度だけでなく T Fe に大きく影響を与える 本モ デルではいずれもがパラメータであり 脱炭速度と T Fe の変化に合うように決められるが ここでは直接脱炭率を 原則的に 50% として T Fe の変化に合うよう GCO を決め た 用いた実験データの概要を以下に示す A 社 300 kg 規模誘導溶解炉での実験で フラックスと Fig. 4. Open window of the MPSR model. 酸化鉄を初期一括添加している 酸素ガスは用い ず 撹拌ガスはランスインジェクションで供給さ れている B 社 数トン規模誘導溶解炉での実験で フラックスと 酸化鉄は初期一括添加している 酸素ガスは上吹 きで 撹拌ガスは炉底ノズルから供給されている C 社 200 kg 規模誘導溶解炉での実験で フラックスは 初期一括添加 酸化剤は酸素ガスのみを上吹きで 供給し酸化鉄は用いていない 撹拌ガスは炉底ノ ズルから供給されている D 社 100 kg 規模誘導溶解炉での実験で フラックスを Fig. 5. E xample of the input data for Parameter 1 in the MPSR model. 初期一括添加している 酸化鉄は連続的に分割添 加されているが 酸素ガスは用いていない 撹拌 ガスは炉底ノズルから供給されている 尚 一部 の実験ではフラックスと酸化鉄を同時に連続添加 している E 社 実機上底吹き転炉での実験で フラックスと酸化 鉄は初期一括添加している 酸素ガスは上吹きで 供給し 撹拌ガスは炉底羽口から供給されている 4 1 A 社実験への適用 実験は撹拌ガス流量を変化させた他は一定条件で行われ た フラッグスは生石灰 40 mm 以下 と SiO2 1 mm 以下 を用い 鉄鉱石は 10 mm 以下の細粒のものを用いた 尚 Fig. 6. Example of the output data after the calculation. 62
5 495 Si % mmc 2 S 1/2 m 2 60 s h h% 4chs Table 2 Fig.7 %P %Mn %C T Fe B 社実験への適用 5 25 mm Si % mm C 2 S 1/5 m 5 60 s h DCR 50% 2PCR Table 3 Fig.8.1 %P Fig. 7. Calculation results for the experiments carried out by A- Company ( -cal indicates the calculated lines and -exp indicates the experimental result.) Fig. 8. Calculation results for the experiments carried out by B- Company ( -cal indicates the calculated line and -exp indicates the experimental result.) Table 2. Parameters to calculate the experiments carried out by A-Company. Stirring Gas Flux Diameter k m Gco h Nm 3 /min/t mm m/s mol/(m 2 s) % E E E E E E E E E E E E-03 63
6 496 %Mn.3 k m 4 3 C 社実験への適用 CaO SiO 2 1 mm Si 0%B 0.5 mm C 2 S 1/7 m 7 Table 4 Fig.9 %P %Mn %FeO %C %FeO CaO SiO D 社実験への適用 CaO SiO 2 Si 0% FeO A 5 mm C 2 S 1/5 m 5 Table 5 CaO SiO 2 CaO SiO 2 Table 5 Calc/Exp Fig.10 %P %C %FeO %Mn Table5 G CO G CO 4 5 E 社実験への適用 mm Si % B Fig. 9. Calculation results for the experiments carried out by C- Company ( -cal indicates the calculated line and -exp indicates the experimental result.) Table 3. Parameters to calculate the experiments carried out by B-Company. Top Blown O 2 Stirring Gas Flux Diameter k m Gco h PCR DCR Nm 3 /min/t Nm 3 /min/t mm m/s mol/(m 2 s) % % % E E E E E E E E E Table 4. Parameters to calculate the experiments carried out by C-Company. Top Blown O 2 Stirring Gas Flux Diameter k m Gco h PCR DCR Nm 3 /min/t Nm 3 /min/t mm m/s mol/(m 2 s) % % % E E E E E E E E E
7 mm C 2 S 1/2 m 2 4chs Table 6 Fig.11 %FeO.2 50% m Fig. 10. Calculation results for the experiments carried out by D-Company ( -cal indicates the calculated line and -exp indicates the experimental result.) Fig. 11. Calculation results for the experiments carried out by E- Company ( -cal indicates the calculated line and -exp indicates the experimental result.) Table 5. Parameters to calculate the experiments carried out by D-Company. Stirring Gas Flux Diameter k m Gco h Calc./Exp Nm 3 /min/t mm m/s mol/(m 2 s) % CaO SiO E E E E E E E E E E E E Table 6. Parameters to calculate the experiments carried out by E-Company. Top Blown O 2 Stirring Gas Flux Diameter k m Gco h PCR DCR Nm 3 /min/t Nm 3 /min/t mm m/s mol/(m 2 s) % % % E E E E E E E E E E E E
8 考察 C 2 S 1/m 2 7 k m CO G CO D CO k m 19 Fig B W/t k m E H m Fig.13 CO G CO Fig.14 B %CaO / %SiO 2 G CO Nagasaka 21 FeO CO Nagasaka FeO Fe 3+ /Fe 2+ Fig.14 C 2 R % Fig.15 G CO R Nm 3 /t Nm 3 /t Q g Nm 3 /min W t T L K P a Pa T n K h 0 m D m Fig. 13. Relation between mass transfer coefficient in metal phase and stirring energy considering the size of the equipment. Fig. 12. Relation between mass transfer coefficient in metal phase and stirring energy. Fig. 14. Relation between rate constant of CO gas formation and average basicity of slag. 66
9 499 CO Fig. 15. Relation between rate constant of CO gas formation and oxygen gas ratio. 謝辞 B JFE CO 結言 B MPSR Multi-Phase Slag Refining Windows Microsoft C s CSV Microsoft Excel 5 文 1 ) S.Kitamura: Proc. of 8th International Conference on Molten Slags, Fluxes and Salts, Santiago, (2009), ) S.Kitamura: CAMP-ISIJ, 23(2010), 527, CD-ROM. 3 ) W.Fix, H.Heymann and R.Heinke: J. Am. Ceram. Soc., 52(1969), ) K.Ito, M.Yanagisawa and N.Sano: Tetsu-to-Hagané, 68(1982), ) R.Inoue and H.Suito: ISIJ Int., 46(2006), ) F.Tsukihashi: Tetsu-to-Hagané, 95(2009), ) K.Ito and M.Terasawa: Proc. of 13th VDEh-ISIJ Joint Meeting of New Scope of Iron and Steelmaking Consistent with Environment, ISIJ, Tokyo, (2008), ) S.Ohguchi, D.G.C.Robertson, B.Deo, P.Grieveson and J.H.E.Jeffes: Ironmaking Steelmaking, 11(1984), ) S.Kitamura, T.Kitamura, E.Aida, R.Sakomura, T.Kaneko and T.Nuibe: ISIJ Int., 31(1991), ) S.Kitamura, K.Miyamoto, H.Shibata, N.Maruoka and M.Matsuo: ISIJ Int., 49(2009), ) S.Kitamura, H.Shibata and N.Maruoka: Steel Res., 79(2008), ) K.Ito and M.Mori: CAMP-ISIJ, 25(2012), 188, CD-ROM. 13) M.Hanao, M.Kawamoto, T.Tanaka and M.Nakamoto: ISIJ Int., 46(2006), ) M.Susa, N.Tsuchida, R.Endo and Y.Kobayashi: Tetsu-to-Hagané, 95(2009), ) F.Pahlevani, S.Kitamura, H.Shibata and N.Maruoka: ISIJ Int., 50(2010), ) S.Ban-ya: ISIJ Int., 33(1993), 2. 17) M.Matsushima, S.Yadoomaru, K.Mori and Y.Kawai: Trans. Iron Steel Inst. Jpn., 17(1977), ) M.Umakoshi, K.Mori and Y.Kawai: Trans. Iron Steel Inst. Jpn., 24(1984), ) S.Kitamura, T.Kitamura, K.Shibata, Y.Mizukami, S.Mukawa and J.Nagakawa: ISIJ Int., 31(1991), ) K.Mori and M.Sano: Tetsu-to-Hagané, 67(1981), ) T.Nagasaka, Y.Iguchi and S.Ban-ya: Tetsu-to-Hagané, 75(1989), 74. 献 67
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