二氧化硅杂质对重晶石碳热还原反应的影响及其相变行为分析
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摘要
二氧化硅(SiO_2)是重晶石矿中的主要杂质,本工作以贵州镇宁重晶石矿为研究对象,对SiO_2在重晶石中的赋存状态及其对重晶石碳热还原反应的影响进行了研究,并采用XRD物相分析结合HSC热力学分析对SiO_2在重晶石碳热还原过程中的相变行为进行了探讨。结果表明:重晶石中SiO_2主要以独立矿物石英的形式与硫酸钡伴生,并存在少量SiO_2以硫酸钡包裹体和隐晶质存在。SiO_2对重晶石碳热还原反应的影响主要是以独立矿物形式存在的SiO_2影响为主,在重晶石碳热还原过程中,SiO_2杂质分散在体系中,由石英相向鳞石英相及方石英相转变,对体系传热、传质形成一定阻碍,使得体系最佳反应温度升高约100℃。同时,SiO_2晶型重构过程活性高,使其易与体系中钡盐反应生成BaSiO_3及Ba_2SiO_4,从而导致体系硫化钡转化率降低,酸溶性钡转化率增大。
Silica is the main impurity in barite. Taking the barite mine from Zhenning,Guizhou province as the research object,the occurrence state of SiO_2 in barite and its impact on barite carbothermal reduction were studied. XRD phase analysis and HSC thermodynamic analysis were carried out to study the phase transformation behavior of SiO_2. The results showed that SiO_2 in barite was mainly associated with barium sulfate in the form of independent mineral quartz,and a small amount of SiO_2 existed in barium sulfate inclusions and cryptocrystalline. SiO_2 in the form of independent minerals played a dominant role in affecting the carbothermal reduction of barite. In the carbothermal reduction process of barite,SiO_2 impurities were dispersed in the system and experienced crystal transition from quartz phase to squamous quartz phase and cristobalite phase,which blocked heat transfer and mass transfer of the system and resulted in a 100 ℃ rise of the optimized carbothermal reaction temperature. Meanwhile,the high activity of SiO_2 in the process of crystal reconstruction made it easy to react with barium salt to form BaS iO 3 and Ba2 SiO 4,which caused the decrease of barium sulfide conversion and the increase of acid-soluble barium conversion.
Silica is the main impurity in barite. Taking the barite mine from Zhenning,Guizhou province as the research object,the occurrence state of SiO_2 in barite and its impact on barite carbothermal reduction were studied. XRD phase analysis and HSC thermodynamic analysis were carried out to study the phase transformation behavior of SiO_2. The results showed that SiO_2 in barite was mainly associated with barium sulfate in the form of independent mineral quartz,and a small amount of SiO_2 existed in barium sulfate inclusions and cryptocrystalline. SiO_2 in the form of independent minerals played a dominant role in affecting the carbothermal reduction of barite. In the carbothermal reduction process of barite,SiO_2 impurities were dispersed in the system and experienced crystal transition from quartz phase to squamous quartz phase and cristobalite phase,which blocked heat transfer and mass transfer of the system and resulted in a 100 ℃ rise of the optimized carbothermal reaction temperature. Meanwhile,the high activity of SiO_2 in the process of crystal reconstruction made it easy to react with barium salt to form BaS iO 3 and Ba2 SiO 4,which caused the decrease of barium sulfide conversion and the increase of acid-soluble barium conversion.
引文
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16 Jamshidi S, Salem A. Thermochimica Acta,2010,503-504,108.
17 Snell F D, Hilton C L, Ettre L S. Encyclopedia of industrial chemical analysis, Interscience Publishers, New York, 1968.
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19 German Iron and Steel Federation.Slag Atlas.Wang J, Peng Y Q, Mao Y W, trans. Metallurgical Industry Press, China,1989(in Chinese).德国钢铁工程师协会. 渣图集. 王俭, 彭育强, 毛裕文, 译. 冶金工业出版社,1989.
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2 Li W Y, Yu H Y. China barite deposit. Geological Publishing House, China,1991(in Chinese).李文炎,余洪云. 中国重晶石矿床,地质出版社,1991.
3 Yuan J G, Qu Y Y, Liu X L, et al.Modern Chemical Industry, 2017,37(6),1(in Chinese).袁建国, 屈云燕, 柳霞丽, 等.现代化工,2017,37(6),1.
4 Wang Q W, Zhang Y Y. Modern Chemical Industry, 2014,34(12), 5(in Chinese).王庆伟, 张元元.现代化工,2014,34(12),5.
5 Mcketta J J, Executive E D. Encyclopedia of chemical processing and design, vol. 4, Marcel Dekker, New York,1976.
6 Jamshidi S, Salem A. Thermochimica Acta,2010,503,108.
7 Salem A, Osgouei Y T. Materials Research Bulletin,2009,44,1489.
8 Jyotsna A. Materials Today: Proceedings,2017,4,104.
9 Pelovski Y, Taniguchi M. Journal of Thermal Analysis,1988,33(3),603.
10 Pelovski Y, Ninova K, Gruncharov I, et al. Journal of Thermal Analysis,1990,36(6),2037.
11 Jamshidi E, Ebrahim H A. Chemical Engineering and Processing,2008,47(9),1567.
12 Alizadeh R, Jamshidi E, Ebrahim H A. Thermochimica Acta,2007,460(1),44.
13 Hlabela P S, Neomagus H W J P, Waanders F B, et al.Thermochimica Acta,2010,498 (1-2), 67.
14 Gao J B, Yang R D, Tao P, et al. Acta Sedimentologica Sinica,2012,30(3),422(in Chinese).高军波, 杨瑞东, 陶平, 等.沉积学报,2012,30(3),422.
15 Zhao Y. Flotation technology of low grade barite and adsorption mechanism of collectors. Master’s thesis, Kunming university of science and technology, China,2014(in Chinese).赵阳. 低品位重晶石浮选工艺及捕收剂吸附机理研究. 硕士学位论文,昆明理工大学,2014.
16 Jamshidi S, Salem A. Thermochimica Acta,2010,503-504,108.
17 Snell F D, Hilton C L, Ettre L S. Encyclopedia of industrial chemical analysis, Interscience Publishers, New York, 1968.
18 Fang W X, Hu R Z, Su W C, et, al. Acta Petrologica Sinica,2002,18(2),247(in Chinese).方维萱, 胡瑞忠, 苏文超, 等.岩石学报,2002,18(2),247.
19 German Iron and Steel Federation.Slag Atlas.Wang J, Peng Y Q, Mao Y W, trans. Metallurgical Industry Press, China,1989(in Chinese).德国钢铁工程师协会. 渣图集. 王俭, 彭育强, 毛裕文, 译. 冶金工业出版社,1989.
20 Lu P W. Fundamentals of inorganic materials science: silicate physical chemistry, Wuhan Industrial University Press, China,1996(in Chinese).陆佩文.无机材料科学基础:硅酸盐物理化学,武汉工业大学出版社,1996.