硅酸盐学报

铜冶炼精炼炉用镁铬质耐火材料损毁机制

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李君霞 ¹^,² , 段锋 ¹ , 丁冬海 ¹ , 靳恩东 ¹ , 闫光辉 ³

硅酸盐学报 | 研究论文 2024,52(12): 3841-3848

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硅酸盐学报 |研究论文 2024 , 52 (12) : 3841 -3848

铜冶炼精炼炉用镁铬质耐火材料损毁机制

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李君霞¹^,², 段锋¹, 丁冬海¹, 靳恩东¹, 闫光辉³

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．濮阳濮耐高温材料（集团）股份有限公司，河南濮阳 457100

^3．郑州海迈高温材料有限公司，郑州 452370

通讯作者:

段锋（1970—），男，副教授。

作者简介:

李君霞（1983—），女，硕士研究生，工程师。

Degradation Mechanism of Magnesia-Chrome Refractory for Nerin-Gutai-Lu Copper Refining Furnace

Junxia LI¹^,², Feng DUAN¹, Donghai DING¹, Endong JIN¹, Guanghui YAN³

Affiliations

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

^2.Puyang Refractories Group Co., Ltd., Puyang 457100, Henan, China

^3.Zhengzhou Haimai High Temperature Materials Co., Ltd., Zhengzhou 452370, China

Corresponding Author:

DUAN Feng (1970-), male, Associate Professor. E-mail: xjddf@163.com

LI Junxia (1983-), female, Master candidate, Engineer. E-mail: ljx1115@126.com

出版时间: 2024-12-20 doi: 10.14062/j.issn.0454-5648.20240356

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摘要

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镁铬质耐火材料作为一种优异的抗熔渣侵蚀材料，在铜冶炼领域具有广泛的应用前景。国内外关于铜冶炼耐火材料损毁机理研究主要集中在铜精矿火法炼铜工艺的熔炼炉、转炉、阳极炉等炉型，再生铜精炼炉用耐火材料损毁机理却鲜有研究。瑞林固体块料精炼炉（NGL）对废杂铜再生利用有重要意义，能缓解铜精矿资源的不足。采用扫描电子显微镜、能谱仪、衍射仪探讨了铜冶炼NGL炉用后镁铬质耐火材料侵蚀损毁机理。结果表明：镁铬砖受炉渣与铜熔体的双重作用，橄榄石相的形成与方镁石晶粒的溶解是炉衬材料化学损毁的主要原因。随着熔渣的渗透、方镁石晶粒的溶解，粗铜及铜的氧化物等熔体表现出更强的渗透能力，基质铬铁矿颗粒边缘及镁质骨料的晶界、气孔或裂纹处被大量的粗铜、铜的氧化物熔体填充，破坏了镁铬砂、铬铁矿尖晶石、方镁石的直接结合，这种金属熔体能够深入镁铬砖的内部结构，可达260 mm以上。含SO₂-O₂的气体扩散到残砖冷面的类原砖层，由于晶界处的钙镁橄榄石的离解，气相介质中SO₂/SO₃与砖中CaO反应生成了CaSO₄，XRD结果证实，残砖冷面反应层存在CaSO₄物相。SO₂-O₂的气体扩散作用下的相关反应会引起体积膨胀，导致结构疏松，加剧了耐火材料的熔融侵蚀。

关键词

铜冶炼 / 镁铬砖 / 显微结构 / 损毁机理

Abstract

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Introduction

Copper is a kind of strategic resource to support low carbon transition and economic development. The main sources of raw materials for copper smelting are copper concentrate and recycled copper resources. The existing researches on the damage mechanism of refractories that are used in copper smelting mainly focus on the smelting furnace, converter, anode furnace and other furnace types for copper concentrate pyrometallurgical copper refining process. However, there is little research on the damage mechanism of refractory, used in recycled copper refining furnace. Nerin-Gutai-Lu (NGL) has a great significance for the recycled of waste copper and alleviates the shortage of copper concentrate resources. The copper smelting process is characterized by intense chemical reactions, fast speed, high heat intensity and complex furnace atmosphere (i.e., O₂ and SO₂) in the furnace, which can easily damage the furnace lining refractories. The magnesia-chrome refractories have extensive applications in coppers smelting because of its excellent slag corrosion resistance. In this study, the damage mechanism of magnesia-chrome brick used in NGL recycled copper refining furnace was investigated. The macroscopic morphology, phase composition, and microstructure of the used magnesia-chrome brick were analyzed.

Methods

The sample was selected from magnesia-chrome brick used in the NGL furnace of a copper plant in Jiangxi Province, China, and their corrosion behavior and mechanism were analyzed. The residual brick was horizontally cut and divided into different areas according to the degree of corrosion, which were the reaction layer, infiltrated zone and the similar original brick zone. The chemical and phase composition of different areas of the residual brick were characterized by X-ray fluorescence (XRF) and X-ray diffraction (XRD), and the bulk density and apparent porosity were measured based on the Archimedes principle using water as a medium. The degradation on mechanism and microstructure of the sample were analyzed by scanning electron microscopy (SEM), and the composition of the sample was identified by attached energy dispersive spectrometry (EDS).

Results and discussion

The magnesia-chrome brick is destroyed through chemical damage by NGL slag and copper melt due to the forsterite phase and the dissolution of periclase grains. The crude copper and copper oxides exhibit an intense permeability due to the penetration of slag (containing gas) and dissolution of periclase particles. With a large number of crude copper and copper oxides melting, the direct combination of fused magnesia-chrome, and periclase is destroyed. This metal melt can penetrate into the internal structure of magnesia-chrome brick and reach over 260 mm, which distributes in the matrix around the chromite particles and the grain boundaries, and pores or cracks of magnesia aggregate. Subsequently, SO₂ and O₂ are diffused to the similar original brick layer on the cold face of the residual brick due to the dissociation of monticellite at the grain boundary. SO₂/SO₃ in gas-phase medium reacts with CaO in brick to form CaSO₄. The XRD patterns indicate that the main component of the reaction layer on the cold face of the residual brick is CaSO₄ phase. The related reaction under the gas diffusion of SO₂-O₂ can cause a volume expansion, leading to the structural looseness and exacerbating the melting corrosion of refractories.

Conclusions

The diffusion of metal elements in NGL refining slag, i.e., ferrum, nickel and zinc, led to the interaction between slag and periclase grains, resulting in the formation of forsterite (containing Fe) and (Mg, Fe, Ni)O solid solutions, which reacted with chromite to form (Mg, Fe, Ni)(Cr, Al, Fe)₂O₄ multiphase spinel. The reasons of chemical damage in magnesia-chrome refractories included the formation of forsterite phase and the dissolution of periclase grains. The corrosion of refractories by metal melts, such as Cu-Cu_xO, was mainly infiltrated. The gases containing SO₂-O₂ diffused into the similar original brick layer of the residual brick cold surface, generating low melting point alkaline earth metal sulfides mainly composed of MgSO₄ and CaSO₄. The relevant reactions under the action of SO₂-O₂ could cause a volume expansion, resulted in a loose structure of magnesia-chrome refractories and exacerbating the melting corrosion of refractories. The uniform microstructure of the fused magnesia-chrome block in the furnace lining was a mixture of magnesia-chrome spinel and periclase, which could effectively resist the infiltration of copper melt. In addition, the high-Fe spinel ring formed at the edge of chromite particles also enhanced the slag corrosion resistance.

Key words

copper smelting / magnesia chrome brick / microstructure / damage mechanism

引用本文

李君霞, 段锋, 丁冬海, 靳恩东, 闫光辉. 铜冶炼精炼炉用镁铬质耐火材料损毁机制. 硅酸盐学报, 2024 , 52 (12) : 3841 -3848 . DOI: 10.14062/j.issn.0454-5648.20240356

Junxia LI, Feng DUAN, Donghai DING, Endong JIN, Guanghui YAN. Degradation Mechanism of Magnesia-Chrome Refractory for Nerin-Gutai-Lu Copper Refining Furnace[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (12) : 3841 -3848 . DOI: 10.14062/j.issn.0454-5648.20240356

基金

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陕西省科技厅项目(2023-YBGY-421)

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2024年第52卷第12期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240356

接收时间：2024-05-21
首发时间：2026-10-22
出版时间：2024-12-20

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收稿日期：2024-05-21
修回日期：2024-07-22

基金

陕西省科技厅项目(2023-YBGY-421)

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．濮阳濮耐高温材料（集团）股份有限公司，河南濮阳 457100

^3．郑州海迈高温材料有限公司，郑州 452370

通讯作者:

段锋（1970—），男，副教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240356

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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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