Preparation of iron oxide red by sinking iron slag in zinc smelting hematite process
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摘要: 針對赤鐵礦渣中存在雜質，影響其綜合回收利用的問題，開展赤鐵礦渣高溫水熱法脫雜，制備鐵紅的研究。研究了不同酸度、溫度、時間和液固比條件，對鐵紅產品中鐵、鋅、硫含量以及鋅、硫脫除率和鐵溶出率的影響。實驗結果表明：pH值為1，溫度220 ℃，保溫時間3 h，液固比6∶1，轉速400 r·min?1條件下，鐵紅產品中鐵質量分數由58.66%上升為66.83%；赤褐鐵類礦物含鐵由占總鐵質量分數94.05%，上升為97.79%；硫質量分數由2.96%下降至0.82%；鋅質量分數由1.03%下降至0.18%。經X射線衍射檢測，與赤鐵礦渣相比，鐵紅產品中氧化鐵信號峰值提高，雜峰減少。通過掃描電鏡/能量散射X射線分析，鐵紅產品表面附著的硫酸鹽等雜質經高溫水熱法處理后明顯減少；實驗前后，赤鐵礦渣與鐵紅產品顆粒形貌與大小沒有發生變化。實驗處理后的鐵紅產品經檢測，滿足國家標準氧化鐵紅含鐵量C級，水溶物和水溶性氯化物及硫酸鹽含量III型，篩余物2型，105 ℃揮發物V2型，來源a型標準。Abstract: In wet zinc smelting process, iron slag generated by hematite process has high iron content, uniform particle size, and stable thermodynamics, which have evident advantages. However, impurities are present in hematite slag, including jarosite, basic ferric sulfate, adsorptive salts, and small amounts of iron carbonate and iron silicate, that limit its comprehensive recovery and utilization. In view of these impurities in hematite slag, in this study, iron oxide red was prepared using a high-temperature hydrothermal method. The effects of different acidity levels, temperatures, preparation times, and liquid–solid ratios on the contents of iron, zinc, and sulfur were studied, as were the removal rates of zinc and sulfur and dissolution rate of iron. The experimental results show that the iron content in the iron oxide red products increases from 58.66% to 66.83% at following parameters: pH 1, temperature 220 ℃, preparation time 3 h, liquid–solid ratio 6∶1, and rotation speed 400 r·min?1. The iron content of the ferrous minerals increases from 94.05% to 97.79%, sulfur content decreases from 2.96% to 0.82%, and zinc content decreases from 1.03% to 0.18%. As determined by X-ray diffraction, compared with hematite slag, the peak value of the iron oxide signal in the iron oxide red products is higher and that of the miscellaneous peak is lower. Scanning electron microscopy analysis/energy dispersive analysis of X-rays show that the amounts of sulfate and other impurities on the surface of the iron oxide red products are significantly reduced after high-temperature hydrothermal treatment. However, the morphologies and sizes of the hematite slag and red iron oxide product particles do not change. After the experimental treatment, the iron oxide red products are determined to meet the national standard: iron oxide red content grade C, water soluble substance and water-soluble chloride and sulfate content type III, sieve residue type 2, 105 ℃ volatile type V2, source type a standard.
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圖 2 不同酸度對鐵紅產品質量，鋅、硫脫除率以及鐵溶出率的影響。（a）鐵紅產品中鐵、鋅、硫質量分數；（b）鋅、硫脫除率以及鐵溶出率
Figure 2. Effects of different acidity levels on iron oxide red content, impurity removal rate, and iron dissolution rate: (a) iron, zinc, sulfur mass fraction in iron oxide red products; (b) removal rate of zinc and sulfur and iron dissolution rate
圖 4 不同溫度對鐵紅產品質量，鋅、硫脫除率以及鐵溶出率的影響。（a）鐵紅產品中鐵、鋅、硫質量分數；（b）鋅、硫脫除率以及鐵溶出率
Figure 4. Effects of different temperatures on iron oxide red product content, impurity removal rate, and iron dissolution rate: (a) iron, zinc, sulfur mass fraction in iron oxide red products; (b) removal rate of zinc and sulfur and iron dissolution rate
圖 5 不同反應時間對鐵紅產品質量，鋅、硫脫除率以及鐵溶出率的影響。（a）鐵紅產品中鐵、鋅、硫質量分數；（b）鋅、硫脫除率以及鐵溶出率
Figure 5. Effects of different preparation times on iron oxide red product content, impurity removal rate, and iron dissolution rate: (a) iron, zinc, sulfur mass fraction in iron oxide red products; (b) removal rate of zinc and sulfur and iron dissolution rate
圖 6 不同液固比對鐵紅產品質量，鋅、硫脫除率以及鐵溶出率的影響。（a）鐵紅產品中鐵、鋅、硫質量分數；（b）鋅、硫脫除率以及鐵溶出率
Figure 6. Effects of different liquid–solid ratios on iron oxide red product content, impurity removal rate, and iron dissolution rate: (a) iron, zinc, sulfur mass fraction in iron oxide red products; (b) removal rate of zinc and sulfur and iron dissolution rate
圖 7 赤鐵礦渣與綜合實驗條件產出鐵紅產品X射線衍射圖
Figure 7. X-ray diffraction pattern of slag compared with that of raw material
表 1 赤鐵礦渣中主要元素含量(質量分數)
Table 1. Content of main elements in hematite
% Fe Zn S K Na 58.66 1.03 2.96 0.028 0.061 
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表 2 赤鐵礦渣中鐵物相含鐵占比(質量分數)
Table 2. Proportions of iron content in hematite slag
% Iron in magnetic iron minerals Iron in iron carbonate minerals Iron in silicate minerals Iron in sulfate minerals Iron in red brown iron minerals 1.23 0.58 1.74 2.39 94.05
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表 3 赤鐵礦渣浸出毒性檢測結果
Table 3. Hematite residue leaching toxicity test results
mg·L?1 Index Fluoride Cyanide Hexavalent chromium Copper Lead Zinc Cadmium Beryllium Standard 100 5 5 100 5 100 1 0.02 Content 0.09 — — 0.253 0.084 75.7 0.045 0.0015 Index Nickel Total chromium Arsenic Selenium Barium Mercury Silver Standard 5 15 5 1 100 0.1 5 Content 0.027 0.012 0.010 0.0072 0.0066 0.0002 —
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表 4 檢測最佳條件處理的鐵紅產品與赤鐵礦渣中各鐵物相含鐵質量分數占比
Table 4. Proportion of iron content in the iron phase between the iron red product and the hematite residue under the best condition
Sample types Iron in magnetic iron minerals/% Iron in iron carbonate minerals/% Iron in silicate minerals/% Iron in sulfate minerals/% Iron in red brown iron minerals/% Hematite slag 1.23 0.58 1.74 2.39 94.05 Iron red products <0.75 0.10 0.75 0.58 97.79
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表 5 鐵紅產品與赤鐵礦渣中鐵，鋅，硫質量分數對比
Table 5. Comparison of zinc, iron, and sulfur mass fractions in iron oxide red products and hematite slag
% Sample types Fe Zn S Hematite slagIron 58.66 1.03 2.96 Iron oxide red products 66.83 0.18 0.82
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