A review on the production technologies of high-purity magnesia and magnesium oxide ceramics

doi:10.16085/j.issn.1000-6613.2018-1135

Abstract

Abstract:

High-purity magnesia is an important heat-resistant material and magnesium oxide ceramics are widely used in the field of transparent materials. It has great theoretical and practical significance to study the production process of the two materials. Various technologies of producing high-purity magnesia and magnesium from magnesite and brine, sintering methods of magnesium oxide ceramics and the influence of sintering additives on the sintering process are systematically reviewed. The preparation technologies of high-purity magnesia from magnesite, the preparation technologies of high-purity magnesia by brine precipitation method and by direct pyrolysis of brine method and the preparation technologies of high-purity magnesia by electrical fusion method are introduced. The advantages and disadvantages of each production technology and the research and development directions in the future are pointed out. Various sintering methods and research progress of magnesium oxide ceramics are introduced, including conventional sintering, hot pressing sintering, hot isostatic pressing sintering, spark plasma sintering, microwave sintering and vacuum sintering. The influence of sintering additives on the sintering process and the influence mechanism are summarized. The future research emphases of magnesium oxide ceramics such as powder synthesis technology, densification sintering technology and sintering additives are pointed out.

Key words: high-purity magnesia, magnesium oxide ceramics, magnesite, brine, pyrolysis, sintering

摘要：

高纯镁砂是重要的耐高温材料，氧化镁陶瓷则广泛应用于透光材料领域，对两种材料的生产工艺开展研究具有重要理论和实际意义。本文系统地综述了利用菱镁矿、卤水生产高纯氧化镁及镁砂的各种技术，以及氧化镁陶瓷的烧结方法和烧结助剂对烧结过程的影响；介绍了菱镁矿制备高纯镁砂，卤水沉淀法、卤水直接热解法制备高纯氧化镁，以及电熔法制备高纯镁砂等技术。指出了每种生产技术的优缺点及今后的研究与发展方向。介绍了常压烧结、热压烧结、热等静压烧结、放电等离子烧结、微波烧结和真空烧结等氧化镁陶瓷烧结技术及其进展，总结了烧结助剂对烧结过程的影响及其机理，指出氧化镁陶瓷未来的研究关键主要在于对粉体合成技术、致密化烧结技术及烧结助剂的研究。

关键词: 高纯镁砂, 氧化镁陶瓷, 菱镁矿, 卤水, 热解, 烧结

CLC Number:

TQ132.2

Yingchun CHEN, Jiafen ZHOU, Guimin LU, Jianguo YU. A review on the production technologies of high-purity magnesia and magnesium oxide ceramics[J]. Chemical Industry and Engineering Progress, 2019, 38(01): 505-515.

陈英春, 周佳芬, 路贵民, 于建国. 高纯镁砂及氧化镁陶瓷研究进展[J]. 化工进展, 2019, 38(01): 505-515.

Figures/Tables 1

References 57

1	刘弘 . 高纯镁砂的制取方法: CN101475323A[P]. 2009-07-08.
	LIU H . Preparation method of high purity magnesia: CN101475323A[P]. 2009-07-08.
2	赵磊, 王蒙岩, 林江顺, 等 . 一种利用菱镁矿精矿一步焙烧高纯镁砂的生产线: CN205774134U[P]. 2016-12-07.
	ZHAO L , WANG M Y , LIN J S , et al . Utilize production line of one step of high-purity magnesia of calcination in magnesite concentrate: CN205774134U[P]. 2016-12-07.
3	徐徽, 蔡勇, 陈白珍, 等 . 用低品位菱镁矿制取高纯镁砂[J]. 中南大学学报(自然科学版), 2006, 37(4): 698-702.
	XU H , CAI Y , CHEN B Z , et al . Preparation of high purity magnesia from low-grade magnesite[J]. Journal of Central South University(Science and Technology), 2006, 37(4): 698-702.
4	RANJITHAM A M , KHANGAONKAR P R . Leaching behaviour of calcined magnesite with ammonium chloride solutions[J]. Hydrometallurgy, 1990, 23(2): 177-189.
5	章柯宁, 张一敏, 王昌安, 等 . 从低品级菱镁矿中提取高纯氧化镁的研究[J]. 武汉科技大学学报(自然科学版), 2006, 29(6): 558-560.
	ZHANG K N , ZHANG Y M , WANG C A , et al . Obtaining high-grade mgo from low-grade magnesite[J]. Journal of Wuhan University of Science and Technology(Natural Science Edition), 2006, 29(6): 558-560.
6	章柯宁, 张一敏, 王昌安, 等 . 碳化法从菱镁矿中提取高纯氧化镁的研究[J]. 武汉科技大学学报(自然科学版), 2004, 27(4): 352-353.
	ZHANG K N , ZHANG Y M , WANG C A , et al . Soaking high-grade MgO from magnesite by carbonate method[J]. Journal of Wuhan University of Science and Technology(Natural Science Edition), , 2004, 27(4): 352-353.
7	马鹏程 . 高活性氧化镁和高密度烧结镁砂的研究[D]. 沈阳: 东北大学, 2014.
	MA P C . Study on high-activity and high-density MgO[D]. Shenyang: Northeastern University, 2014.
8	王云山, 杨刚, 杨平 . 高纯镁砂湿火一体法装置及制备高纯镁砂的方法: CN104108733B[P]. 2015-12-09.
	WANG Y S , YANG G , YANG P . High-purity magnesia wet-pyrogenic integrated device and method for preparing high-purity magnesia: CN104108733B[P]. 2015-12-09.
9	谢垚 . 用六水氯化镁制备高纯镁砂工艺[D]. 太原: 太原理工大学, 2014.
	XIE Y . Research on preparation of high purity magnesite with MgCl₂·6H₂O[D]. Taiyuan: Taiyuan University of Technology, 2014.
10	李陇岗 . 青海盐湖水氯镁石制备高纯镁砂研究[D]. 成都: 成都理工大学, 2005.
	LI L G . Studies on preparation of high purity magnesia from bischofite in Qinghai salt lakes[D]. Chengdu: Chengdu University of Technology, 2005.
11	黄琼珠 . 废弃水氯镁石热解制备高纯镁砂研究[D]. 上海: 华东理工大学, 2013.
	HUANG Q Z . Preparation of high purity magnesia from waste bischofite by pyrolysis[D]. Shanghai: East China University of Science and Technology, 2013.
12	EPSTEIN J A . Utilization of the dead sea minerals (a review)[J]. Hydrometallurgy, 1976, 2(1): 1-10.
13	郭如新 . 合成法氧化镁、氢氧化镁生产现状与前景展望[J]. 无机盐工业, 2011, 43(11): 1-5,18.
	GUO R X . Present production status and developing prospect of MgO and Mg(OH)₂ by synthetic processes[J]. Inorganic Chemicals Industry, 2011, 43(11): 1-5,18.
14	AMAN J J . Improvements in or relating to the thermal decomposition of certain chlorides and sulphates: GB793700A[P]. 1958-04-23.
15	路贵民, 黄琼珠, 于建国, 等 . 一种用水氯镁石热解制备碱式氯化镁和氧化镁的方法: CN101624198A[P]. 2010-01-13.
	LU G M , HUANG Q Z , YU J G , et al . Method for preparing basic magnesium chloride and magnesium oxide by pyrolyzing bischofite: CN101624198A[P]. 2010-01-13.
16	刘源滔 . 水氯镁石热解机理与中间产物结构演变[D]. 上海: 华东理工大学, 2017.
	LIU Y T . Study on the mechanism and structure transition of thermal decomposition of MgCl₂∙6H₂O[D]. Shanghai: East China University of Science and Technology, 2017.
17	刘富舟 . 水氯镁石喷雾热解制备氧化镁工艺设计及实验研究[D]. 上海: 华东理工大学, 2015.
	LIU F Z . Process design and experimental study on preparation of magnesium oxide from bischofite by spray pyrolysis[D]. Shanghai: East China University of Science and Technology, 2015.
18	DU W , SUN Z , LU G M , et al . The two-phase high-speed stream at the centerline of a hollow-cone spray produced by a pressure-swirl nozzle[J]. Industrial & Engineering Chemistry Research, 2017, 56(1): 359-367.
19	DU W , SUN Z , LU G M , et al . Interaction between a hollow-cone spray and the co-axial swirling stratified flow in a novel spray pyrolysis furnace[J]. The Canadian Journal of Chemical Engineering, 2018, 96(5): 1079-1088.
20	DU W , SUN Z , LU G M , et al . CFD aided design of integrated spray pyrolysis furnace for liquid ore exploitation[J]. Chemical Engineering and Processing: Process Intensification, 2017, 122: 245-257.
21	陈侠, 陈丽芳 . 用六水氯化镁工业化生产高纯氧化镁的新工艺[J]. 盐业与化工, 2008, 37(3): 13-16.
	CHEN X , CHEN L F . New process for industrial production of high-purity magnesium oxide from magnesium chloride hexahydrate[J]. Journal of Salt Science and Chemical Industry, 2008, 37(3): 13-16.
22	闫岩, 卢旭晨, 王体壮, 等 . 利用老卤生产高纯氧化镁技术研究进展[J]. 化工进展, 2016, 35(10): 3251-3257.
	YAN Y , LU X C , WANG T Z , et al . A review on the technologies of high-purity magnesia production from brine[J]. Chemical Industry and Engineering Progress, 2016, 35(10): 3251-3257.
23	LU X C , YAN Y . Method and device for producing high-purity magnesium oxide and co-producing industrial concentrated hydrochloric acid through partially hydrated magnesium chloride fluidization pyrolysis: CN105197968A[P]. 2015-12-30.
24	HUANG Q Z , LU G M , WANG J , et al . Thermal decomposition mechanisms of MgCl₂·6H₂O and MgCl₂·H₂O[J]. Journal of Analytical and Applied Pyrolysis, 2011, 91(1): 159-164.
25	HUANG Q Z , LU G M , WANG J , et al . Mechanism and kinetics of thermal decomposition of MgCl₂·6H₂O[J]. Metallurgical and Materials Transactions B, 2010, 41(5): 1059-1066.
26	PUN D , ALI S . Unsupervised clustering for electrofused magnesium oxide sorting[C]//2009 IEEE International Conference on Industrial Engineering and Engineering Management. 2009: 698-702.
27	谢祥 . 盐湖卤水热解氧化镁制备高纯电熔镁砂的研究[D]. 上海: 华东理工大学, 2015.
	XIE X . Study on the high purity electro-fused magnesia produced by salt lake brine[D]. Shanghai: East China University of Science and Technology, 2015.
28	路贵民, 谢祥, 杜玮, 等 . 一种生产大结晶电熔镁砂的添加剂: CN103864119A[P]. 2014-06-18.
	LU G M , XIE X , DU W , et al . Additive for producing macrocrystalline fused magnesite: CN103864119A[P]. 2014-06-18.
29	仝永娟 . 电熔镁系统节能新工艺研究[D]. 沈阳: 东北大学, 2010.
	TONG Y J . Study on advanced technology of fused magnesia process based on system's energy conservation theory[D]. Shenyang: Northeastern University, 2010.
30	WANG Z , WANG N H . Numerical simulation of melt convection in an AC electro-fused magnesia furnace for MgO production[J]. IET Electr. Power Appl., 2018, 12(5): 701-707.
31	MA W L, ZHU S X . Intelligent control algorithm of electric-fused magnesia furnace based on neural network[C]
	//XING Song, CHEN Suting , WEI Zhanming , et al . Unifying Electrical Engineering and Electronics Engineering. Proceedings of the 2012 International Conference on Electrical and Electronics Engineering. New York: Springer, 2014: 1877-1886.
32	FANG Z , YANG J , TAO S F , et al . A real-time embedded control system for electro-fused magnesia furnace[J]. J. Control. Sci. Eng., 2013, 2013: 12. DOI: 10.1155/2013/719683. DOI URL
33	吉亚明, 蒋丹宇, 冯涛, 等 . 透明陶瓷材料现状与发展[J]. 无机材料学报, 2004, 19(2): 275-282.
	JI Y M , JIANG D Y , FENG T , et al . Fabrication and developments of transparent ceramics[J]. Journal of Inorganic Materials, 2004, 19(2): 275-282.
34	CHEN D Y , JORDAN E H , GELL M . Pressureless sintering of translucent MgO ceramics[J]. Scripta Materialia, 2008, 59(7): 757-759.
35	EHRE D , GUTMANAS E Y , CHAIM R . Densification of nanocrystalline MgO ceramics by hot-pressing[J]. Journal of the European Ceramic Society, 2005, 25(16): 3579-3585.
36	ITATANI K , TSUJIMOTO T , KISHIMOTO A . Thermal and optical properties of transparent magnesium oxide ceramics fabricated by post hot-isostatic pressing[J]. Journal of the European Ceramic Society, 2006, 26(4): 639-645.
37	CHAIM R , SHEN Z J , NYGREN M . Transparent nanocrystalline MgO by rapid and low-temperature spark plasma sintering[J]. Journal of Materials Research, 2004, 19(9): 2527-2531.
38	SUN H B , ZHANG Y J , GONG H Y , et al . Microwave sintering and kinetic analysis of Y₂O₃-MgO composites[J]. Ceram Int., 2014, 40(7): 10211-10215.
39	MISAWA T , MORIYOSHI Y , Y Y . Effect of silica and boron oxide on transparency of magnesia ceramics[J]. Journal of the Ceramic Society of Japan, 1999, 107(1244): 343-348.
40	周佳芬 . 透光氧化镁陶瓷制备工艺及性能研究[D]. 上海: 华东理工大学, 2018.
	ZHOU J F . Study on the preparation and properties of translucent mgo ceramics[D]. Shanghai: East China University of Science and Technology, 2018.
41	LAYDEN G K , MCQUARRIE M C . Effect of minor additions on sintering of MgO[J].AmJ.Ceram. Soc., 1959, 42(2): 89-92.
42	RICE R W . Hot-pressing of MgO with NaF[J]. Journal of the American Ceramic Society, 1971, 54(4): 205-207.
43	RHODES W , SELLERS D , VASILOS T . Development and evaluation of transparent magnesium oxide[R]. Watertown, Massachusetts: U. S. Army Materials Research Agency, 1967.
44	BENECKE M W , OLSON N E , PASK J A . Effect of LiF on hot-pressing of MgO[J].AmJ.Ceram. Soc., 1967, 50(7): 365-368.
45	FANG Y , AGRAWAL D , SKANDAN G , et al . Fabrication of translucent MgO ceramics using nanopowders[J]. Materials Letters, 2004, 58(5): 551-554.
46	KAN A , MORIYAMA T , TAKAHASHI S , et al . Low-temperature sintering and microwave dielectric properties of MgO ceramic with LiF addition[J]. Japanese Journal of Applied Physics, 2011, 50(9): 1489-1496.
47	KÖBEL S , SCHNEIDER D , SCHÜLER C C , et al . Sintering of vanadium-doped magnesium oxide[J]. Journal of the European Ceramic Society, 2004, 24(8): 2267-2274.
48	LEE Y B , PARK H C , OH K D , et al . Sintering and microstructure development in the system MgO-TiO₂ [J]. Journal of Materials Science, 1998, 33(17): 4321-4325.
49	HAN B Q , LI Y S , GUO C C , et al . Sintering of MgO-based refractories with added WO₃ [J]. Ceram. Int., 2007, 33(8): 1563-1567.
50	PENG C , LI N , HAN B . Effect of zircon on sintering, composition and microstructure of magnesia powders[J]. Science of Sintering, 2009, 41(1): 11-17.
51	于忞, 罗旭东, 张国栋, 等 . TiO₂对氧化镁陶瓷烧结性能及抗热震性能的影响[C]//第十九届全国高技术陶瓷学术年会. 2016: 52-53.
	YU M , LUO X D , ZHANG G D , et al . Effect of TiO₂ on sintering and thermal shock resistance of MgO ceramic[C]// The Nineteenth National Academic Annual Meeting of High Tech Ceramics. 2016: 52-53.
52	YU M , LUO X D , ZHANG G D , et al . Effect of Al₂O₃ on sintering and thermal shock resistance of MgO ceramic[J]. Journal of Synthetic Crystals, 2017, 46(3): 507-513.
53	YU M , LUO X D , ZHANG G D , et al . Effect of La₂O₃ on sintering properties and thermal shock properties of MgO ceramic[J]. Journal of Synthetic Crystals, 2016, 45(9): 2251-2256.
54	彭子钧, 罗旭东, 于忞, 等 . Al₂O₃和TiO₂添加量对共沉淀法制备MgO基陶瓷性能的影响[J]. 机械工程材料, 2018, 42(4): 35-39.
	PENG Z J , LUO X D , YU M , et al . Effect of Al₂O₃ and TiO₂ addition amount on properties of MgO-based ceramics by coprecipitation method[J]. Materials for Mechanical Engineering, 2018, 42(4): 35-39.
55	KARPINOS D M , GROSHEVA V M , MOROZOVA V N , et al . Some properties of magnesium oxide ceramic reinforced with filamentary crystals of zirconium dioxide[J]. Refractories, 1978, 19(11/12): 782-786.
56	饶东生, 林彬荫, 朱伯铨 . 降低高纯氧化镁烧结温度的研究[J]. 硅酸盐学报, 1989, 17(1): 75-81.
	RAO D S , LIN B Y , ZHU B Q . Study on decreasing sintering temperature of high purity magnesite[J]. Journal of the Chinese Ceramic Society, 1989, 17(1): 75-81.
57	徐智清, 卓育华 . 影响氧化镁陶瓷芯性能的几个因素[J]. 铸造, 1996(10): 11-14.
	XU Z Q , ZHUO Y H . Factors influencing properties of magnesia ceramic core[J]. Foundry, 1996(10): 11-14.

[1]	LI Zhiyuan, HUANG Yaji, ZHAO Jiaqi, YU Mengzhu, ZHU Zhicheng, CHENG Haoqiang, SHI Hao, WANG Sheng. Characterization of heavy metals during co-pyrolysis of sludge with PVC [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4947-4956.
[2]	LI Haidong, YANG Yuankun, GUO Shushu, WANG Benjin, YUE Tingting, FU Kaibin, WANG Zhe, HE Shouqin, YAO Jun, CHEN Shu. Effect of carbonization and calcination temperature on As(Ⅲ) removal performance of plant-based Fe-C microelectrolytic materials [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3652-3663.
[3]	YAO Liming, WANG Yazhuo, FAN Honggang, GU Qing, YUAN Haoran, CHEN Yong. Treatment status of kitchen waste and its research progress of pyrolysis technology [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3791-3801.
[4]	ZHANG Shan, ZHONG Zhaoping, YANG Yuxuan, DU Haoran, LI Qian. Enrichment of heavy metals in pyrolysis of municipal solid waste by phosphate modified kaolin [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3893-3903.
[5]	LI Ruolin, HE Shaolin, YUAN Hongying, LIU Boyue, JI Dongli, SONG Yang, LIU Bo, YU Jiqing, XU Yingjun. Effect of in-situ pyrolysis on physical properties of oil shale and groundwater quality [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 3309-3318.
[6]	LI Dongxian, WANG Jia, JIANG Jianchun. Producing biofuels from soapstock via pyrolysis and subsequent catalytic vapor-phase hydrotreating process [J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2874-2883.
[7]	WANG Zhiwei, GUO Shuaihua, WU Mengge, CHEN Yan, ZHAO Junting, LI Hui, LEI Tingzhou. Recent advances on catalytic co-pyrolysis of biomass and plastic [J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2655-2665.
[8]	LIANG Yijing, MA Yan, LU Zhanfeng, QIN Fusheng, WAN Junjie, WANG Zhiyuan. Experimental investigation on the anti-coking performance of La_1-_x Sr _x MnO₃ perovskite coating [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1769-1778.
[9]	LIU Jing, LIN Lin, ZHANG Jian, ZHAO Feng. Research progress in pore size regulation and electrochemical performance of biomass-based carbon materials [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1907-1916.
[10]	YANG Ziqiang, LI Fenghai, GUO Weijie, MA Mingjie, ZHAO Wei. Review on phosphorus migration and transformation during municipal sewage sludge heat treatment [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2081-2090.
[11]	ZHAO Jiaqi, HUANG Yaji, LI Zhiyuan, DING Xueyu, QI Shuaijie, ZHANG Yuyao, LIU Jun, GAO Jiawei. Characteristics of three-phase products from co-pyrolysis of sewage sludge and PVC [J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2122-2129.
[12]	PAN Yuhan, XU Jun, ZHAO Guangjie, LIN Chengqian, JIN Liang, XUE Zhiliang, ZHOU Yonggang, HUANG Qunxing. Development of pilot-plant for the step pyrolysis of waste tires and analysis of product characteristics [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1240-1247.
[13]	HE Yangdong, CHANG Honggang, WANG Dan, CHEN Changjie, LI Yaxin. Development of methane pyrolysis based on molten metal technology for coproduction of hydrogen and solid carbon products [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1270-1280.
[14]	ZHENG Yunwu, PEI Tao, LI Donghua, WANG Jida, LI Jirong, ZHENG Zhifeng. Production of hydrocarbon-rich bio-oil by catalytic biomass pyrolysis over metal oxide improved P/HZSM-5 catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1353-1364.
[15]	CAO Min, MAO Yujiao, WANG Qianqian, LI Sha, YAN Xiaoliang. Sintering mechanism and sintering-resistant strategies for metal-based catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(2): 744-755.