硅酸盐学报

顶吹炉镍渣作用下碱/弱酸性耐火材料的侵蚀行为对比

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袁蝴蝶 ¹ , 刘宇驰 ¹ , 尹洪峰 ¹ , 辛亚楼 ¹ , 汤云 ¹ , 任小虎 ¹ , 高云琴 ¹^,² , 归冬云 ¹ , 张新悦 ¹

硅酸盐学报 | 碳中和与耐火材料专题—研究论文 2025,53(9): 2568-2576

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硅酸盐学报 |碳中和与耐火材料专题—研究论文 2025 , 53 (9) : 2568 -2576

顶吹炉镍渣作用下碱/弱酸性耐火材料的侵蚀行为对比

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袁蝴蝶¹, 刘宇驰¹, 尹洪峰¹, 辛亚楼¹, 汤云¹, 任小虎¹, 高云琴¹^,², 归冬云¹, 张新悦¹

作者信息

^1．西安建筑科技大学材料科学与工程学院，西安 710055

^2．矿山生态修复与固废资源化厅市共建山西省重点实验室培育基地，山西阳泉 045000

通讯作者:

刘宇驰（1997—），男，博士，讲师。

作者简介:

袁蝴蝶（1982—），女，博士，高级实验师。

Corrosion Behaviors of Basic and Weak Acid Refractories with Nickel Slag from Top-Blown Furnaces

Hudie YUAN¹, Yuchi LIU¹, Hongfeng YIN¹, Yalou XIN¹, Yun TANG¹, Xiaohu REN¹, Yunqin GAO¹^,², Dongyun GUI¹, Xinyue ZHANG¹

Affiliations

^1.College of Materials Science and Engineering, Xi'an University of Architecture &Technology, Xi'an 710055, China

^2.The Cultivation Base of Shanxi Key Laboratory of Mining Area Ecological Restoration and Solid Wastes Utilization, Shanxi Institute of Technology, Shanxi Yangquan 045000, China

Corresponding Author:

LiU Yuchi (1997-), male, Ph.D., Lecturer. E-mail: liuyuchi@xauat.edu.cn

YUAN Hudie (1982-), female, Ph.D., Senior-Experimentalist. E-mail: yuanhudie@xauat.edu.cn

出版时间: 2025-09-20 doi: 10.14062/j.issn.0454-5648.20240773

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摘要

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镁铬砖以其优异的高温使用性能常被用于镍熔炼炉的工作衬，随着国家环保监管力度不断加强，环境执法力度持续强化，镁铬砖使用过程中产生的Cr⁶⁺对环境与人体的危害不容忽视。为明晰不同性质耐火材料与镍渣的侵蚀作用机理，从相组成和显微结构入手，对比了半再结合镁铬砖、高铝砖和黏土砖与镍渣的侵蚀行为变化。借助高温热力学计算，构建3种耐火材料与镍渣的界面侵蚀反应模型。结果表明：镁铬砖与镍渣侵蚀反应过程中生成的尖晶石隔离层阻滞了熔渣向材料内部的渗透；当刚玉相在渣中达到饱和溶解度后，高铝砖中可形成侵蚀隔离层；黏土砖无法通过侵蚀反应形成隔离层，但随着莫来石向渣中的不断溶解，熔渣中SiO₂含量增加，Si-O的网状结构增大了熔渣黏度，使得渣向黏土砖中的渗透减少。

关键词

镍渣 / 显微结构 / 热力学结算 / 界面侵蚀反应模型 / 黏度

Abstract

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Introduction

To improve the quality and efficiency of the nickel metal melting process, the performance of oxygen-rich top-blown melting furnaces must be considered, particularly the furnace lining material used in the melt pool area. As a furnance lining, the refractory material is exposed to the mechanical and thermal stresses, and the corrosion of the refractories by the slag is an important cause of their failure. Investigating the corrosion resistance of refractories is thus a prerequisite to improve the service life of materials and ensure the product quality. Semi-rebonded magnesia-chrome bricks with a superior high-temperature performance is currently the first option for oxygen-rich top-blown furnace linings. However, the effect of Cr⁶⁺ after using magnesia-chrome bricks should not be ignored due to environmental protection requirements. The development of refractories with a superior high-temperature performance can replace the semi-rebonded magnesia-chrome bricks used directly in the oxygen-rich top-blown molten furnace bath, which is imperative. In this paper, different types of bricks (i.e., semi-rebonded magnesia-chrome bricks, high alumina bricks, and clay bricks) were used, and their phase compositions and microstructures were analyzed. In addition, the mechanism of high-temperature corrosion of nickel slag and refractories was also investigated via thermodynamic simulations, thus providing a theoretical reference for the design and manufacture of environmentally friendly furnace lining materials.

Methods

The corrosion resistances of semi-rebonded magnesia-chrome bricks (Beijing Yenai Jiye New Technology Co., China), high alumina bricks (Zhengzhou Rongsheng Kiln Refractories Co., China), and clay bricks (Zhengzhou Rongsheng Kiln Refractories Co., China) to nickel slag with the size of 325 mesh (Jinchuan Group Co., Ltd., China) from the top-blown furnaces were analyzed by a static crucible method. The crucible specimens used were cylindrical specimens with a diameter of φ50 mm×50 mm and holes with a diameter of φ 20 mm×20 mm in the center, which were drilled with a rock drilling and coring machine. The dried crucible was filled with 25 g of nickel slag powder and reacted at 1450 ℃ for 3, 7, and 11 h to obtain specimens after corrosion. The corroded specimens were then cut uniformly along the axial direction, and their cross-sections were analyzed. After fixing the corroded specimens with epoxy resin, the specimens were polished to obtain specimens for microstructure analysis.

The microstructures of the corroded specimens were determined by field-emission scanning electron microscopy in the back-scattered electron mode (FE-SEM, Gemini 500, ZEISS Co., Germany). The phase compositions of the corroded specimens were analyzed by X-ray diffraction (XRD; D/MAX 2000PC, Rigaku Co., Japan). The corrosion reaction was simulated by a software named Factsage (version 7.0) for thereaction, equilib, and viscosity modules of the thermodynamics simulation.

Results and discussion

The semi-rebonded magnesia-chrome bricks, high alumina bricks, and clay bricks are exposed to nickel slag corrosion at high temperatures. The semi-rebonded magnesia-chrome bricks are found to be more resistant to nickel slag corrosion and penetration because of the formation of a spinel isolation layer at the interface between the slag and the refractory. The slag content in both the high alumina bricks and clay bricks during reaction with nickel slag corrosion is higher than that in the semi-rebonded magnesia-chrome bricks under the same conditions. Al₂O₃ in the clay bricks continuously dissolves in the slag due to the presence of more SiO₂ in the slag, resulting in a poor resistance of the clay brick to nickel slag corrosion. The viscosity of the slag gradually increases due to the grid structure formed by Si-O, weakening the penetration of the slag into the clay brick. Although high alumina bricks have some resistance to nickel slag corrosion, their resistance to nickel slag penetration is worse than that of clay bricks.

Conclusions

The spinel isolation layer formed during the corrosion reaction between the semi-rebonded magnesia-chrome bricks and nickel slag effectively blocked the penetration of slag into the interior of the material. High-alumina bricks could only form a corrosion isolation layer when corundum reached a saturation solubility in the slag. A corrosion isolation layer could not be formed during the corrosion reaction of the clay bricks. However, as mullite continued to dissolve in the slag, SiO₂ content in the molten slag increased and the network structure composed of Si-O enhanced the viscosity of the slag, thus weakening its ability to penetrate the interior of the clay bricks.

Key words

nickel slag / microstructure / thermodynamic calculation / interface corrosion reaction model / viscosity

引用本文

袁蝴蝶, 刘宇驰, 尹洪峰, 辛亚楼, 汤云, 任小虎, 高云琴, 归冬云, 张新悦. 顶吹炉镍渣作用下碱/弱酸性耐火材料的侵蚀行为对比. 硅酸盐学报, 2025 , 53 (9) : 2568 -2576 . DOI: 10.14062/j.issn.0454-5648.20240773

Hudie YUAN, Yuchi LIU, Hongfeng YIN, Yalou XIN, Yun TANG, Xiaohu REN, Yunqin GAO, Dongyun GUI, Xinyue ZHANG. Corrosion Behaviors of Basic and Weak Acid Refractories with Nickel Slag from Top-Blown Furnaces[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (9) : 2568 -2576 . DOI: 10.14062/j.issn.0454-5648.20240773

基金

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陕西省自然科学基础研究计划一般项目（青年）(2025JC-YBQN-646)

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2025年第53卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240773

接收时间：2024-12-04
首发时间：2026-10-21
出版时间：2025-09-20

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收稿日期：2024-12-04
修回日期：2024-12-26

基金

陕西省自然科学基础研究计划一般项目（青年）(2025JC-YBQN-646)

作者信息

^1．西安建筑科技大学材料科学与工程学院，西安 710055

^2．矿山生态修复与固废资源化厅市共建山西省重点实验室培育基地，山西阳泉 045000

通讯作者:

刘宇驰（1997—），男，博士，讲师。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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