分段尝试法研究碱金属对铁氧化物还原的影响
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摘要
为了研究碱金属在高炉内对Fe_2O_3还原的影响,采用热重分析方法研究含有不同碱金属含量的Fe_2O_3在不同温度下的还原特性。通过分析试样的还原度曲线,讨论温度和碱金属含量对还原过程的影响,发现随着温度的升高,反应速率增加,试样的还原度增加,接近完全还原的反应时间缩短;Na_2O对Fe_2O_3的还原有抑制作用,抑制作用随着Na_2O含量增加而加强,但这种抑制作用随着Na_2O含量增加不是均匀增长的,会存在饱和点。针对还原过程的特点,采用分段尝试法建立了前期化学反应控速的未反应核模型和后期收缩核内扩散模型,并对实验数据进行分段拟合,求得相关动力学参数,同时定量地给出了不同的温度条件下2种控制转换的时间点。从拟合结果看,实验数据和模型取得了很好的吻合,说明所建模型与实际情况相符。
In order to study the effect of alkali metal on the reduction of Fe_2O_3 in the blast furnace, thermogravimetric analysis was used to study the reduction characteristics of Fe_2O_3 containing different alkali metal contents at different temperatures. By analyzing reduction curves of the sample, the effects of temperature and alkali metal content on the reduction process were discussed. The results show that with the increase of temperature, the reaction rate and degree of reduction of the sample increase with the reaction time near to complete reduction shortens; Na_2O has an inhibitory effect on the reduction of Fe_2O_3, and the effect increases with Na_2O content increasing. However, this inhibition does not increase linearly and there is a saturation point. At the same time, according to the characteristics of the reduction process, the unreacted nuclear model and the shrinking intranuclear diffusion model were established by the sectioning method. The experimental data were fitted and the relevant kinetic parameters were calculated. The time points of the two control transitions under different temperature conditions were quantitatively given. From the fitting results, the experimental data and the model are in good agreement, indicating that the model is consistent with the actual situation. The sectioning method, as a new method for studying kinetics, is suitable for studying the reduction process of iron oxides and other reaction process kinetics.
In order to study the effect of alkali metal on the reduction of Fe_2O_3 in the blast furnace, thermogravimetric analysis was used to study the reduction characteristics of Fe_2O_3 containing different alkali metal contents at different temperatures. By analyzing reduction curves of the sample, the effects of temperature and alkali metal content on the reduction process were discussed. The results show that with the increase of temperature, the reaction rate and degree of reduction of the sample increase with the reaction time near to complete reduction shortens; Na_2O has an inhibitory effect on the reduction of Fe_2O_3, and the effect increases with Na_2O content increasing. However, this inhibition does not increase linearly and there is a saturation point. At the same time, according to the characteristics of the reduction process, the unreacted nuclear model and the shrinking intranuclear diffusion model were established by the sectioning method. The experimental data were fitted and the relevant kinetic parameters were calculated. The time points of the two control transitions under different temperature conditions were quantitatively given. From the fitting results, the experimental data and the model are in good agreement, indicating that the model is consistent with the actual situation. The sectioning method, as a new method for studying kinetics, is suitable for studying the reduction process of iron oxides and other reaction process kinetics.
引文
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[8] 张兵, 吴铿, 杜瑞玲, 等. 半焦与烧结矿混合还原反应过程动力学[J]. 钢铁研究学报, 2017, 29(12):960.(Zhang B, Wu K, Du R L, et al. Kinetics of mixed reduction process of semi-coke and sinter[J]. Journal of Iron and Steel Research, 2017, 29(12):960.)
[9] 杜瑞玲, 吴铿, 刘启航, 等. 分段法研究兴隆庄煤热解反应过程动力学[J]. 哈尔滨工业大学学报, 2016, 48(4):172.(Du R L, Wu K, Liu Q H, et al. Research on the kinetics of Xinglongzhuang coal pyrolysis reaction process by sectioning method[J]. Journal of Haerbin Institute of Technology, 2016, 48(4):172.)
[10] 张黎, 吴铿, 杜瑞玲, 等. 分段尝试法研究半焦/CO2气化反应过程动力学[J]. 工程科学学报, 2016, 38(11):1539.(Zhang L, Wu K, Du R L, et al. A sectioning method to study gasification reaction kinetics of semi-coke with CO2[J]. Journal of Engineering and Science, 2016, 38(11):1539.)
[11] 潘文, 吴铿, 赵勇, 等. 碱金属对铁氧化物气-固还原行为的影响[J]. 钢铁, 2013, 48(6):7.(Pan W, Wu K, Zhao Y. Effect of alkali on the gas-solid reduction behavior of iron oxide [J]. Iron and Steel, 2013, 48(6):7.)
[12] 何启林, 王德明. 煤的氧化和热解反应的动力学研究[J]. 北京科技大学学报, 2006, 28(1):1.(He Q L, Wang D M. Study on the kinetics of oxidation and pyrolysis of coal [J]. Journal of University of Science and Technology Beijing, 2006, 28(1):1.)
[13] 张长瑞, 杨以文, 张光. 扩散控制的固相反应动力学模型[J]. 物理化学学报, 1988, 4(5):539.(Zhang C R, Yang Y W, Zhang G. Kinetic model of solid-state reaction controlled by diffusion [J]. Acta Physico-Chimica Sinica, 1988, 4(5):539.)
[14] 赵勇, 吴铿, 潘文, 等. 分段法研究烧结矿还原的动力学过程[J]. 东北大学学报:自然科学版, 2013, 34(9):1282.(Zhao Y, Wu K, Pan W, et al. Investigation of the reduction kinetics process of sinter ore by section stepwise method[J]. Journal of Northeastern University: Natural Science, 2013, 34(9):1282.)
[15] 冯向鹏. 矿物组成及显微结构对低硅烧结矿质量的影响[D]//唐山: 河北理工大学, 2003.(Feng X P. The influence of mineral composition and microstructure on the quality of the low silicon sinter[D]. Tang-shan: Hebei Polytechnic University, 2003.)
[2] 潘文, 吴铿, 王洪远, 等. 配加南非粉对首钢烧结矿质量影响的研究[J]. 烧结球团, 2011, 36(4):1.(Pan W, Wu K, Wang H Y. Study on the effect of addition of South African fines on of Shougang sinter quality output[J]. Sintering and Pelletizing, 2011, 36(4):1.)
[3] 郭汉杰, 尹志明, 古特, 等. 宣钢特优钢用活性石灰反应过程动力学研究[J]. 北京科技大学学报, 2007, 29(s1):154.(Guo H J, Yin Z M, Gu T, et al. Dynamics model of producting active lime in Xuanhua Steel[J]. Journal of University of Science and Technology Beijing, 2007, 29(1):154.)
[4] 杨先觉. 高碱度烧结矿还原特性分析[J]. 烧结球团, 2000, 25(4):8.(Yang X J. Analysis of reduction characteristics of high alkalinity sinter[J]. Sintering and Pelletizing, 2000, 25(4):8.)
[5] 潘文, 吴铿, 朝霞, 等. 首钢烧结矿还原动力学[J]. 北京科技大学学报, 2013, 35(1):35.(Pan W, Wu K, Zhao X, et al. Reduction kinetics of Shougang iron ore sinter[J]. Journal of University of Science and Technology Beijing, 2013, 35(1):35.)
[6] 吴铿, 折媛, 朱利, 等. 对建立冶金反应工程学学科体系的思考[J]. 钢铁研究学报, 2014, 26(12):1.(Wu K, She Y, Zhu L, et al. Consideration on the subject system of metallurgical reaction engineering[J]. Journal of Iron and Steel Research, 2014, 26(12):1.)
[7] 吴铿, 王宁, 湛文龙, 等. 冶金反应过程动力学的分段尝试法[J]. 辽宁科技大学学报, 2016, 39(1):7.(Wu K, Wang N, Zhan W L, et al. Sectional method of reaction kinetics in metallurgical reaction engineering[J]. Journal of Anshan of Science and Technology, 2016, 39(1):7.)
[8] 张兵, 吴铿, 杜瑞玲, 等. 半焦与烧结矿混合还原反应过程动力学[J]. 钢铁研究学报, 2017, 29(12):960.(Zhang B, Wu K, Du R L, et al. Kinetics of mixed reduction process of semi-coke and sinter[J]. Journal of Iron and Steel Research, 2017, 29(12):960.)
[9] 杜瑞玲, 吴铿, 刘启航, 等. 分段法研究兴隆庄煤热解反应过程动力学[J]. 哈尔滨工业大学学报, 2016, 48(4):172.(Du R L, Wu K, Liu Q H, et al. Research on the kinetics of Xinglongzhuang coal pyrolysis reaction process by sectioning method[J]. Journal of Haerbin Institute of Technology, 2016, 48(4):172.)
[10] 张黎, 吴铿, 杜瑞玲, 等. 分段尝试法研究半焦/CO2气化反应过程动力学[J]. 工程科学学报, 2016, 38(11):1539.(Zhang L, Wu K, Du R L, et al. A sectioning method to study gasification reaction kinetics of semi-coke with CO2[J]. Journal of Engineering and Science, 2016, 38(11):1539.)
[11] 潘文, 吴铿, 赵勇, 等. 碱金属对铁氧化物气-固还原行为的影响[J]. 钢铁, 2013, 48(6):7.(Pan W, Wu K, Zhao Y. Effect of alkali on the gas-solid reduction behavior of iron oxide [J]. Iron and Steel, 2013, 48(6):7.)
[12] 何启林, 王德明. 煤的氧化和热解反应的动力学研究[J]. 北京科技大学学报, 2006, 28(1):1.(He Q L, Wang D M. Study on the kinetics of oxidation and pyrolysis of coal [J]. Journal of University of Science and Technology Beijing, 2006, 28(1):1.)
[13] 张长瑞, 杨以文, 张光. 扩散控制的固相反应动力学模型[J]. 物理化学学报, 1988, 4(5):539.(Zhang C R, Yang Y W, Zhang G. Kinetic model of solid-state reaction controlled by diffusion [J]. Acta Physico-Chimica Sinica, 1988, 4(5):539.)
[14] 赵勇, 吴铿, 潘文, 等. 分段法研究烧结矿还原的动力学过程[J]. 东北大学学报:自然科学版, 2013, 34(9):1282.(Zhao Y, Wu K, Pan W, et al. Investigation of the reduction kinetics process of sinter ore by section stepwise method[J]. Journal of Northeastern University: Natural Science, 2013, 34(9):1282.)
[15] 冯向鹏. 矿物组成及显微结构对低硅烧结矿质量的影响[D]//唐山: 河北理工大学, 2003.(Feng X P. The influence of mineral composition and microstructure on the quality of the low silicon sinter[D]. Tang-shan: Hebei Polytechnic University, 2003.)