废弃脱硝催化剂直接合金化的热力学计算和动力学研究
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摘要
运用热力学软件Factsage 7.1计算了废弃脱硝催化剂直接合金化过程中还原温度以及TiO_2-CaO-CaF_2-Na_2O-SiO_2渣系中配铝量对还原效果的影响。还原温度1 550℃后钢中单质钛不再升高,但钛氧化物的含量随温度升高而持续升高;在1 600℃,钢中Ti含量随着配铝量增加而增加,铝渣比0.4左右时,钛含量可以达到最大值4.25%。铝还原废弃脱硝催化剂的反应在923℃左右发生,属于液—固反应。利用Freeman-Carroll法计算了废弃脱硝催化剂直接合金化还原过程的动力学参数,得出表观活化能E=243.33 kJ/mol,反应级数n=0.13。
The thermodynamic software Factsage 7.1 was used to calculate the effects of reduction temperature and aluminum amount of the TiO_2-CaO-CaF_2-Na_2O-SiO_2 slag system during the direct alloying process of the abandoned denitration catalyst.When the reduction temperature reaches 1 550 ℃,titanium in the steel almost no longer rises,but the content of titanium oxides continues to increase with the increase of temperature.At 1 600 ℃,titanium content in the steel increases with increase of the amount of aluminum.When the ratio of aluminum to slag is about 0.4,the titanium content can reach to maximum 4.25%.The reaction for reduction of the abandoned denitration catalyst by aluminum occurs at around 923 ℃ and belongs to a liquid-solid reaction.The kinetics parameters of the direct alloying reduction process were calculated by Freeman-Carroll method,with the obtained apparent activation energy E=243.33 kJ/mol and the reaction order n=0.13.
The thermodynamic software Factsage 7.1 was used to calculate the effects of reduction temperature and aluminum amount of the TiO_2-CaO-CaF_2-Na_2O-SiO_2 slag system during the direct alloying process of the abandoned denitration catalyst.When the reduction temperature reaches 1 550 ℃,titanium in the steel almost no longer rises,but the content of titanium oxides continues to increase with the increase of temperature.At 1 600 ℃,titanium content in the steel increases with increase of the amount of aluminum.When the ratio of aluminum to slag is about 0.4,the titanium content can reach to maximum 4.25%.The reaction for reduction of the abandoned denitration catalyst by aluminum occurs at around 923 ℃ and belongs to a liquid-solid reaction.The kinetics parameters of the direct alloying reduction process were calculated by Freeman-Carroll method,with the obtained apparent activation energy E=243.33 kJ/mol and the reaction order n=0.13.
引文
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[4] China Environmental Protection Industry Association Desulfurization and Denitrification Committee.Summary of the development of desulfurization and denitrification industry in China in 2013[J].China Environmental Protection Industry,2014(9):4-15.(中国环境保护产业协会脱硫脱硝委员会.我国脱硫脱硝行业2013年发展综述[J].中国环保产业,2014(9):4-15.)
[5] Tang Dingling,Song Hao,Liu Dingding,et al.Leaching kinetics of extraction of vanadium and tungsten by alkali leaching[J].Chinese Journal of Environmental Engineering,2017,11(2):1093-1100.(唐丁玲,宋浩,刘丁丁,等.废弃脱硝催化剂碱浸提取钒和钨的浸出动力学研究[J].环境工程学报,2017,11(2):1093-1100.)
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[7] Wang Dezhi,Wu Gang,Xiao Yuting,et al.Method for recovering tungsten component from selective catalytic reduction denitration catalyst,Chinese patent:CN103088217A[P].2013-05-08.(汪德志,吴刚,肖雨亭,等.从选择性催化还原脱硝催化剂中回收钨组分的方法,中国专利:CN103088217A[P].2013-05-08.)
[8] Zhu Yue,He Sheng,Zhang Yang.Method for recovering metal oxide from waste flue gas denitration catalyst,Chinese patent:CN101921916A[P].2010-12-22.(朱跃,何胜,张扬.从废烟气脱硝催化剂中回收金属氧化物的方法,中国专利:CN101921916A[P].2010-12-22.)
[9] Zhao Wei,Yu Aihua,Wang Hu,et al.Wet process recovery of titanium,vanadium,molybdenum in plate-type SCR waste catalyst[J].Chemical Industry and Engineering Progress,2014,34(7):2039-2042.(赵炜,于爱华,王虎,等.湿法工艺回收板式SCR废弃催化剂中钛、钒、钼[J].化工进展,2014,34(7):2039-2042.)
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[11] Chen Guangyu,Kang Jialong,Liu Junjie,et al.Direct alloying of abandoned denitration catalyst[J].Iron Steel Vanadium Titanium,2018,39(6):99-102.(陈广玉,康嘉龙,刘俊杰,等.废弃脱硝催化剂直接合金化研究[J].钢铁钒钛,2018,39(6):99-102.)
[12] Cheng Chu,Dou Zhihe,Zhang Ting’an,et al.Thermodynamics and kinetics of Ti-6Al-4V alloy prepared by aluminothermic reduction[J].Journal of Northeastern University,2018,39(5):33-37.(程楚,豆志河,张廷安,等.铝热还原制备Ti-6Al-4V合金的热力学和动力学[J].东北大学学报(自然科学版),2018,39(5):33-37.)
[13] Niu Liping,Zhang Ting’an,Zhang Hanbo,et al.Thermodynamics and kinetics of preparation of high titanium iron by aluminothermic reduction[J].The Chinese Journal of Nonferrous Metals,2010,20(b10):425-428.(牛丽萍,张廷安,张含博,等.铝热还原制备高钛铁的热力学和动力学[J].中国有色金属学报,2010,20(b10):425-428.)
[14] Duan Shengchao,Wang Zhuqing,Guo Hanjie,et al.Thermodynamics and kinetics of preparation of vanadium aluminium alloy by aluminothermic method[J].Iron Steel Vanadium Titanium,2017,38(6):47-54.(段生朝,王竹青,郭汉杰,等.铝热法制备钒铝合金热力学及动力学研究[J].钢铁钒钛,2017,38(6):47-54.)
[15] Pouriamanesh R,Vahdati-Khaki J,Mohammadi Q.Coating of Al substrate by metallic Ni through mechanical alloying[J].Journal of Alloys & Compounds,2009,488(1):430-436.
[16] Shen Xing.Differential thermal,thermogravimetric analysis and non-isothermal solid phase reaction kinetics[M].Beijing:Metallurgical Industry Press,1995.(沈兴.差热、热重分析与非等温固相反应动力学[M].北京:冶金工业出版社,1995.)
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