大洋锰结核与药渣共浸出氧化还原过程研究
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摘要
以药渣为大洋锰结核还原剂,研究药渣湿法还原锰结核浸出特性。考察搅拌速率、液固比、硫酸浓度、药渣用量和反应温度对锰浸出的影响,利用稳态极化曲线测定浸出反应动力学参数。研究结果表明:在搅拌速率为400 r/min、液固比为10:1、硫酸浓度为0.94 mol/L、药渣用量为5 g、浸出温度为363 K的条件下浸出300 min,锰浸出率达95.78%。在343~368 K间,浸出过程受化学反应控制,表观活化能为40.74 kJ/mol。在酸性环境下,锰结核与药渣有机物聚团接触碰撞,大分子聚团被锰氧化物氧化为水溶性小分子后,小分子水溶性有机物经腐蚀凹孔进入结核内层,进而氧化成NH_4~+,H_2O和CO_2,锰结核由外向内逐层腐蚀;反应过程中锰氧化物晶格破坏,释放Cu,Co和Ni等有价金属元素。
The reductive leaching of manganese from oceanic manganese nodules was investigated by using pharmaceutical residue as reducing agent. The effects of stirring speed, liquid/solid ratio, sulfuric acid concentration, dosage of pharmaceutical residue and reaction temperature on the manganese extraction were examined. The results show that the leaching efficiency of manganese peaks at 95.78% under the optimal conditions: stirring speed of 400 r/min, liquid/solid ratio of 10:1, sulfuric acid concentration of 0.94 mol/L, pharmaceutical residue dosage of 5 g, and temperature of 363 K for 300 min. At 343-368 K, the kinetic analysis is carried out based on the shrinking core model, which shows that the reductive leaching process is controlled by the chemical reaction, and the apparent activation energy is 40.74 kJ/mol. In acidic solution, with contacting and collision between oceanic manganese nodules and pharmaceutical residue, macromolecular organics is decomposed into water-soluble small molecules and finally into NH_4~+, H_2O and CO_2. Manganese nodules are reduced and dissolved by small organic molecules that contact with manganese nodules inner layer through groove by layer. Moreover, Cu, Co and Ni are released with the lattice of manganese oxides being destroyed.
The reductive leaching of manganese from oceanic manganese nodules was investigated by using pharmaceutical residue as reducing agent. The effects of stirring speed, liquid/solid ratio, sulfuric acid concentration, dosage of pharmaceutical residue and reaction temperature on the manganese extraction were examined. The results show that the leaching efficiency of manganese peaks at 95.78% under the optimal conditions: stirring speed of 400 r/min, liquid/solid ratio of 10:1, sulfuric acid concentration of 0.94 mol/L, pharmaceutical residue dosage of 5 g, and temperature of 363 K for 300 min. At 343-368 K, the kinetic analysis is carried out based on the shrinking core model, which shows that the reductive leaching process is controlled by the chemical reaction, and the apparent activation energy is 40.74 kJ/mol. In acidic solution, with contacting and collision between oceanic manganese nodules and pharmaceutical residue, macromolecular organics is decomposed into water-soluble small molecules and finally into NH_4~+, H_2O and CO_2. Manganese nodules are reduced and dissolved by small organic molecules that contact with manganese nodules inner layer through groove by layer. Moreover, Cu, Co and Ni are released with the lattice of manganese oxides being destroyed.
引文
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[20]TANG Qing,ZHONG Hong,WANG Shuai,et al.Reductive leaching of manganese oxide ores using waste tea as reductant in sulfuric acid solution[J].Transactions of Nonferrous Metals Society of China,2014,24(3):861-867.
[21]冯雅丽,康金星,李浩然,等.焦化废水还原浸出软锰矿动力学[J].中国有色金属学报,2017,27(5):1051-1060.FENG Yali,KANG Jinxing,LI Haoran,et al.The characteristic of polymetallic nodule and low-grade nickel sulfide ore coupled leaching[J].The Chinese Journal of Nonferrous Metals,2017,27(5):1051-1060.
[22]王效山.制药工业三废处理技术[M].北京:化学工业出版社,2010:253-264.WANG Xiaoshan.Waste treatment technology in pharmaceutical industry[M].Beijing:Chemical industry Press,2010:253-264.
[23]钟雨岑.化工危险废物焚烧及烟气处理工艺[J].广东化工,2017,44(2):92-93.ZHONG Yucen.Incineration technology of chemical hazardous waste and flue gas treatment[J].Guangdong Chemical Industry,2017:44(2):92-93.
[2]雷晓力,胡永达,杜轶伦,等.锰矿资源现状及开发利用思考[J].中国矿业,2015,24(1):19-21.LEI Xiaoli,HU Yongda,DU Zhilun,et al.Present situation and development of manganese ore resources[J].China Mining Magazine,2015,24(1):19-21.
[3]CHEN Zhuo,ZHU Guocai,ZHAO Yuna.Study on reduction-roast leaching manganese from low-grade manganese dioxide ores using cornstalk as reductant[J].Hydrometallurgy,2009,96(1/2):176-179.
[4]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):4-14.LI Tongqing.Technology of low grade pyrolusite ore reduction process and recent advances[J].China’s Manganese Industry,2008,26(2):4-13.
[5]张传福,夏楚平,王志坚,等.软锰矿与硫化铋矿交互焙烧过程的热力学分析[J].中南大学学报(自然科学版),2013,44(10):3984-3990.ZHANG Chuanfu,XIA Chuping,WANG Zhijian,et al.Thermodynamic analysis of interactive roasting process of bismuth sulfide ore and pyrolusite[J]Journal of Central South University(Science and Technology),2013,44(10):3984-3990.
[6]DING Fenghua,ZHAN Jing,WANG Zhijian.Simultaneous leaching of low grade bismuthinite and pyrolusite ores in hydrochloric acid medium[J].Hydrometallurgy,2016,166:279-284.
[7]GHOSH S,MOHANTY S,AKCIL A.A greener approach for resource recycling:Manganese bioleaching[J].Chemosphere,2016,154:628-639.
[8]武芳芳,钟宏,王帅.氧化锰矿还原工艺技术研究进展[J].应用化工,2012,41(8):1443-1447.WU Fangfang,ZHONG Hong,WANG Shuai.Research progress on reduction technology of manganese oxide ore[J].Applied Chemical Industry,2012,41(8):1443-1447.
[9]魏汉可,刘咏,谭秀民,等.用SO2从软锰矿中还原浸出锰的试验研究[J].湿法冶金,2015,34(6):458-460.WEI Hanke,LIU Yong,TAN Xiumin,et al.Research in reduction leaching of manganese from pyrolusite using in sulfuric acid medium[J].Hydrometallurgy of China,2015,34(6):458-460.
[10]GHOSH M K,BARIK S P.Sulphuric acid leaching of polymetallic nodules using paper as a reductant[J].Transactions of the Indian of Metals,2008,61(6):477-481.
[11]冯雅丽,易爱飞,李浩然,等.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 Yali,YI Aifei,LI Haoran,et al.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.
[12]SUN Yang,FU Gaofeng,JIANG Lan.Kinetic study of the leaching of low-grade manganese ores by using pretreated sawdust as reductant[J].Mineral,2017,5(7):83.
[13]满瑞林,常伟,吴奇,等.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 Ruilin,CHANG Wei,WU Qi,et al.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.
[14]VEGLIO F,TRIFONI M,PAGNANELLI F.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.
[15]BEOLCHINI F,PAPINI M P,TORO L,et al.Acid leaching of manganiferous ores by sucrose:kinetic modelling and related statistical analysis[J].Minerals Engineering,2001,14(2):175-184.
[16]粟海锋,吕奕菊,崔勍焱,等.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 Haifeng,LüYiju,CUI Qingyan,et al.Leaching kinetics of pyrolusite by macromolecular caramel of molasses alcohol wastewater[J].Journal of Chemical Engineering Colleges and Universities,2011,25(1):43-48.
[17]常伟.低品位软锰矿还原浸出过程及其动力学研究[D].长沙:中南大学化学化工学院,2014:4-8.CHANG Wei.Study on reductive leaching of low-grade pyrolusite ores and leaching kinetics[D].Changsha:Central South University.School of Chemistry and Chemical Engineering,2014:4-8.
[18]LASHEEN T A,EL HAZEK M N,HELAL A S.Kinetics of reductive leaching of manganese oxide ore with molasses[J].Hydrometallurgy,2009,98:314-317.
[19]BABA A A,GHOSH M K,PRADHAN S R,et al.Characterization and kinetic study on ammonia leaching of complex copper ore[J].Transactions of Nonferrous Metals Society of China,2014,24(5):1587-1595.
[20]TANG Qing,ZHONG Hong,WANG Shuai,et al.Reductive leaching of manganese oxide ores using waste tea as reductant in sulfuric acid solution[J].Transactions of Nonferrous Metals Society of China,2014,24(3):861-867.
[21]冯雅丽,康金星,李浩然,等.焦化废水还原浸出软锰矿动力学[J].中国有色金属学报,2017,27(5):1051-1060.FENG Yali,KANG Jinxing,LI Haoran,et al.The characteristic of polymetallic nodule and low-grade nickel sulfide ore coupled leaching[J].The Chinese Journal of Nonferrous Metals,2017,27(5):1051-1060.
[22]王效山.制药工业三废处理技术[M].北京:化学工业出版社,2010:253-264.WANG Xiaoshan.Waste treatment technology in pharmaceutical industry[M].Beijing:Chemical industry Press,2010:253-264.
[23]钟雨岑.化工危险废物焚烧及烟气处理工艺[J].广东化工,2017,44(2):92-93.ZHONG Yucen.Incineration technology of chemical hazardous waste and flue gas treatment[J].Guangdong Chemical Industry,2017:44(2):92-93.