含钛钢渣在熔融NaOH体系中焙烧过程及其反应机理
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摘要
针对高钙、高磷型含钛钢渣的特点,采用Na OH为焙烧剂,考察焙烧温度、焙烧时间、碱矿比对含钛钢渣在熔融Na OH体系中TiO2提取率的影响,并对焙烧过程动力学进行解析。研究结果表明:含钛钢渣在熔融Na OH体系中优化反应条件为焙烧温度450℃,碱矿比6:1,焙烧时间60min;当焙烧温度为350～500℃时,含钛钢渣在熔融Na OH体系中焙烧过程由内扩散控制,反应表观活化能E=10.77k J/mol,其动力学方程可描述为:1-2X/3-(1-X)2/3=1.239exp[-39.4/(RT)]t;含钛钢渣中主要物相Mg2TiO4,Mn Ti2O4和CaTiO3在熔融Na OH体系中焙烧过程中已完全分解,为后续钛的提取创造了有利条件。
With consideration of the high content of calcium and phosphorus, titanium-bearing steel slag was roasted with NaOH to investigate the effects of roasting temperature, roasting time and mass ration of alkali-to-ore on the TiO2 extraction rate. The kinetics of the roasting process were analyzed. The results show that the optimal conditions of titanium-bearing steel slag reacted with NaOH melt are as follows: roasting temperature 450 ℃, alkali-to-ore ratio 6:1 and roasting time 60 min. The roasting process is found to be diffusion controlled at temperature of 350-500 ℃. The apparent activation energy is 10.77 kJ/mol, and the kinetic equation can be described as follows: 1-2X/3-(1-X)2/3= 1.239exp[-39.4/(RT)]t. The complete decomposition of the main phases(Mg2TiO4, MnTi2O4, CaTiO3) in titanium-bearing steel slag after roasting with NaOH has created favorable conditions for the extraction of titanium.
With consideration of the high content of calcium and phosphorus, titanium-bearing steel slag was roasted with NaOH to investigate the effects of roasting temperature, roasting time and mass ration of alkali-to-ore on the TiO2 extraction rate. The kinetics of the roasting process were analyzed. The results show that the optimal conditions of titanium-bearing steel slag reacted with NaOH melt are as follows: roasting temperature 450 ℃, alkali-to-ore ratio 6:1 and roasting time 60 min. The roasting process is found to be diffusion controlled at temperature of 350-500 ℃. The apparent activation energy is 10.77 kJ/mol, and the kinetic equation can be described as follows: 1-2X/3-(1-X)2/3= 1.239exp[-39.4/(RT)]t. The complete decomposition of the main phases(Mg2TiO4, MnTi2O4, CaTiO3) in titanium-bearing steel slag after roasting with NaOH has created favorable conditions for the extraction of titanium.
引文
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[3]YU R,LIU Z,POURPOINT F,et al.Nanoparticulate TiO2(B):an anode for lithium-ion batteries[J].Angewandte Chemie International Edition,2012,51(9):2164-2167.
[4]FENG X J,ZHU K,FRANK A J,et al.Rapid charge transport in dye-sensitized solar cells made from vertically aligned single-crystal rutile TiO2 nanowires[J].Angewandte Chemie International Edition,2012,51(11):2727-2730.
[5]ZHANG Y.Recovery of titanium from titanium bearing blast furnace slag by sulphate melting[J].Canadian Metallurgical Quarterly,2014,53(4):440-443.
[6]王思佳,张悦,薛向欣,等.硫酸铵熔融反应法从含钛高炉渣中回收钛[J].化工学报,2012,63(3):991-995.WANG Sijia,ZHANG Yue,XUE Xiangxin,et al.Recovery of titanium from titanium-bearing blast furnace slag by ammonium sulfate melting method[J].CIESC Journal,2012,63(3):991-995.
[7]霍东兴,梁精龙,李慧,等.含钛高炉渣提取钛的研究进展[J].热加工工艺,2017,46(3):13-15.HUO Dongxing,LIANG Jinglong,LI Hui,et al.Research progress on extracting titanium from blast furnace slag containing titanium[J].Hot Working Technology,2017,46(3):13-15.
[8]李鑫,于洪浩,张侯芳,等.熔盐高效分解含钛高炉渣制备纳米二氧化钛[J].化工学报,2015,66(2):827-833.LI Xin,YU Honghao,ZHANG Houfang,et al.Preparation of nano TiO2 from Ti-bearing blast furnace slag by molten salt method[J].CIESC Journal,2015,66(2):827-833.
[9]HE Siqi,SUN Hongjuan,TAN Daoyong,et al.Recovery of titanium compounds from ti-enriched product of alkali melting Ti-bearing blast furnace slag by dilute sulfuric acid leaching[J].Procedia Environmental Sciences,2016,31:977-984.
[10]熊瑶,李春,梁斌,等.盐酸浸出自然冷却含钛高炉渣[J].中国有色金属学报,2008,18(3):557-563.XIONG Yao,LI Chun,LIANG Bin,et al.Leaching behavior of air cooled Ti-bearing blast-furnace slag in hydrochloric acid[J].The Chinese Journal of Nonferrous Metals,2008,18(3):557-563.
[11]隋丽丽,翟玉春.硫酸氢铵焙烧高钛渣提取Ti O2[J].中国有色金属学报,2014,24(3):826-830.SUI Lili,ZHAI Yuchun.Extraction of TiO2 from high titanium slag through roasting by ammonium bisulfate[J].The Chinese Journal of Nonferrous Metals,2014,24(3):826-830.
[12]WU Zhang,LI Zhang,LI Yuhai,et al.An environmental procedure to extract titanium components and metallic iron from Ti-bearing blast furnace slag[J].Green Processing and Synthesis,2015,4(4):24-27.
[13]GRZMIL B U,GRELA D,KIC B.Hydrolysis of titanium sulphate compounds[J].Chemical Papers,2008,62(1):18-25.
[14]赵昌明,翟玉春,刘岩,等.红土镍矿在Na OH亚熔盐体系中的预脱硅[J].中国有色金属学报,2009,19(5):949-954.ZHAO Changming,ZHAI Yuchun,LIU Yan,et al.Pre-desilication of laterite in NaOH sub-molten salt system[J].The Chinese Journal of Nonferrous Metals,2009,19(5):949-954.
[15]华一新.冶金过程动力学导论[M].北京:冶金工业出版社,2004:188-193.HUA Yixin.Introduction to kinetics of metallurgy progress[M].Beijing:Metallurgical Industry Press,2004:188-193.