焦化废水还原浸出软锰矿动力学
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摘要
以焦化废水为还原剂,在硫酸介质中利用收缩芯模型研究焦化废水加压直接还原浸出软锰矿的动力学,考察搅拌速度、反应温度、软锰矿粒径、硫酸浓度和焦化废水CODcr浓度对锰浸出速率的影响。结果表明:锰浸出率随反应温度、硫酸浓度、焦化废水CODcr浓度的增加和软锰矿粒径的减小而增大。在393 K~423 K间,焦化废水还原浸出软锰矿受固膜扩散控制,表观活化能为15.2 kJ/mol,硫酸和焦化废水CODcr浓度的表观响应级数分别为1.21和0.98。机理分析表明:软锰矿氧化焦化废水中大分子有机物分解成小分子而被还原溶出,或被小分子直接还原溶出;反应过程中,软锰矿表面残留的Fe、Si、Al形成孔洞薄壁而影响锰的溶出过程。
Using the coking wastewater as reducing agent to pressure leaching the pyolusite, the shrinking core model was used to investigate the kinetics of the manganese reductive leaching process in the sulfuric acid solution. The effects of stirring speed, reaction temperature, the particle size of the pyrolusite and the concentrations of H_2SO_4 and coking wastewater on the leaching rate were investigated. The results show that the leaching of manganese increases with the increase of the temperature, the concentrations of H_2SO_4 and coking wastewater, whereas decreases with the increase of particle size. The kinetic equation for the manganese pressure reduction is presented at the temperature ranging from 393 K to 423 K, with the apparent activation energy of the leaching process is obtained to be 15.2 kJ/mol and the reaction orders for the concentration of H_2SO_4 and coking wastewater are 1.21 and 0.98, respectively. It suggests that the reduction of manganese from pyrolusite is controlled by the diffusion through the ash-inert layer. The mechanism analysis shows that pyrolusite is reduced by the multikey macromolecules of coking wastewater through providing the oxygen atom for the macromolecular organic compounds decomposition, or is reduced directly by small organic molecules. The thin-walled with holes superficial layer constituted by residual of Fe, Si, Al affects the Mn leaching.
Using the coking wastewater as reducing agent to pressure leaching the pyolusite, the shrinking core model was used to investigate the kinetics of the manganese reductive leaching process in the sulfuric acid solution. The effects of stirring speed, reaction temperature, the particle size of the pyrolusite and the concentrations of H_2SO_4 and coking wastewater on the leaching rate were investigated. The results show that the leaching of manganese increases with the increase of the temperature, the concentrations of H_2SO_4 and coking wastewater, whereas decreases with the increase of particle size. The kinetic equation for the manganese pressure reduction is presented at the temperature ranging from 393 K to 423 K, with the apparent activation energy of the leaching process is obtained to be 15.2 kJ/mol and the reaction orders for the concentration of H_2SO_4 and coking wastewater are 1.21 and 0.98, respectively. It suggests that the reduction of manganese from pyrolusite is controlled by the diffusion through the ash-inert layer. The mechanism analysis shows that pyrolusite is reduced by the multikey macromolecules of coking wastewater through providing the oxygen atom for the macromolecular organic compounds decomposition, or is reduced directly by small organic molecules. The thin-walled with holes superficial layer constituted by residual of Fe, Si, Al affects the Mn leaching.
引文
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[13]张春晖,何绪文,章丽萍,王春荣.电化学技术在水处理中的研究与应用[M].北京:中国环境出版社,2013:11-25.ZHANG Chun-hui,HE Xu-wen,ZHANG Li-ping,WANG Chun-rong.Research and application of electrochemical technology in water treatment[M].Beijing:China Environmental Science Press,2013:11-25.
[14]刘尚超,薛改凤,张垒,段爱民,张楠.焦化废水处理技术研究进展[J].工业水处理,2012,32(1):15-17.LIU Shang-chao,HUE Gai-feng,ZHANG Lei,DUAN Ai-min,ZHANG Nan.Research progress in the treatment technology of wastewater for coke plants[J].Industrial Water Treatment,2012,32(1):15-17.
[15]谢刚,李怀仁,和晓才,田林.加压湿法冶金技术应用现状及发展趋势[C]//第十六届中国科协年会-分10全国重有色金属冶金技术交流会论文集.北京:中国科学技术协会,2014:1-4.XIE Gang,LI Huai-ren,HE Xiao-cai,TIAN Lin.Application status and development trend on pressure hydrometallurgy technology[C]//The 16th Session of Annual Meeting of the Association of China-10 Proceedings of the National Symposium on heavy non-ferrous metal metallurgy.Beijing:China Association for Science and Technology,2014:1-4.
[16]谢红艳,王吉坤,路辉,嵇晓沧,杨世诚.加压浸出低品位锰矿的工艺[J].中国有色金属学报,2013,23(6):1701-1711.XIE Hong-yan,WANG Ji-kun,LU Hui,JI Xiao-cang,YANG Shi-cheng.Technique of pressure leaching low grade manganese ore[J].The Chinese Journal of Nonferrous Metals,2013,23(6):1701-1711.
[17]李绍英,王海霞,袁喜振,赵留成,孙春宝.金精矿碘化浸出过程动力学[J].中国有色金属学报,2014,24(3):814-819.LI Shao-ying,WANG Hai-xia,YUAN Xi-zhen,ZHAO Liu-cheng,SUN Chun-bao.Leaching dynamics of gold concentrates by iodine-iodide solution[J].The Chinese Journal of Nonferrous Metals,2014,24(3):814-819.
[18]张纯,闵小波,张建强,王蜜,李辕成.锌冶炼中浸渣锌还原浸出机制与动力学[J].中国有色金属学报,2016,26(1):197-203.ZHANG Chun,MIN Xiao-bo,ZHANG Jian-qiang,WANG Mi,LI Yuan-cheng.Mechanisms and kinetics on reductive leaching of zinc from neutral leaching residue[J].The Chinese Journal of Nonferrous Metals,2016,26(1):197-203.
[19]刘静欣,郭学益,刘旸.废弃电路板多金属粉末碱性熔炼产物分形浸出动力学[J].中国有色金属学报,2015,25(2):545-552.LIU Jing-xin,GUO Xue-yi,LIU Yang.Fractal leaching kinetics of alkaline smelting product with metal enrichment from waste printed circuit boards[J].The Chinese Journal of Nonferrous Metals,2015,25(2):545-552.
[20]李洪桂,郑清远,张启修,郑蒂基.湿法冶金学[M].长沙:中南大学出版社,2002:69-87.LI Hong-gui,ZHENG Qing-yuan,ZHANG Qi-xiu,ZHENG Di-ji.Science of hydro-metallurgy[M].Changsha:Central South University Press,2002:69-87.
[21]贺实月,李会泉,李少鹏,李勇辉,解强.煤粉炉高铝粉煤灰碱溶脱硅反应动力学[J].中国有色金属学报,2014,24(7):1888-1894.HE Shi-yue,LI Hui-quan,LI Shao-peng,LI Yong-hui,XIE Qiang.Kinetics of desilication process of fly ash with high aluminum from pulverized coal fired boiler in alkali solution[J].The Chinese Journal of Nonferrous Metals,2014,24(7):1888-1894.
[22]葛琦,王恒,满毅,李富杰,庞立伟.粒度对赤泥直接还原动力学的影响[J].化工进展,2014,33(12):3215-3220.GE Qi,WANG Heng,MAN Yi,LI Fu-jie,PANG Li-wei.Effect of particle size on kinetics of direct reduction of red mud[J].Chemical Industry and Engineering Progress,2014,33(12):3215-3220.
[23]严浩,彭文杰,王志兴,李新海,郭华军,胡启阳.响应曲面法优化点解锰阳极渣还原浸出工艺[J].中国有色金属学报,2013,23(2):528-534.YAN Hao,PENG Wen-jie,WANG Zhi-xing,LI Xin-hai,GUO Hua-jun,HU Qi-yang.Reductive leaching technology of manganese anode slag optimized by response surface methodology[J].The Chinese Journal of Nonferrous Metals,2013,23(2):528-534.
[24]TRIFONI M,TORO L,VEDLIO F.Reductive leaching of manganiferous ores by glucose and H2SO4:Effect of alcohols[J].Hydrometallurgy,2001,59(1):1-14.
[25]马华菊,卢友志,陈东莲,明宪权,李维健,袁爱群,韦冬萍,韦诗晴.乳酸还原浸出低品位软锰矿[J].过程工程学报,2015,15(6):976-981.MA Hua-ju,LU You-zhi,CHEN Dong-lian,MING Xian-quan,LI Wei-jian,YUAN Ai-qun,WEI Dong-ping,WEI Shi-qing.Reductive leaching of low grade pyrolusite ore with lactic acid[J].The Chinese Journal of Process Engineering,2015,15(6):976-981.
[26]袁明亮,梅贤功,庄剑鸣,陈荩,蒋汉瀛.菱锰矿酸浸过程杂质行为[J].中南工业大学学报,1996,27(1):40-43.YUAN Ming-liang,MEI Xian-gong,ZHUANG Jian-ming,CHEN Jin,JIANG Han-ying.The behavior of impurities in the leaching process of manganese carbonate ore[J].Journal of Central South University of Technology,1996,27(1):40-43.
[2]李同庆.低品位软锰矿还原工艺技术与研究进展[J].中国锰业,2008,26(2):4-13.LI Tong-qing.Technology of low grade pyrolusite ore reduction process and recent advances[J].China’s Manganese Industry,2008,26(2):4-13.
[3]MOHAMMAD S B,ALIREZA Z,ZAHRA G,MANDANA A.Reductive dissolution of manganese ore in sulfuric acid in presence of iron metal[J].Hydrometallurgy,2008,90:207-212.
[4]牛莎莎,王志兴,郭华军,李新海,彭文杰,胡启阳,张云河.电解锰阳极渣还原浸出锰[J].中国有色金属学报,2012,22(9):2662-2666.NIU Sha-sha,WANG Zhi-xing,GUO Hua-jun,LI Xin-hai,PENG Wen-jie,HU Qi-yang,ZHANG Yun-he.Reductive leaching of manganese from manganese anode slag[J].The Chinese Journal of Nonferrous Metals,2012,22(9):2662-2666.
[5]常伟.低品位软锰矿还原浸出过程及其动力学研究[D].长沙:中南大学,2014:4-8.CHNAG Wei.Study on reductive leaching of low-grade pyrolusite ores and leaching kinetics[D].Changsha:Central South University,2014:4-8.
[6]FURLANI G,PAGNANELLI F,TORO L.Reductive acid leaching of manganese dioxide with glucose:Identification of oxidation derivatives of glucose[J].Hydrometallurgy,2006,81:234-240.
[7]冯雅丽,易爱飞,李浩然,王维大.玉米秸秆还原浸出高铁低品位锰矿研究[J].东北大学学报(自然科学版),2015,36(8):1184-1187.FENG Ya-li,YI Ai-fei,LI Hao-ran,WANG Wei-da.Reductive leaching of high iron low-grade manganese ore with pre-processed cornstalk[J].Journal of Northeastern University(Natural Sciences),2015,26(8):1184-1187.
[8]SU Hai-feng,LIU Huai-kun,WANG Fan,LüXiao-yan,WEN Yan-xuan.Kinetics of reductive leaching of low-grade pyrolusite with molasses alcohol wastewater in H2SO4[J].Chinese Journal of Chemical Engineering,2010,18(5):730-735.
[9]BEOLCHINI F,PETRANGELIPAPINI M,TORO L,TRIRONO M,VEGLIO F.Acid leaching of manganiferous ores by sucrose:Kinetic modelling and related statistical analysis[J].Minerals Engineering,2001,14(2):175-184.
[10]VEGLīòF,TRIFONI M,PAGNANELLI F,TORO L.Shrinking core model with variable activation energy:A kinetic model of manganiferous ore leaching with sulphuric acid and lactose[J].Hydrometallurgy,2001,60(2):167-179.
[11]粟海锋,吕奕菊,崔勍焱,王凡,吕小艳,文衍宣.糖蜜酒精废液中大分子焦糖色素模拟物浸出软锰矿的动力学[J].高校化学工程学报,2011,25(1):43-48.SU Hai-feng,LüYi-ju,CUI Qing-yan,WANG Fan,LüXiao-yan,WEN Yan-xuan.Leaching kinetics of pyrolusite by macromolecular caramel of molasses alcohol wastewater[J].Journal of Chemical Engineering Colleges and Universities,2011,25(1):43-48.
[12]满瑞林,常伟,吴奇,薛建荣.燕麦秸秆还原浸出低品位软锰矿及其动力学[J].中国有色金属学报,2014,24(8):2158-2163.MAN Rui-lin,CHANG Wei,WU Qi,XUE Jian-rong.Reductive leaching and leaching kinetics of low-grade pyrolusite ores using oat straw as reductant[J].The Chinese Journal of Nonferrous Metals,2014,24(8):2158-2163.
[13]张春晖,何绪文,章丽萍,王春荣.电化学技术在水处理中的研究与应用[M].北京:中国环境出版社,2013:11-25.ZHANG Chun-hui,HE Xu-wen,ZHANG Li-ping,WANG Chun-rong.Research and application of electrochemical technology in water treatment[M].Beijing:China Environmental Science Press,2013:11-25.
[14]刘尚超,薛改凤,张垒,段爱民,张楠.焦化废水处理技术研究进展[J].工业水处理,2012,32(1):15-17.LIU Shang-chao,HUE Gai-feng,ZHANG Lei,DUAN Ai-min,ZHANG Nan.Research progress in the treatment technology of wastewater for coke plants[J].Industrial Water Treatment,2012,32(1):15-17.
[15]谢刚,李怀仁,和晓才,田林.加压湿法冶金技术应用现状及发展趋势[C]//第十六届中国科协年会-分10全国重有色金属冶金技术交流会论文集.北京:中国科学技术协会,2014:1-4.XIE Gang,LI Huai-ren,HE Xiao-cai,TIAN Lin.Application status and development trend on pressure hydrometallurgy technology[C]//The 16th Session of Annual Meeting of the Association of China-10 Proceedings of the National Symposium on heavy non-ferrous metal metallurgy.Beijing:China Association for Science and Technology,2014:1-4.
[16]谢红艳,王吉坤,路辉,嵇晓沧,杨世诚.加压浸出低品位锰矿的工艺[J].中国有色金属学报,2013,23(6):1701-1711.XIE Hong-yan,WANG Ji-kun,LU Hui,JI Xiao-cang,YANG Shi-cheng.Technique of pressure leaching low grade manganese ore[J].The Chinese Journal of Nonferrous Metals,2013,23(6):1701-1711.
[17]李绍英,王海霞,袁喜振,赵留成,孙春宝.金精矿碘化浸出过程动力学[J].中国有色金属学报,2014,24(3):814-819.LI Shao-ying,WANG Hai-xia,YUAN Xi-zhen,ZHAO Liu-cheng,SUN Chun-bao.Leaching dynamics of gold concentrates by iodine-iodide solution[J].The Chinese Journal of Nonferrous Metals,2014,24(3):814-819.
[18]张纯,闵小波,张建强,王蜜,李辕成.锌冶炼中浸渣锌还原浸出机制与动力学[J].中国有色金属学报,2016,26(1):197-203.ZHANG Chun,MIN Xiao-bo,ZHANG Jian-qiang,WANG Mi,LI Yuan-cheng.Mechanisms and kinetics on reductive leaching of zinc from neutral leaching residue[J].The Chinese Journal of Nonferrous Metals,2016,26(1):197-203.
[19]刘静欣,郭学益,刘旸.废弃电路板多金属粉末碱性熔炼产物分形浸出动力学[J].中国有色金属学报,2015,25(2):545-552.LIU Jing-xin,GUO Xue-yi,LIU Yang.Fractal leaching kinetics of alkaline smelting product with metal enrichment from waste printed circuit boards[J].The Chinese Journal of Nonferrous Metals,2015,25(2):545-552.
[20]李洪桂,郑清远,张启修,郑蒂基.湿法冶金学[M].长沙:中南大学出版社,2002:69-87.LI Hong-gui,ZHENG Qing-yuan,ZHANG Qi-xiu,ZHENG Di-ji.Science of hydro-metallurgy[M].Changsha:Central South University Press,2002:69-87.
[21]贺实月,李会泉,李少鹏,李勇辉,解强.煤粉炉高铝粉煤灰碱溶脱硅反应动力学[J].中国有色金属学报,2014,24(7):1888-1894.HE Shi-yue,LI Hui-quan,LI Shao-peng,LI Yong-hui,XIE Qiang.Kinetics of desilication process of fly ash with high aluminum from pulverized coal fired boiler in alkali solution[J].The Chinese Journal of Nonferrous Metals,2014,24(7):1888-1894.
[22]葛琦,王恒,满毅,李富杰,庞立伟.粒度对赤泥直接还原动力学的影响[J].化工进展,2014,33(12):3215-3220.GE Qi,WANG Heng,MAN Yi,LI Fu-jie,PANG Li-wei.Effect of particle size on kinetics of direct reduction of red mud[J].Chemical Industry and Engineering Progress,2014,33(12):3215-3220.
[23]严浩,彭文杰,王志兴,李新海,郭华军,胡启阳.响应曲面法优化点解锰阳极渣还原浸出工艺[J].中国有色金属学报,2013,23(2):528-534.YAN Hao,PENG Wen-jie,WANG Zhi-xing,LI Xin-hai,GUO Hua-jun,HU Qi-yang.Reductive leaching technology of manganese anode slag optimized by response surface methodology[J].The Chinese Journal of Nonferrous Metals,2013,23(2):528-534.
[24]TRIFONI M,TORO L,VEDLIO F.Reductive leaching of manganiferous ores by glucose and H2SO4:Effect of alcohols[J].Hydrometallurgy,2001,59(1):1-14.
[25]马华菊,卢友志,陈东莲,明宪权,李维健,袁爱群,韦冬萍,韦诗晴.乳酸还原浸出低品位软锰矿[J].过程工程学报,2015,15(6):976-981.MA Hua-ju,LU You-zhi,CHEN Dong-lian,MING Xian-quan,LI Wei-jian,YUAN Ai-qun,WEI Dong-ping,WEI Shi-qing.Reductive leaching of low grade pyrolusite ore with lactic acid[J].The Chinese Journal of Process Engineering,2015,15(6):976-981.
[26]袁明亮,梅贤功,庄剑鸣,陈荩,蒋汉瀛.菱锰矿酸浸过程杂质行为[J].中南工业大学学报,1996,27(1):40-43.YUAN Ming-liang,MEI Xian-gong,ZHUANG Jian-ming,CHEN Jin,JIANG Han-ying.The behavior of impurities in the leaching process of manganese carbonate ore[J].Journal of Central South University of Technology,1996,27(1):40-43.