镁质贫镍红土矿热分解理论计算与实验研究
|
摘要
以镁质贫镍红土矿为原料,对其进行焙烧热分解实验,研究红土矿受热分解过程中的脱羟基反应与重结晶过程的物相转变。以蛇纹石热分解物相转变的实验研究为基础进行模拟结果验证,通过理论计算模拟了实验过程,以阐明镁质红土矿升温过程中的物相转变作用机制。结果表明,红土矿中主要成分是蛇纹石相(Mg_3Si_2O_5(OH)_4),升温至612℃后发生脱羟基反应,生成非晶态硅酸盐;继续加热至817℃发生重结晶反应,生成橄榄石和顽辉石相以及少量的SiO_2。通过密度泛函理论(DFT)计算Mg_3Si_2O_5(OH)_4原子的键长、态密度、密立根布居等参数,对其热分解过程进行分子动力学计算模拟。结果显示,动力学模拟条件下,蛇纹石内部羟基以氢氧根的形式直接脱离,生成非晶态硅酸盐产物,继续升温,非晶态硅酸盐中SiO_2有离解分离的趋势,参与重结晶过程,生成结晶度良好且致密的橄榄石和顽辉石相,计算模拟结果与实验结果吻合较好。
The high-magnesium low-nickel laterite was taken as raw material,the thermal decomposition experiment by calcination was carried out to study the phase transformation of dehydroxylation and re-crystallization during the thermal decomposition of laterite. Based on the experimental study on phase transformation of thermal decomposition of serpentine,the experimental process was simulated by theoretical calculation to clarify the phase transformation of magnesite laterite during heating process. The results indicated that Mg_3Si_2O_5(OH)_4 was the major ingredient of laterite,dehydroxylation reaction occurred when temperature exceeded 612 ℃,and amorphous silicate mineral generated. Subsequently,the recrystallization occurred when heating up to 817 ℃,generating peridot phase,enstatite,as well as a small amount of SiO_2. By means of density functional theory( DFT),the atomic bond length,state density and Millikan population of Mg_3Si_2O_5(OH)_4 were calculated,and its molecular dynamics calculation during thermal decomposition was simulated. The results showed that under the condition of kinetic simulation,the hydroxyl groups in Mg_3Si_2O_5(OH)_4 would be separated directly in the form of hydroxyl to form amorphous silicate products. With the rising temperature,the SiO_2 in amorphous silicate tended to dissociate and separate,participating in re-crystallization process and producing peridot phase and enstatite with better crystallinity. The calculation simulated results were well fitted with the experimental results.
The high-magnesium low-nickel laterite was taken as raw material,the thermal decomposition experiment by calcination was carried out to study the phase transformation of dehydroxylation and re-crystallization during the thermal decomposition of laterite. Based on the experimental study on phase transformation of thermal decomposition of serpentine,the experimental process was simulated by theoretical calculation to clarify the phase transformation of magnesite laterite during heating process. The results indicated that Mg_3Si_2O_5(OH)_4 was the major ingredient of laterite,dehydroxylation reaction occurred when temperature exceeded 612 ℃,and amorphous silicate mineral generated. Subsequently,the recrystallization occurred when heating up to 817 ℃,generating peridot phase,enstatite,as well as a small amount of SiO_2. By means of density functional theory( DFT),the atomic bond length,state density and Millikan population of Mg_3Si_2O_5(OH)_4 were calculated,and its molecular dynamics calculation during thermal decomposition was simulated. The results showed that under the condition of kinetic simulation,the hydroxyl groups in Mg_3Si_2O_5(OH)_4 would be separated directly in the form of hydroxyl to form amorphous silicate products. With the rising temperature,the SiO_2 in amorphous silicate tended to dissociate and separate,participating in re-crystallization process and producing peridot phase and enstatite with better crystallinity. The calculation simulated results were well fitted with the experimental results.
引文
1 Peng B,Qing R.The Engineer of Non-Ferrous Metal,2011,1(4),15(in Chinese).彭犇,清瑞.有色金属工程,2011,1(4),15.
2 Pang J M,Guo P M,Zhao P,et al.Journal of Iron and Steel Research,2011,23(6),1(in Chinese).庞建明,郭培民,赵沛,等.钢铁研究学报,2011,23(6),1.
3 Liu Y,Zhai Y C,Wang H.Materials Review,2006,20(3),79(in Chinese).刘岩,翟玉春,王虹.材料导报,2006,20(3),79.
4 Zhao J F,Sun Z,Zheng P,et al.Non-ferrous Minging and Metallurgy,2012,28(6),39(in Chinese).赵景富,孙镇,郑鹏,等.有色矿冶,2012,28(6),39.
5 Zhu D Q,Cui Y,Hapugoda S,et al.Transactions of Nonferrous Metals Society of China,2012,22(4),907.
6 Li J H,Li Y Y,Zheng S,et al.Nonferrous Metals Science and Engineering,2015(1),35.李金辉,李洋洋,郑顺,等.有色金属科学与工程,2015(1),35.
7 Li Y Y,Li J H,Zhang Y F,et al.Materials Review A:Review Papers,2015,29(9),79(in Chinese).李洋洋,李金辉,张云芳,等.材料导报:综述篇,2015,29(9),79.
8 Parr R G.Chemical&Engineering News,1983,68(1),2470.
9 Xu G X,Li L M,Wang D M.Quantum chemistry:Fundamentals and abinitio methods,Science Press,China,2009(in Chinese).徐光宪,黎乐民,王德民.量子化学:基本原理和从头计算法,科学出版社,2009.
10 Balan E,Saitta A M,Mauri F,et al.American Mineralogist,2002,87(10),1286.
11 Prencipe,Noel M,Bruno Y,et al.American Mineralogist,2009,94(7),986.
12 Wen S M,Deng J S,Xian Y J,et al.Transactions of Nonferrous Metals Society of China,2013,23(3),796.
13都兴红,刘慧,牛亚慧,等.全国冶金物理化学学术会议.昆明,2013,pp.6.
14 Li Q,Li B,Wei Y G,et al.Chinese Journal of Rare Metals,2016,40(5),485.李谦,李博,魏永刚,等.稀有金属,2016,40(5),485.
15 Ma G H.Controllable synthesis and growth mechanism of serpentine nanostructures.Master’s Thesis,Chinese Academy of Engineering Phy-sics,China,2012(in Chinese).马国华.蛇纹石结构纳米材料的可控合成与生长机理研究.硕士学位论文,中国工程物理研究院,2012.
16 Hu L,Liu D C,Chen X M,et al.The Chinese Journal of Nonferrous Metals,2014(9),2410(in Chinese).胡亮,刘大春,陈秀敏,等.中国有色金属学报,2014(9),2410.
17 Perdew J P,Burke K,Physical Review Letters,1996,77(18),3865.
18 Perdew J P,Zunger A.Physical Review B,1981,23(10),5048.
19 Qin Y H,Qiao Y J.Functional Materials,2015,46(22),22058(in Chinese).秦永和,乔英杰.功能材料,2015,46(22),22058.
20 Fischer T H,Almlof J.The Journal of Physical Chemistry,1992,96(24),9768.
21 Arias T A,Payne M C,Joannopoulos J D.Physical Review Letters,1992,69(7),1077.
22 Yuan Q G.Research on the properties of slag with low-lime in nickel laterite smelting process with electric furnace.Master’s Thesis,Chongqing University,China,2014(in Chinese).袁秋刚.红土镍矿电炉冶炼工艺低钙渣系性质研究.硕士学位论文,重庆大学,2014.
23 Li H Z,Guo H J.Ferro-Alloys,2014,45(4),40(in Chinese).李好泽,郭汉杰.铁合金,2014,45(4),40.
24 Li B,Wei Y G,Wang H,et al.The Chinese Journal of Nonferrous Metals,2013(5),1440(in Chinese).李博,魏永刚,王华,等.中国有色金属学报,2013(5),1440.
25 Lu Y.Theoretical calculation of Al2O3carbothermic products chlorination and Al N chlorination.Master’s Thesis,Kunming University of Science and Technology,China,2016(in Chinese).卢勇.Al2O3碳热产物及Al N氯化机理研究.硕士学位论文,昆明理工大学,2016.
26 Zhou S,Wei Y,Li B,et al.Journal of Alloys&Compounds,2017,713,180.
27 Barbottin G,Vapaille A.Instabilities in Silicon Devices:Silicon Passivation and Related Instabilities,Elsevier Science Publishers,USA,1986.
2 Pang J M,Guo P M,Zhao P,et al.Journal of Iron and Steel Research,2011,23(6),1(in Chinese).庞建明,郭培民,赵沛,等.钢铁研究学报,2011,23(6),1.
3 Liu Y,Zhai Y C,Wang H.Materials Review,2006,20(3),79(in Chinese).刘岩,翟玉春,王虹.材料导报,2006,20(3),79.
4 Zhao J F,Sun Z,Zheng P,et al.Non-ferrous Minging and Metallurgy,2012,28(6),39(in Chinese).赵景富,孙镇,郑鹏,等.有色矿冶,2012,28(6),39.
5 Zhu D Q,Cui Y,Hapugoda S,et al.Transactions of Nonferrous Metals Society of China,2012,22(4),907.
6 Li J H,Li Y Y,Zheng S,et al.Nonferrous Metals Science and Engineering,2015(1),35.李金辉,李洋洋,郑顺,等.有色金属科学与工程,2015(1),35.
7 Li Y Y,Li J H,Zhang Y F,et al.Materials Review A:Review Papers,2015,29(9),79(in Chinese).李洋洋,李金辉,张云芳,等.材料导报:综述篇,2015,29(9),79.
8 Parr R G.Chemical&Engineering News,1983,68(1),2470.
9 Xu G X,Li L M,Wang D M.Quantum chemistry:Fundamentals and abinitio methods,Science Press,China,2009(in Chinese).徐光宪,黎乐民,王德民.量子化学:基本原理和从头计算法,科学出版社,2009.
10 Balan E,Saitta A M,Mauri F,et al.American Mineralogist,2002,87(10),1286.
11 Prencipe,Noel M,Bruno Y,et al.American Mineralogist,2009,94(7),986.
12 Wen S M,Deng J S,Xian Y J,et al.Transactions of Nonferrous Metals Society of China,2013,23(3),796.
13都兴红,刘慧,牛亚慧,等.全国冶金物理化学学术会议.昆明,2013,pp.6.
14 Li Q,Li B,Wei Y G,et al.Chinese Journal of Rare Metals,2016,40(5),485.李谦,李博,魏永刚,等.稀有金属,2016,40(5),485.
15 Ma G H.Controllable synthesis and growth mechanism of serpentine nanostructures.Master’s Thesis,Chinese Academy of Engineering Phy-sics,China,2012(in Chinese).马国华.蛇纹石结构纳米材料的可控合成与生长机理研究.硕士学位论文,中国工程物理研究院,2012.
16 Hu L,Liu D C,Chen X M,et al.The Chinese Journal of Nonferrous Metals,2014(9),2410(in Chinese).胡亮,刘大春,陈秀敏,等.中国有色金属学报,2014(9),2410.
17 Perdew J P,Burke K,Physical Review Letters,1996,77(18),3865.
18 Perdew J P,Zunger A.Physical Review B,1981,23(10),5048.
19 Qin Y H,Qiao Y J.Functional Materials,2015,46(22),22058(in Chinese).秦永和,乔英杰.功能材料,2015,46(22),22058.
20 Fischer T H,Almlof J.The Journal of Physical Chemistry,1992,96(24),9768.
21 Arias T A,Payne M C,Joannopoulos J D.Physical Review Letters,1992,69(7),1077.
22 Yuan Q G.Research on the properties of slag with low-lime in nickel laterite smelting process with electric furnace.Master’s Thesis,Chongqing University,China,2014(in Chinese).袁秋刚.红土镍矿电炉冶炼工艺低钙渣系性质研究.硕士学位论文,重庆大学,2014.
23 Li H Z,Guo H J.Ferro-Alloys,2014,45(4),40(in Chinese).李好泽,郭汉杰.铁合金,2014,45(4),40.
24 Li B,Wei Y G,Wang H,et al.The Chinese Journal of Nonferrous Metals,2013(5),1440(in Chinese).李博,魏永刚,王华,等.中国有色金属学报,2013(5),1440.
25 Lu Y.Theoretical calculation of Al2O3carbothermic products chlorination and Al N chlorination.Master’s Thesis,Kunming University of Science and Technology,China,2016(in Chinese).卢勇.Al2O3碳热产物及Al N氯化机理研究.硕士学位论文,昆明理工大学,2016.
26 Zhou S,Wei Y,Li B,et al.Journal of Alloys&Compounds,2017,713,180.
27 Barbottin G,Vapaille A.Instabilities in Silicon Devices:Silicon Passivation and Related Instabilities,Elsevier Science Publishers,USA,1986.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |