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摘要: 為打通轉爐煉鋼過程錳礦熔融還原技術路徑，提高錳的收得率，對錳礦熔融還原過程和提高錳收得率的工藝參數進行了熱力學探討，并在某鋼廠200 t轉爐上開展了工業試驗研究。研究結果表明：高效穩定的鐵水“三脫”預處理技術是錳礦熔融還原技術成功的基本前提；通過理論計算，在爐渣中的(MnO)質量分數為5%～10%，終點[C]質量分數控制在0.13%～0.36%時，終點鋼液[Mn]質量分數可控制在0.3%以上。工業試驗主要通過采用雙渣法冶煉操作，在確保前期鐵水低磷的條件下盡可能控制少渣量、降低爐渣中氧化鐵，從而實現加入錳礦后提高錳收得率；并在現有工藝控制條件下，錳礦加入10 kg·t?1以內時，工業試驗可使錳礦還原過程錳收得率超過40%，平均為51.40%；為進一步提高錳收得率，建議嚴格將錳礦熔融還原渣料總量控制在40～60 kg·t?以內，石灰加入量控制在10～15 kg·t?1以內；研究結果為錳礦熔融還原技術的開發和應用提供重要參考。Abstract: The smelting reduction of manganese ore in the converter has been reported in China since the 1990s, and some steel enterprises have successively carried out industrial tests of this technology. However, the recovery ratio of Mn in manganese ore is low and fluctuates greatly due to various reasons such as inadequate hot-metal pretreatment, the poor bottom blowing effect of the converter furnace, and unreasonable positioning of the smelting end point. The smelting reduction of manganese ore has not been successfully applied in converter steelmaking and failed to benefit steel enterprises. In this study, the thermodynamic parameters of manganese ore melting reduction were discussed to improve the recovery ratio and yield of manganese and find a way to directly use manganese ore in a converter. The industrial test was carried out in a 200 t converter at a steel mill. Results showed that the efficient and stable ‘tri-de’ (dephosphorization/desulphurization/desiliconization) hot-metal pretreatment was the basic premise for the success of manganese ore smelting reduction. The theoretical calculation revealed that when the content of MnO in slag is 5%–10% and the terminal content of [C] is 0.13%–0.36%, the end-point of [Mn] in molten steel can be controlled above 0.3%. For an improved recovery ratio of Mn in manganese, the industrial test mainly adopted the smelting operation of double-slag operation to ensure that the amount of slag and iron oxide in the slag was reduced as much as possible under low phosphorus content in molten iron in the early stage. Under the existing process control conditions, the industrial test results showed a manganese yield of more than 40% and an average value of 51.40% when the added amount of manganese ore was under 10 kg·t?1. For an excellent manganese yield, the total amount of manganese smelting reduction slag must be strictly controlled from 40 kg·t?1 to 60 kg·t?1, and the amount of lime must be 10–15 kg·t–1. This work provides an important reference for the development and direct application of manganese ore in the converter.
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圖 1 試驗用錳礦XRD物相分析. (a)高品位錳礦；(b)低品位錳礦
Figure 1. XRD phase analysis of the manganese ore used in the experiment: (a) high grade manganese ore; (b) low grade manganese ore
圖 2 試驗用錳礦巖相照片。(a)高品位錳礦；(b)低品位錳礦
Figure 2. Lithofacies photos of the manganese ore used in the experiment: (a) high grade manganese ore; (b) low grade manganese ore
圖 3 煉鋼溫度下
$\Delta_{{\rm{r}}}G^{\ominus}- T $ 圖Figure 3.
$\Delta_{{\rm{r}}}G^{\ominus}- T $ diagram at steelmaking temperature
圖 4 終點碳含量和錳含量的平衡關系
Figure 4. Equilibrium relationship between end-point carbon content and manganese content
圖 5 渣中(FeO)和終點錳含量的平衡關系
Figure 5. Equilibrium relationship between end-point manganese content and (FeO) in slag
圖 6 不同錳礦加入量下終點碳含量和錳含量的平衡關系
Figure 6. Equilibrium relationship between end-point carbon content and manganese content under different amounts of manganese ore input
圖 7 不同錳礦品位時各試驗爐次錳收得率
Figure 7. Manganese recovery ratio of different manganese ore grades
圖 8 轉爐前期脫磷率與轉爐終點錳收得率之間的關系
Figure 8. Relationship between the dephosphorization ratio of the early process in the converter and the manganese recovery ratio of end-point
圖 9 轉爐終點碳含量對錳收得率的影響
Figure 9. Effects of the end-point carbon content of converter on the recovery ratio of manganese
圖 10 轉爐終點碳含量對錳分配比的影響
Figure 10. Effects of the end-point carbon content on manganese distribution ratio in the converter
圖 12 典型爐次爐渣的礦相組成. (a)堿度為3.10；(b)堿度為3.28
Figure 12. Typical mineral phase composition of slag: (a)basicity is 3.10; (b) basicity is 3.28
表 1 國內外鋼鐵廠轉爐錳礦熔融還原工藝（國內僅限于工業試驗）[14-21]
Table 1. Smelting reduction of manganese ore in converter worldwide (industrial test in domestic) [14-21]
Steel plant Year Converter capacity/
tManganese ore addition/
(kg?t?1)Total manganese mass fraction in manganese ore/% End point carbon mass fraction/
%Alloying process Manganese yield/
%Fukuyama 1987 250 15–20 54.4 0.1 Hot metal triple stripping + less slag smelting 65–70 Kobe 1990 100 10 49.2 0.25 70 Keihin 1990 250 10 47 0.20 65 Oita 1992 340 12–13 43.2 0.14 70–80 Pansteel 1988 120 4–6 17.44 Traditional smelting process of converter 20 Shanggang No.5 plant 1992 15 22 20.3 30 Laiwu Steel 2001 120 4 27 0.11 23 Jinan Steel 2002 25 10 30 0.1 36 Tangshan Steel 2004 30 6–10 24 0.07 13–27 WISCO 2010 100 4–4.3 42 0.097 30 Linyi steel pipe 2012 120 4 42 0.119 25–35 Xingtai Steel 2014 50 20 15 0.084 26.1 Guofeng Steel 2014 120 5 32 0.06 13 Fushun Xingang 2015 45 10.16 12.68 0.06 48 Baosteel 2002 300 5–8.7 35 0.05 Hot metal triple stripping + less slag smelting 50–67 Baosteel 2005 300 5–15 35 0.05 Hot metal triple stripping + duplex process 70 WISCO 2013 10–20 48.24 0.04~0.05 Desulfurization of hot metal + double slag process 35–45 
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表 2 某鋼廠試驗鋼種82B化學成分（質量分數）
Table 2. Chemical composition of 82B from a steel plant
% Steel grade C Si Mn P S Cr V SWRH82B-L 0.79–0.86 0.15–0.35 0.60–0.90 $\leqslant$0.025 $\leqslant$0.025 0.15–0.35 0.040–0.060 Target value 0.82–0.82 0.20 0.80 $\leqslant$0.020 $\leqslant$0.010 0.25 0.050 Internal control value 0.74–0.81 0.18–0.22 0.72–0.78 $\leqslant$0.020 $\leqslant$0.010 0.23–0.27 0.048–0.052
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表 3 研究試驗方案
Table 3. Test plan of the experiments
No. Manganese ore type Manganese ore scheme addition/
(kg·t?1)Actual addition amount
of manganese ore/
tActual addition amount of manganese ore/
(kg·t?1)Remarks 1-1 High-grade manganese ore 7.5 1548 7.7 Effect of manganese ore addition on manganese yield 1-2 10 1974 9.4 1-3 15 2929 14.1 2-1 Low-grade manganese ore 5 1000 4.9 Effect of manganese ore addition on manganese yield 2-2 997 4.9 2-3 1043 5.4 2-4 1048 5.3 2-5 1050 5.3 2-6 7.5 1625 7.7 2-7 1654 8.0 2-8 10 2048 10.6 2-9 12.5 2554 13.4 2-10 15 2547 14.1 2-11 20 4069 20.3
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表 4 試驗用錳礦的化學成分（質量分數)
Table 4. Chemical composition of the manganese ore for the industrial test
% Name T.Mn SiO2 T.Fe S P High-grade manganese ore 48 10.86 8.31 0.004 0.0038 Low-grade manganese ore 35 8.46 4.67 0.034 0.0019
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表 5 鐵水條件和鋼水終點情況
Table 5. Molten iron condition and terminal condition of molten steel
No. Hot metal condition End-point condition Manganese yield/% w[P]/% T/℃ w[C]/% w[Mn]/% w[P]/% w[S]/% T/℃ 1-1 0.117 1303 0.16 0.19 0.015 0.017 1594 40.61 1-2 0.114 1258 0.16 0.211 0.0144 0.016 1597 49.10 1-3 0.146 1270 0.14 0.21 0.018 0.015 1620 32.43 2-1 0.132 1351 0.20 0.13 0.014 0.011 1580 46.77 2-2 0.13 1248 0.11 0.134 0.0171 0.014 1594 48.13 2-3 0.138 1289 0.16 0.2 0.017 0.013 1587 79.30 2-4 0.144 1277 0.16 0.18 0.014 0.011 1595 48.39 2-5 0.137 1280 0.18 0.12 0.011 0.014 1575 37.67 2-6 0.13 1252 0.21 0.207 0.0181 0.009 1580 60.99 2-7 0.124 1305 0.14 0.218 0.0171 0.014 1604 60.01 2-8 0.141 1266 0.15 0.21 0.014 0.01 1588 43.04 2-9 0.136 1279 0.12 0.20 0.015 0.016 1610 29.85 2-10 0.13 1293 0.11 0.18 0.011 0.013 1586 26.26 2-11 0.146 1264 0.12 0.22 0.015 0.014 1569 23.95
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表 6 轉爐終點爐渣成分
Table 6. Composition of converter terminal slag
No. Composition of converter final slag Slag basicity wCaO/% $w_{ {\rm{Si} }{\rm{O} }_{2} }$/% wMgO/% wT.Fe/% w$w_{ {\rm{P} }_{2}{\rm{O} }_{5} }$/% wMn/% $w_{{\rm{Al} }_{2}{\rm{O} }_{3}}$/% 1-1 42.47 10.94 6.79 19.73 2.66 5.84 1.22 3.88 1-2 45.09 11.12 7.81 14.48 2.68 8.01 1.71 4.05 1-3 The final slag sample was not obtained 2-1 43.69 14.65 5.92 9.12 3.10 3.67 1.5 3.10 2-2 41.20 13.31 5.02 13.53 2.97 4.71 1.35 4.84 2-3 49.25 10.17 8.88 14.76 2.61 4.88 1.11 4.57 2-4 48.58 10.62 8.01 15.98 2.65 4.63 1.13 4.13 2-5 46.72 11.30 10.88 14.96 2.85 4.40 1.10 3.28 2-6 43.36 13.23 4.76 11.65 3.12 4.80 1.38 3.25 2-7 43.23 13.31 4.72 11.50 3.12 4.79 1.38 4.05 2-8 45.71 11.29 8.06 16.44 2.86 6.36 1.11 3.68 2-9 46.58 12.66 7.54 14.45 2.88 6.34 1.00 4.19 2-10 43.44 10.36 7.35 18.76 2.17 7.23 1.02 3.88 2-11 The final slag sample was not obtained
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表 7 爐渣物相質量分數和堿度
Table 7. Slag phase mass fraction and slag basicity
No. Mass fraction of each phase, % Slag basicity C3S C2S RO C2F f-CaO a 35-40 30-35 5-10 5-10 3-5 3.10 b 35-40 20-25 10-15 10-15 3-5 3.28
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