新型再利用脫硫劑於高週波爐與盛鋼桶精煉爐之脫硫研究 * Investigations of desulfurization of new re-used desulfurizer in high frequncy induction furnace and ladle furnace 1 2 3 3 C.M. Lin, J.Y. Uan, W.J. Tseng, W. Wu 50 % CaO 1:1 CaO (%) (%) CaO content in steel (%) = 0.00178 + 0.000155383 (Desulfurization ability,%) CaO 1:1 (13 ) 2 % 40 0.045 wt% 0.018 wt% 60 % CaO 1:1 (106 ) 0.76 % 30 0.045 wt% 0.0304 wt% 32.4 % CaO 1 1 關鍵詞 : CaO This investigation successfully uses the high frequncy induction furnace to execute the experiment of refining desulfurization by adding the new re-used desulfurization agent. Results reveal that the new re-used desulfurization agent possesses the 50 % desulfurization ability, as the ratio of supplement CaO and refining slag in the new reused desulfurization agent is approach 1:1. The relative equation between CaO ratio of desulfurization agent in steel and desulfurization ratio after 30 min reaction performed mathematical calculation by computer simulation is CaO content in steel (%) = 0.00178 + 0.000155383 (Desulfurization ability,%). The molten steel with 13 tons (medium-scale steel plant) is successfully refined from the initial sulfur content of about 0.045 wt% to the sulfur content of about 0.018 wt% at 40 minutes, as the desulfurization agent with 50 % supplement CaO and 50 % refining slag is 2 wt% of the total weight of the molten steel. The desulfurization ratio is about 60%. In this investigation, the new re-used desulfurization agent is also applied in the lardescale steel plant to refine desulfurization (106 ton). As the desulfurization agent with 50 % supplement CaO and 50 % refining slag is 0.76 wt% of the total weight of the molten steel, the molten steel with 106 tons (large-scale steel plant) is successfully refined from the initial sulfur content of about 0.045 wt% to the sulfur content of about 0.0304 wt% at 30 minutes. The desulfurization ratio is about 32.4 %. Therefore, this study shows that the new re-used desulfurization agent can be successfully applied in the medium-scale and largescale steel plants to refine desulfurization and the sulfur content conforms the degree of steel bar, as the ratio of supplement CaO and refining slag is approach 1:1. Key words: New re-used desulfurization agent, Refining slag, Supplement CaO, Desulfurization ratio * 1 2 3 鑛冶 57/4-51-
一 前言 C Si Mn P S H O P S P Fe 2 P S Fe FeS (1) (2) 2006 65.5% 32% 2009 43.0% 43.6% 61.7% 43.0% ( ) (Ladle Furnace) ( ) ( ) ( ) -CaO (Ls) (1) [ ] ( ) (1) (CaO) [O] S CaO-SiO 2 -Al 2 O 3 -MgO (3) CaO ( 1600 ) CaO CaO (Ls) -1 Al 2 O 3 -CaO-SiO 2-5wt%MgO SiO 2 10 wt% (Ls) CaO Al 2 O 3 CaO -CaO -CaO (4,5) CaO CaO CaO CaF 2 6~12% (6-8) -52- 一 二年十二月
CaF 2 CaO (9) CaF 2 CaF 2 [FeS] + (CaO) = (CaS) + [FeO] (1) -1 1600 o C Al 2 O 3 -CaO-SiO 2-5wt%MgO 15 20 CO 2 (CaF 2 ) CO 2 (10-12) -CaO (13,14) Yoshie (14) 70% (13 ) (106 ) 二 研究方法 ( ) (CaO) -2 鑛冶 57/4-53-
-2 2.1 鋼材選用與脫硫劑設計 -1 ( -2 ) (CaO) -3-1 Chemical composition (wt%) Material C Si Mn P S Fe Test steel 0.14 0.17 0.42 0.014 0.012 Bal. -2 Chemical composition (wt%) Material CaO A-CaO SiO 2 Al 2 O 3 MgO FeO MnO CaF 2 CaS Re-used slag 47.90 0.16 11.30 33.30 4.73 1.06 0.37 0.08 1.78-3 Prescription Material Re-used slag Supplement (CaO) A 100% 0 B 75% 25% C 65% 35% D 50% 50% -54- 一 二年十二月
2.2 脫硫實驗 60 1.2 50g 48 wt% S (FeS) 0.05 wt% 1620 1615-1625 10 30 g 90 g ( 0.15 wt%) 30 200 g FeS 0.05 wt% 1620 1615-1625 10 20 ppm 30 200 g 2.3 鋼液品質與爐渣成份定量分析 (Spark) C-S X (WDS-XRF) CaO SiO 2 Al 2 O 3 MgO MnO WDS-XRF CaF 2 SiF 4 -CaO (A-CaO) (C 12 H 22 O 11 ) OH A-CaO Ca(OH) 2 OH C 12 H 22 O 11 CaO 2H 2 O Ca 2+ KOH EDTA ph 13 EDTA Ca 2+ (2) A-CaO 3~5 CaO Ca(OH) 2 OH Ca 2+ EDTA Ca 2+ Ca 2+ CaO Ca(OH) 2 Ca 2+ A-CaO (2) M EDTA (M) V EDTA (ml) W (g) 鑛冶 57/4-55-
CaO(%)= M V 56.08 1000 (2) W 1000 CaO+H 2 O=Ca(OH) 2 (3) Ca(OH) 2 +C 12 H 22 O 11 =C 12 H 22 O 11 CaO 2H 2 O (4) C 10 H 16 N 2 O 8 + C 12 H 22 O 11 CaO 2H 2 O= Ca(C 10 H 14 N 2 O 8 )+C 12 H 22 O 11 +3H 2 O (5) Fe WDS-XRF Fe Fe 2+ WDS-XRF Fe Fe 2+ Fe 3+ Fe Fe 2(FeCl 3 ) 3(FeCl 2 ) 5C 15-20 ml 5-8 SDPA 0.1N K 2 Cr 2 O 7 ( ) Fe Fe Fe 2+ Fe Fe 2+ 30 ml HCl 5-10 ml 150 ml 20 ml ( ) 5-8 SDPA 0.1 N K 2 Cr 2 O 7 ( ) Fe Fe 2+ 3.1 實驗室高週波爐之精煉脫硫結果 三 分析結果與討論 -3 DTA 1330 o C -4 C 5 CaO 10 CaO -3 DTA -56- 一 二年十二月
-4 C -4 ( ) Chemical composition of test steel at 0 min (wt%) Prescription C Si Mn P S Fe A 0.113 0.109 0.146 0.0140 0.0460 Bal. B 0.127 0.173 0.319 0.0139 0.0521 Bal. C 0.124 0.167 0.253 0.0173 0.0462 Bal. D 0.121 0.150 0.267 0.0142 0.0479 Bal. -4-5 -4 A 0.113 wt% 0.0460 wt% B 0.127 wt% 0.0521 wt% C 0.124 wt% 0.0462 wt% D 0.121 wt% 0.0479 wt% -5 30 A 0.126 wt% 0.0500 wt% B 0.132 wt% 0.0422 wt% C 0.121 wt% 0.0333 wt% D 0.130 wt% 0.0212 wt% 鑛冶 57/4-57-
-5 30 Prescription Chemical composition of test steel at 30 min (wt%) C Si Mn P S Fe A 0.126 0.170 0.257 0.0140 0.0500 Bal. B 0.132 0.192 0.342 0.0233 0.0422 Bal. C 0.121 0.208 0.306 0.0258 0.0333 Bal. D 0.130 0.202 0.374 0.0139 0.0212 Bal. -5 CaO CaO CaO -5 CaO (%) (%) (6) 50 % CaO 1:1 CaO 1:1 (13 ) (100 ) -6 30 active- CaO CaO CaO content in steel(%)= 0.00178 + 0.000155383 (Desulfurization ability,%) (6) -5 CaO -58- 一 二年十二月
-6 30 Chemical composition (wt%) Prescription CaO A-CaO SiO 2 Al 2 O 3 MgO FeO MnO CaS BI A 37.1 0.19 15.5 39.7 4.88 1.35 0.79 0.96 2.39 B 40.7 0.12 12.4 31.2 3.25 1.78 0.48 1.46 3.28 C 50.5 0.89 10.6 31.2 3.25 1.43 0.63 2.41 4.76 D 43.8 0.15 11.7 31.5 8.38 1.56 0.39 2.53 3.74 3.2 中型在地鋼廠盛鋼桶精煉爐之精煉脫硫結果 CaO 1:1 (13 ) 13000 Kg 260 Kg ( 2%) 1620 20 ppm 1650 1620-6 0.045 wt% 20 0.045 wt% 0.021 wt% 40 0.018 wt% CaO 1:1 40 min 0.045 wt% 0.018 wt% 60 % -6 13T 鑛冶 57/4-59-
13T 40-7 active-cao 5 % CaO -7 (Cs) S active-cao -7 13T 40 Chemical composition (wt%) First slag CaO A-CaO SiO 2 Al 2 O 3 MgO FeO MnO CaS BI 13T 43.04 5.07 17.73 16.28 16.98 1.69 2.05 0.36 2.43 3.3 大型在地鋼廠盛鋼桶精煉爐之精煉脫硫結果 (106T) CaO 1:1 2 % active-cao CaO 1:1 (106 ) 106000 Kg 810 Kg ( 0.76 %) 1620 C 20 ppm -7 0.045 wt% 20 0.045 wt% 0.033 wt% 30 0.0304 wt% CaO 1:1 30 min 0.045 wt% 0.0304 wt% 32.4 % 106T -8 10 mim active-cao 1.35 % 10 min 20 mim 30 min active-cao 1.35 % 10 mim S active-cao -60- 一 二年十二月
-7 106T -8 106T First slag 106T Time (min) Chemical composition (wt%) CaO A-CaO SiO 2 Al 2 O 3 MgO FeO MnO CaS 10 42.06 1.35 29.89 5.83 8.86 0.54 1.47 1.23 1.41 20 41.88 1.35 30.84 6.18 9.28 0.60 0.96 1.26 1.36 30 41.62 1.34 30.63 6.66 9.97 0.93 1.08 1.05 1.36 BI 四 結論 50% CaO 1:1 CaO (%) (%) CaO content in steel(%) = 0.00178 + 0.000155383 (Desulfurization ability,%) CaO 1:1 (13 ) 2 % 40 0.045 wt% 0.018 wt% 60 % active-cao( 5.07 %) CaO CaO 1:1 (106 ) 0.76 % 30 0.045 wt% 鑛冶 57/4-61-
0.0304 wt% 32.4 % active-cao( 1.35 %) 五 致謝 (NSC101-3111-E-005-001) 六 參考文獻 (1) 1-6 2009 (2) 2010 2-13-2-48 2010 (3) A. Muan and E.F. Osborn, Phase equilibria among oxides in steelmaking, Addison-Wesley Publishing Company, Inc., pp. 103-142, 1965. (4) * B 2 O 3 CaF 2 CaO Vol. 56, No. 2, pp. 82-90, 2012. (5) C.M. Lin, L.H. Chen, K.Y. Wang, C.H. Wu and W. Wu, Effects of Recycling Desulfurization Slag on the Characteristics of Molten Steel, IUMRS-ICA 2011, Taipei, Taiwan, September, 2011. (6) H. Wang, T. Zhang, H. Zhu, G. Li, Y. Yan and J. Wang, Effect of B 2 O 3 on melting temperature, viscosity and desulfurization capacity of Cao-based refining flux, ISIJ International, Vol. 51, No. 5, pp. 702-706, 2011. (7) L. Wu, J. Gran and D. Sichen, The effect of calcium fluoride on slag viscosity, Metallurgical and Materials Transactions B, Vol. 42B, pp. 928-931, 2011. (8) H.M. Wang, G.R. Li, Z.T. Ding, Q.X. Dai and B. Li, Effect of additives on melting point of LATS refining ladle slag, ISIJ International, Vol. 46, pp. 637-640, 2006. (9) 14-33 2007 (10) J.M. Manso, A. Rodriguez, A. Aragon and J.J. Gonzalez, The durability of masonry mortars made with ladle furnace slag, Construction and Building Materials, Vol. 25, pp. 3508-3519, 2011. (11) A. Rodriguez, J.M. Manso, A. Aragon, and J.J. Gonzalez, Strength and workability of masonry mortars manufactured with ladle furnace slag, Resources, Conservation and Recycling, Vol. 53, pp. 645-651, 2009. (12) D. Durinck, F. Engstrom, S. Arnout, J. Heulens, P.T. Jones, B. Bjorkman, B. Blanpain, and P. Wollants, Hot stage processing of metallurgical slags, Resources, Conservation and Recycling, Vol. 52, pp. 1121-1131, 2008. (13) M. Francesco, M. Carlo and G. Marta, Recycling of ladle slag in the EAF: A way to improve environmental conditions and reduce variable costs in steel plants, Iron and Steel Technology, Vol. 4, No. 2, pp. 68-76, 2007. (14) N. Yoshie, K. Naoki, I. Maki, N. Seiji, and K. Yasuo, Development of slag recycling process in hot metal desulfurization with mechanical stirring, Steel Research International, Vol. 80, No. 10, pp. 727-732, 2009. -62- 一 二年十二月