TiO<sub>2</sub>对高铝高炉渣性能和结构的影响研究

闫华; 刘华军; 陈布新; 扈玫珑

doi:10.7513/j.issn.1004-7638.2022.02.018

TiO₂对高铝高炉渣性能和结构的影响研究

doi: 10.7513/j.issn.1004-7638.2022.02.018

1.
重庆惠能标普科技有限公司, 重庆401121
2.
重庆大学材料科学与工程学院, 重庆400044

基金项目: 国家重大专项研发计划项目(2018YFC190050404)。

详细信息

作者简介:
闫华（1982—），男，重庆人，高级工程师，主要研究方向为冶金工程及工程设计，E-mail：54927517@qq.com

通讯作者:
扈玫珑（1980—），女，甘肃白银人，教授，主要研究方向为冶金工程，E-mail：hml@cqu.edu.cn

中图分类号: TF534.1
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出版历程
- 收稿日期: 2021-12-18
- 网络出版日期: 2022-05-11
- 刊出日期: 2022-04-28

Effect of TiO₂ on physicochemical properties and structure of high-alumina blast furnace slag

Yan Hua^1
,,
Liu Huajun¹,
Chen Buxin²,
Hu Meilong^{2
, ,}

1.
Chongqing Huineng Biaopu Technology Co., Ltd., Chongqing 401121, China
2.
College of Material Science and Engineering, Chongqing University, Chongqing 400044, China

摘要

摘要: 随着国内各钢铁企业高炉配加经济性较高的高铝原料的增加，炉渣中Al₂O₃含量增加，渣铁流动性变差，给高炉冶炼带来一系列问题。以CaO-SiO₂-Al₂O₃-MgO-TiO₂五元渣系为研究对象，通过相图理论计算结合试验研究和炉渣结构分析，研究了高铝渣中不同TiO₂含量（低钛：5%，中钛：15%，高钛：25%）对高铝高炉渣黏度、熔化性温度的影响，并通过炉渣结构研究解析了影响炉渣物化性能的原因。结果表明：固定碱度R₂为1.25，TiO₂质量分数增加至25%过程中，炉渣熔化温度先下降后增高，当TiO₂质量分数为7%时，炉渣液相析出相由斜长石类的钙铝硅酸盐(Ca₂Al₂SiO₇)转变为高熔点钛酸钙（CaTiO₃），其熔点为1975 ℃，炉渣熔化温度增加；TiO₂含量由低钛5%增加至高钛25%时，炉渣黏度和熔化性温度均降低。温度越高，炉渣流动性越好，渣中TiO₂以[TiO₆]^8-八面体结构存在，可使渣中复杂硅氧网状结构解体；TiO₂含量由5%增加至25%时，炉渣中复杂结构单元Si(Q² + Q³)的含量降低，简单结构单元Si(Q⁰ + Q¹)的含量升高，Si(Q² + Q³)/Si (Q⁰ + Q¹)降低，炉渣结构简单化，即炉渣中无论是在低钛、中钛、还是高钛含量，TiO₂在炉渣中起炉渣修饰子作用，对降低炉渣黏度、改善炉渣流动性有积极作用，可作为高铝冶炼调控手段之一。
- 高铝高炉渣 /
- TiO₂ /
- 理化性能 /
- 炉渣结构
Abstract: With the increase of the high-alumina raw materials with high economy in blast furnace (BF) of domestic iron and steel enterprises, the content of Al₂O₃ in slag increases and the fluidity of the slag iron becomes worse, which brings a series of problems to BF smelting. Taking five-component CaO-SiO₂-Al₂O₃-MgO-TiO₂ slag system as the research object, through phase diagram theoretical calculation, experimental research and slag structure analysis, the effects of different TiO₂ content (low titanium 5%, medium titanium 15%, and high titanium 25%) in high-alumina slag on the viscosity and melting temperature of high-alumina BF slag were studied, The reasons affecting the physicochemical properties of slag are analyzed by slag structure. The results show that the fixed alkalinity R₂ is 1.25, the mass fraction of TiO₂ increases from 1% to 25% and the melting temperature of slag in the phase diagram first decreases and then increases. When the mass fraction of TiO₂ is 7%, the liquid phase of slag first precipitates from plagioclase calcium aluminosilicate (Ca₂Al₂SiO₇) to calcium titanate (CaTiO₃) with melting point of 1975 ℃, and the melting temperature of slag increases. When the TiO₂ content increases from 5% (low titanium) to 25% (high titanium) the slag viscosity and melting temperature decrease. The higher the temperature, the better the fluidity of slag, that is, TiO₂ in slag exists in [TiO₆]8- octahedron structure, which can disintegrate the complex silica network structure in slag. When the content of TiO₂ increases from 5% to 25%, the content of complex structural unit Si(Q²+Q³) in the slag decreases, the content of simple structural unit Si(Q⁰+Q¹) increases, Si(Q²+Q³)/Si(Q⁰+Q¹) decreases, and the slag structure is simplified, that is, TiO₂ acts as a slag modifier in the slag whether in low, medium or high titanium content, which is helpful to reduce the viscosity and it plays a positive role in improving slag fluidity.
- high-alumina blast furnace slag /
- TiO₂ /
- physicochemical properties /
- slag structure

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图 1 CaO-SiO₂-17 %Al₂O₃-8 %MgO-TiO₂五元渣系液相线

Figure 1. Liquidus diagram of five-component CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂ slag system

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图 2 黏度试验装置

Figure 2. Viscosity test device

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图 3 CaO-SiO₂-17%Al₂O₃-8 %MgO-TiO₂五元渣系液相投影

Figure 3. Liquid phase projection of five-component CaO-SiO₂-17 %Al₂O₃-8%MgO-TiO₂ slag system

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图 4 五元渣系熔化温度随TiO₂含量变化曲线

Figure 4. Temperature change curve of the five-component slag system with TiO₂ increasing

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图 5 五元渣系理论黏度计算图随TiO₂变化曲线

Figure 5. Viscosity change curve of the five-component slag system with TiO₂ increasing

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图 6 TiO₂含量对CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂渣系黏度的影响

Figure 6. Effect of w(TiO₂) on viscosity of CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂ slag system

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图 7 w(TiO₂)对CaO-SiO₂- 17%Al₂O₃-8%MgO-TiO₂渣系熔化性温度的影响

Figure 7. Effect of w(TiO₂) on melting temperature of CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂ slag system

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图 8 CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂渣系黏温曲线（R₂=1.25）

Figure 8. Viscosity temperature curve of CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂ slag system (R₂ = 1.25)

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图 9 CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂渣系Raman光谱

Figure 9. Raman spectra of CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂ slag

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图 10 CaO-SiO₂-8%MgO-17%Al₂O₃-TiO₂渣系Raman光谱分峰拟合

Figure 10. Raman spectral peak fitting of CaO-SiO₂-8%MgO-17%Al₂O₃-TiO₂ slag system

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图 11 CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂渣系炉渣各结构单元与TiO₂含量的关系

Figure 11. Relationship between structural units of CaO-SiO₂-17%Al₂O₃-8%MgO-TiO₂ slag and TiO₂ content

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表 1 CaO-SiO₂-17 %Al₂O₃-8 %MgO-TiO₂渣系黏度和熔化性温度测试结果

Table 1. Viscosity and melting temperature test results of CaO-SiO₂-17 %Al₂O₃-8 %MgO-TiO₂ slag system

编号	R₂	w/%
编号	R₂	CaO	SiO₂	MgO	TiO₂	Al₂O₃
1	1.25	38.89	31.11	8	5	17
2	1.25	36.11	28.89	8	10	17
3	1.25	27.78	22.22	8	25	17

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表 2 熔渣结构单元拉曼光谱特征峰

Table 2. Raman-active vibrations for various structure units of slag

结构单元	NBO/T[Qn]	波数/cm⁻¹
[SiO₄]⁴⁻	4(Q⁰)	850～880
[Si₂O₇]⁶⁻	3(Q¹)	900～920
[SiO₃]²⁻	2(Q²)	950～980
[Si₂O₇]²⁻	1(Q³)	1050～1100

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