镁铬耐火材料及高温装备绿色化应用研究进展

doi:10.11896/cldb.18110166

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Abstract Magnesia-chromium refractory is an alkaline refractory material with periclase and spinel (Mg, Fe) (Cr, Al, Fe)₂O₄ as the main crystalline phases. It has high refractoriness, high strength under high temperature, excellent thermal shock resistance, fine slag corrosion resistance and good economical efficiency, and has been widely used in iron and steel metallurgy, non-ferrous smelting, cement and other industries. Magnesium chromium refractories are the dominant materials in many key parts of high-temperature furnace. However, Cr³⁺ of Cr₂O₃ will be partly converted to Cr⁶⁺ at a certain temperature in oxidizing atmosphere or with alkaline oxides such as K₂O, Na₂O, CaO, etc., resulting in hexavalent chromium pollution, which is not line with green, environmentally friendly and efficient for high temperature industry. It is impossible to eliminate the hidden danger caused by Cr⁶⁺ in magnesium chromium refractories by regulating the industrial chain and taking a series of measures to restrain the formation of hexavalent chromium compounds. However, the most consistent and permanent way is to carry out the research and application of chromium-free refractories.
In view of the pollution caused by the application of magnesia-chromium refractories in high-temperature industrial furnace, refractory resear-chers all over the world have successively carried out green refractories research and application for high temperature furnace. A large number of chromium-free research results have been achieved for cement rotary kiln and RH refining furnace, and positive social benefits have been achieved along with the production practice, especially the chromium-free refractories used in burning zone in cement rotary kiln. At present, the magnesia-calcium-zirconium refractories and magnesia spinel refractories have achieved better application effect in burning zone of cement rotary kiln, which can replace magnesia chromium bricks very well. The application result above-mentioned has greatly promoted the research and practice of chromium-free for RH refining furnace in iron and steel metallurgy. At present, refractories of chromium-free for RH refining furnace have been successfully developed, and there are many alternative refractories of chromium-free, for example, composite magnesia alumina spinel bricks are most widely used. Refractories for some RH refining furnace have been chromium-free in many countries, and the development idea of greenization has been realized. There are two points by summarizing the above experience: (i) relying on industry independent technological innovation to realize the social value of enterprises; (ii) relying on the improvement of public awareness of environmental protection and the guiding role of government policies related to environmental protection industry. The joint forces of above two can promote application and development of greenization of high temperature furnaces
At present and some time to come in the future, magnesia-chromium refractories are still difficult to be replaced in high temperature furnace of non-ferrous smelting and the dominant materials in many key parts of high-temperature furnace. It is a long way to carry out effective research and application of chromium-free bricks. Therefore, it is still an important subject to improve the properties of magnesia-chromium refractories, improve service life and reduce material consumption. Therefore, the following two points of work need to be done well: (i) improving the corrosion resis-tance of materials to FeO-SiO₂ slag, (ii) improving resistance to copper-sulfur penetration. While drawing on the successful experience of chro-mium-free practice in other fields, we should also see that with the implementation of new high temperature industrial processes and the emergence of new technologies and furnace, magnesium chromium refractories still have certain application prospects in some new fields. Therefore, the research and application in greenization for high temperature furnace is still a lasting and continuous progressive process.
This paper summarizes the characteristics of magnesia-chromium refractory and its application and damage mechanism in high-temperature furnace. It emphatically introduces the positive progress in the research and application of greenization for cement rotary kiln and RH furnace, and analyses the main difficulties and research directions of greenization of copper furnace, to achieve less consumption of magnesia-chromium bricks in copper furnace while actively promoting greenization of rotary kiln and RH furnace.

Key words： magnesium chromium refractories high temperature furnace chromium-free greenization

Published: 30 September 2019

CLC number:	TQ175.7
	X773

Fund:This work was financially supported by the National Natural Science Foundation of China (51772277, 51372231), and National Key Basic Research Special Foundation of China (2017YFB0304000).

About author:: Fan Qian received his M.S. degree from Luoyang Institute of Refractories Research in 2010 under the supervision of Prof. Hongxia Li. He is a senior engineer and focuses on the development of functional refractories and ceramics of high thermal shock resistance, and has won the first prize of Scientific and Technological Progress in Henan Province. In recent years, more than 20 acade-mic papers have been published in the field, and more than 10 invention patents have been authorized.
Hongxia Li received her B.S., M.S. degrees in inorganic non-metal materials science and engineering from Tianjin University in 1987 and 1992, respectively, and received her Ph.D. degree from Shanghai Institute of Ceramics, the Chinese Academy of Sciences in 1994.Her interests are mainly in high temperature structured ceramics, carbon-containing refractories,function refractories for continuous casting and kiln furniture,on which she has authored or co-authored over 180 papers, and more than 30 patents have been authorized. Due to her achievement, she was conferred the title of “Outstanding Refractories Fellow” of the Associations of China Refractories Industry in 2010, “Central Scholar” in 2013, and “National Outstanding Engineer Award” in 2018. Now she is the vice chief-engineer of Sinosteel Corporation, the president of Sinosteel Luoyang Institute of Refractories Research Co., Ltd. and Refractories Branch of the Chinese Society for Metals.

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Cite this article:

QIAN Fan,DUAN Xueke,YANG Wengang, et al. Research Progress of Magnesia Chrome Refractories and Their Applicationin Greenization for High Temperature Furnace[J]. Materials Reports, 2019, 33(23): 3882-3891.

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http://www.mater-rep.com/EN/10.11896/cldb.18110166 OR http://www.mater-rep.com/EN/Y2019/V33/I23/3882

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