CaO-Al2O3-MgO-SiO2-Ce2O3渣系活度计算模型

俞成; 邱吉雨; 刘承军

doi:10.7513/j.issn.1004-7638.2022.04.019

CaO-Al₂O₃-MgO-SiO₂-Ce₂O₃渣系活度计算模型

doi: 10.7513/j.issn.1004-7638.2022.04.019

俞成^{1, 2,},
邱吉雨^{1, 2, ,},
刘承军^{1, 2}

1.
多金属共生矿生态化冶金教育部重点实验室, 辽宁沈阳 110819
2.
东北大学冶金学院, 辽宁沈阳 110819

基金项目: 国家自然科学基金联合基金项目（U1908224）；博士后基金面上基金项目（N2125019）。

详细信息

作者简介:
俞成（1998—），男，硕士研究生，主要从事稀土钢精炼渣系设计，E-mail： 1261779780@qq.com

通讯作者:
邱吉雨（1992—），男，博士，讲师，主要从事冶金熔体热力学研究，E-mail： qiujiyu@smm.neu.edu.cn

中图分类号: TF769
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- 文章访问数: 145
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出版历程
- 收稿日期: 2022-01-27
- 刊出日期: 2022-09-14

Development of activity calculation model for the CaO-Al₂O₃-MgO-SiO₂-Ce₂O₃ slag system

Yu Cheng^{1, 2
,},
Qiu Jiyu^{1, 2
, ,},
Liu Chengjun^{1, 2}

1.
Key Laboratory for Ecological Metallurgy of Multimetallic Mineral (Ministry of Education), Shenyang 110819, Liaoning, China
2.
School of Metallurgy, Northeastern University, Shenyang 110819, Liaoning, China

摘要

摘要: 稀土钢冶炼过程中，含稀土钢液与熔渣间存在强烈的渣金反应，导致钢中溶解态稀土含量波动严重，影响其在钢中的作用效果。然而，由于含稀土渣系热力学数据的缺失，限制了相关研究工作的开展。依据分子离子共存理论，建立了CaO-Al₂O₃-MgO-SiO₂-Ce₂O₃渣系的活度计算模型，并绘制组元的等活度线图，讨论w(CaO)/w(Al₂O₃)、w(Ce₂O₃)等成分变化对渣系中各组元活度的影响。计算结果表明，CaO-Al₂O₃基精炼渣的SiO₂活度范围（4×10⁻¹⁹~7×10⁻¹⁸）远小于CaO-SiO₂基精炼渣的活度范围（0.003~0.4），即对于稀土钢而言，CaO-Al₂O₃基精炼渣更为适用；对于CaO-Al₂O₃基精炼渣，提高熔渣的w(CaO)/w(Al₂O₃)和w(Ce₂O₃)可增加Ce₂O₃活度、减小Al₂O₃活度，能够减弱含稀土钢液与熔渣中Al₂O₃间的反应。
- 稀土钢 /
- 精炼渣系 /
- 活度 /
- 分子离子共存理论
Abstract: During smelting steel containing rare earth elements, there exists strong reaction between the molten steel and the slag, which may result in significant content fluctuation of dissolved rare earth and then reduce its effect in steel. However, the lack of thermodynamic data of rare earth-containing slag system limits the development of related research work. In this paper, based on the ion and molecule coexistence theory, an activity calculation model of the CaO-Al₂O₃-MgO-SiO₂-Ce₂O₃ slag system has been established, which can be used to construct the iso-activity diagram and investigate w(CaO)/w(Al₂O₃), w(Ce₂O₃) and other composition changes on the activity of each component of the slag system. The results show that the SiO₂ activity range (4×10⁻¹⁹~7×10⁻¹⁸) of CaO-Al₂O₃-based refining slag is much smaller than that of CaO-SiO₂-based refining slag (0.003~0.4), that is, CaO-Al₂O₃-based slag is more suitable for rare earth steel. For CaO-Al₂O₃-based refining slag, increasing the w(CaO)/w(Al₂O₃) and w(Ce₂O₃) of the slag can increase the activity of Ce₂O₃ and decrease the activity of Al₂O₃ , which may restrain the reaction between the rare earth-containing molten steel and Al₂O₃ in the slag.
- rare earth steel /
- slag system /
- activity /
- ion and molecule coexistence theory

HTML全文

图 1 Ce与CaO、Al₂O₃、SiO₂反应的标准吉布斯自由能

Figure 1. Standard Gibbs free energy of Ce reaction with CaO, Al₂O₃ and SiO₂

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图 2 CaO-Al₂O₃-SiO₂三元相图

Figure 2. CaO-Al₂O₃-SiO₂ ternary phase diagram

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图 3 CaO-Al₂O₃-5%MgO-SiO₂-Ce₂O₃渣系中SiO₂等活度图

(a) CaO-Al₂O₃基；(b) CaO-SiO₂基

Figure 3. Iso-activity diagram of SiO₂ in CaO-Al₂O₃-5%MgO-SiO₂-Ce₂O₃ slag system

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图 4 CaO-Al₂O₃-5%MgO-7%SiO₂-Ce₂O₃渣系中Ce₂O₃等活度图

Figure 4. Iso-activity diagram of Ce₂O₃ in CaO-Al₂O₃-5%MgO-7%SiO₂-Ce₂O₃ slag system

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图 5 CaO-Al₂O₃-5%MgO-7%SiO₂-Ce₂O₃渣系Al₂O₃等活度图

Figure 5. Iso-activity diagram of Al₂O₃ in CaO-Al₂O₃-5%MgO-7%SiO₂-Ce₂O₃ slag system

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表 1 CaO-Al₂O₃-MgO-SiO₂-Ce₂O₃结构单元

Table 1. Structural units of CaO-Al₂O₃-MgO-SiO₂-Ce₂O₃

体系	结构单元
基本结构单元	Ca²⁺、Ce³⁺、Mg²⁺、Al₂O₃、SiO₂
Al₂O₃-CaO	CaO∙Al₂O₃、3CaO∙Al₂O₃、CaO∙2Al₂O₃、CaO∙6Al₂O₃
Al₂O₃-Ce₂O₃	Ce₂O₃·Al₂O₃、Ce₂O₃·11Al₂O₃
Al₂O₃-SiO₂	3Al₂O₃·2SiO₂
Al₂O₃-MgO	MgO·Al₂O₃
SiO₂-CaO	CaO·SiO₂、3CaO·2SiO₂、2CaO·SiO₂、3CaO·SiO₂
SiO₂-Ce₂O₃	Ce₂O₃·SiO₂、Ce₂O₃·2SiO₂、Ce_4.67Si₃O₁₃
SiO₂-MgO	2MgO·SiO₂、MgO·SiO₂
CaO-Al₂O₃-SiO₂	2CaO·Al₂O₃·SiO₂、CaO·Al₂O₃·2SiO₂、CaO·Al₂O₃·SiO₂、3CaO·Al₂O₃·3SiO₂
CaO-SiO₂-MgO	CaO·MgO·2SiO₂、CaO·MgO·SiO₂、2CaO·MgO·2SiO₂、3CaO·MgO·2SiO₂
MgO-Al₂O₃-SiO₂	2MgO·2Al₂O₃·5SiO₂、4MgO·5Al₂O₃·2SiO₂、3MgO·Al₂O₃·3SiO₂
CaO-Al₂O₃-Ce₂O₃	2CaO·Al₂O₃·Ce₂O₃、2CaO·3Al₂O₃·Ce₂O₃
CaO-Al₂O₃-MgO	3CaO·MgO·2Al₂O₃、CaO·MgO·7Al₂O₃、CaO·2MgO·8Al₂O₃
CaO-Al₂O₃-SiO₂	CaO·3SiO₂·2Ce₂O₃

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表 2 CaO·3SiO₂·2Ce₂O₃化合物的热力学数据

Table 2. Thermodynamic data of CaO·3SiO₂·2Ce₂O₃ compounds

化合物	H²⁹⁸/ (kJ·mol⁻¹)	S²⁹⁸ /[J.(mol·K)⁻¹]	C_p(T)=a+b×10⁻³T+c×10⁵T⁻² [J·(mol·K)⁻¹]
化合物	H²⁹⁸/ (kJ·mol⁻¹)	S²⁹⁸ /[J.(mol·K)⁻¹]	a	b	c
CaO·3SiO₂·2Ce₂O₃	−7330.568	466.137	477.948	67.814	−88.2

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CaO-Al₂O₃-MgO-SiO₂-Ce₂O₃渣系活度计算模型

doi: 10.7513/j.issn.1004-7638.2022.04.019

作者简介:
俞成（1998—），男，硕士研究生，主要从事稀土钢精炼渣系设计，E-mail： 1261779780@qq.com

通讯作者:
邱吉雨（1992—），男，博士，讲师，主要从事冶金熔体热力学研究，E-mail： qiujiyu@smm.neu.edu.cn

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Development of activity calculation model for the CaO-Al₂O₃-MgO-SiO₂-Ce₂O₃ slag system

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