盐酸-磷酸分解钼酸钙的动力学（英文）
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摘要
钼酸钙是钼的一次资源,也是钼湿法和火法冶金过程中重要的中间产物。采用盐酸-磷酸混酸浸出钼酸钙以提取钼,为了了解浸出过程的机理,通过对浸出过程5个主要影响因素的研究,进行浸出过程动力学分析。结果表明:钼酸钙在该体系中的分解速率不受搅拌速度的影响,而受盐酸浓度、温度和粒径的影响比较显著;随着盐酸浓度增加和反应温度上升,浸出速率增加;随着粒径增大,反应速率降低。钼酸钙在该体系中的反应受收缩核模型的化学反应控制,所得反应的表观活化能为70.879 kJ/mol,并建立描述反应过程的半经验动力学方程。
Calcium molybdate(CaMoO_4) is the main component of powellite and is a predominant intermediate in the pyrometallurgical and hydrometallurgical process of molybdenum. The extraction of Mo from CaMoO_4 by a combination of phosphoric acid and hydrochloric acid was investigated. For further understanding of the leaching mechanism, the effects of five key factors were studied to describe the leaching kinetics. The results indicated that the dissolution rate of CaMoO_4 was independent of the stirring speed. Mo extraction significantly increased with increasing HCl concentration and temperature, but decreased with increasing particle size. A shrinking core model with surface chemical reaction was found to withstand the dissolution of CaMoO_4.The apparent activation energy was calculated to be 70.879 kJ/mol, and a semi-empirical equation was derived for the rate of reaction.
Calcium molybdate(CaMoO_4) is the main component of powellite and is a predominant intermediate in the pyrometallurgical and hydrometallurgical process of molybdenum. The extraction of Mo from CaMoO_4 by a combination of phosphoric acid and hydrochloric acid was investigated. For further understanding of the leaching mechanism, the effects of five key factors were studied to describe the leaching kinetics. The results indicated that the dissolution rate of CaMoO_4 was independent of the stirring speed. Mo extraction significantly increased with increasing HCl concentration and temperature, but decreased with increasing particle size. A shrinking core model with surface chemical reaction was found to withstand the dissolution of CaMoO_4.The apparent activation energy was calculated to be 70.879 kJ/mol, and a semi-empirical equation was derived for the rate of reaction.
引文
[1]LASHEEN T A,EL-AHMADY M E,HASSIB H B,HELAL A S.Molybdenum metallurgy review:Hydrometallurgical routes to recovery of molybdenum from ores and mineral raw materials[J].Mineral Processing and Extractive Metallurgy Review,2015,36(3):145-173.
[2]LI Hong-gui.Production of high purity APT from scheelite and complex tungsten raw materials with a high Mo content[J].Transactions of Nonferrous Metals Society of China,2004,14(2):366-369.
[3]JUNEJA J M,SINGH S,BOSE D K.Investigations on the extraction of molybdenum and rhenium values from low grade molybdenite concentrate[J].Hydrometallurgy,1996,41(2-3):201-209.
[4]GAN Min,FAN Xiao-hui,CHEN Xu-ling,WU Cheng-qin,JIZhi-yun,WANG Song-rong,WANG Guo-jing,QIU Guan-zhou,JIANG Tao.Reaction mechanisms of low-grade molybdenum concentrate during calcification roasting process[J].Transactions of Nonferrous Metals Society of China,2016,26(11):3015-3023.
[5]ZHANG Qi-xiu,ZHAO Qin-sheng.Tungsten and molybdenum metallurgy[M].Beijing:Metallurgical Industry Press,2007.(in Chinese)
[6]LUO L,KEJUN L,SHIBAYAMA A,YEN W,FUJITA T,SHINDOO,KATAI A.Recovery of tungsten and vanadium from tungsten alloy scrap[J].Hydrometallurgy,2004,72(1):1-8.
[7]ZENG Li,CHENG Chu-yong.A literature review of the recovery of molybdenum and vanadium from spent hydrodesulphurisation catalysts:Part I:Metallurgical processes[J].Hydrometallurgy,2009,98(1):1-9.
[8]SWINKELS P L J,van der WEIJDEN R D,AJAH A N,ARIFIN Y,LOE H L,MANIK M H,SIRISKI I,REUTER M A.Conceptual process design as a prerequisite for solving environmental problems:A case study of molybdenum removal and recovery from wastewater[J].Minerals Engineering,2004,17(2):205-215.
[9]SINGH S,CHETTY M K,JUNEJA J M,SEHRA J C,GUPTA C K.Studies on the processing of a low grade molybdenite concentrate by lime roasting[J].Minerals Engineering,1988,1(4):337-342.
[10]WANG Ming-yu,WANG Xue-wen,LIU Wan-li.A novel technology of molybdenum extraction from low grade Ni-Mo ore[J].Hydrometallurgy,2009,97(1):126-130.
[11]DOUGLAS D A,MENASHI J,RAPPAS A S.Process for recovering chromium,vanadium,molybdenum and tungsten values from a feed material:US 4298581[P].1981-11-3.
[12]WANG Ming-shuang,WEI Chang,FAN Gang,DENG Zhi-gan,WANG Si-fu,WU Jun.Molybdenum recovery from oxygen pressure water leaching residue of Ni-Mo ore[J].Rare Metals,2013,32(2):208-212.
[13]NGUYEN T H,LEE M S.Development of a hydrometallurgical process for the recovery of calcium molybdate and cobalt oxalate powders from spent hydrodesulphurization(HDS)catalyst[J].Journal of Cleaner Production,2015,90:388-396.
[14]ILHAN S,KALPAKLI A O,KAHRUMAN C,YUSUFOGLU I.The use of Langmuir-Hinshelwood mechanism to explain the kinetics of calcium molybdate leaching in oxalic acid solution[J].Hydrometallurgy,2012,127:91-98.
[15]ZHANG Wen-juan,LI Jiang-tao,ZHAO Zhong-wei,HUANGShao-bo,CHEN Xing-yu,HU Kai-long.Recovery and separation of W and Mo from high-molybdenum synthetic scheelite in HCl solutions containing H2O2[J].Hydrometallurgy,2015,155:1-5.
[16]XIA Wen-tang,ZHAO Zhong-wei,LI Hong-Gui.Thermodynamic analysis on sodium carbonate decomposition of calcium molybdenum[J].Transactions of Nonferrous Metals Society of China,2007,17(3):622-625.
[17]PAN Mao-sen,ZHU Yun.Experimental study on leaching molybdenum at high-pressure from calcium molybdate[J].China Molybdenum Industry,2005,29(6):19-21.(in Chinese)
[18]ZHANG Wen-juan,YANG Jin-hong,ZHAO Zhong-wei,WANGWen-qiang,LI Jiang-tao.Coordination leaching of tungsten from scheelite concentrate with phosphorus in nitric acid[J].Journal of Central South University,2016,23(6):1312-1317.
[19]XUIN G H,YU D Y,SU Y F.Leaching of scheelite by hydrochloric acid in the presence of phosphate[J].Hydrometallurgy,1986,16(1):27-40.
[20]LI Jiang-tao,ZHAO Zhong-wei.Kinetics of scheelite concentrate digestion with sulfuric acid in the presence of phosphoric acid[J].Hydrometallurgy,2016,163:55-60.
[21]KAHRUMAN C,YUSUFOGLU I.Leaching kinetics of synthetic Ca WO4 in HCl solutions containing H3PO4 as chelating agent[J].Hydrometallurgy,2006,81(3-4):182-189.
[22]PETTERSSON L,ANDERSSON I,?HMAN L O.Multicomponent polyanions.35.A 31P NMR study of aqueous molybdophosphates[J].Acta Chem Scand,1985,39:53-58.
[23]PETTERSSON L,ANDERSSON I,?HMAN L O.Multicomponent polyanions.39.Speciation in the aqueous H+-MoO42--HPO42-system as deduced from a combined Emf-phosphorus-31P NMR study[J].Inorganic Chemistry,1986,25(26):4726-4733.
[24]SPEIGHT J G.Lange’s handbook of chemistry[M].New York:McGraw-Hill,2005.
[25]YANG Jin-hong,HE Li-hua,LIU Xu-heng,DING Wen-tao,SONGYun-feng,ZHAO Zhong-wei.Comparative kinetic analysis of conventional and ultrasound-assisted leaching of scheelite by sodium carbonate[J].Transactions of Nonferrous Metals Society of China,2018,28(4):775-782.
[26]YANG Hong-ying,LI Xue-jiao,TONG Lin-lin,JIN Zhe-nan,YINLu,CHEN Guo-bao.Leaching kinetics of selenium from copper anode slimes by nitric acid-sulfuric acid mixture[J].Transactions of Nonferrous Metals Society of China,2018,28(1):186-192.
[2]LI Hong-gui.Production of high purity APT from scheelite and complex tungsten raw materials with a high Mo content[J].Transactions of Nonferrous Metals Society of China,2004,14(2):366-369.
[3]JUNEJA J M,SINGH S,BOSE D K.Investigations on the extraction of molybdenum and rhenium values from low grade molybdenite concentrate[J].Hydrometallurgy,1996,41(2-3):201-209.
[4]GAN Min,FAN Xiao-hui,CHEN Xu-ling,WU Cheng-qin,JIZhi-yun,WANG Song-rong,WANG Guo-jing,QIU Guan-zhou,JIANG Tao.Reaction mechanisms of low-grade molybdenum concentrate during calcification roasting process[J].Transactions of Nonferrous Metals Society of China,2016,26(11):3015-3023.
[5]ZHANG Qi-xiu,ZHAO Qin-sheng.Tungsten and molybdenum metallurgy[M].Beijing:Metallurgical Industry Press,2007.(in Chinese)
[6]LUO L,KEJUN L,SHIBAYAMA A,YEN W,FUJITA T,SHINDOO,KATAI A.Recovery of tungsten and vanadium from tungsten alloy scrap[J].Hydrometallurgy,2004,72(1):1-8.
[7]ZENG Li,CHENG Chu-yong.A literature review of the recovery of molybdenum and vanadium from spent hydrodesulphurisation catalysts:Part I:Metallurgical processes[J].Hydrometallurgy,2009,98(1):1-9.
[8]SWINKELS P L J,van der WEIJDEN R D,AJAH A N,ARIFIN Y,LOE H L,MANIK M H,SIRISKI I,REUTER M A.Conceptual process design as a prerequisite for solving environmental problems:A case study of molybdenum removal and recovery from wastewater[J].Minerals Engineering,2004,17(2):205-215.
[9]SINGH S,CHETTY M K,JUNEJA J M,SEHRA J C,GUPTA C K.Studies on the processing of a low grade molybdenite concentrate by lime roasting[J].Minerals Engineering,1988,1(4):337-342.
[10]WANG Ming-yu,WANG Xue-wen,LIU Wan-li.A novel technology of molybdenum extraction from low grade Ni-Mo ore[J].Hydrometallurgy,2009,97(1):126-130.
[11]DOUGLAS D A,MENASHI J,RAPPAS A S.Process for recovering chromium,vanadium,molybdenum and tungsten values from a feed material:US 4298581[P].1981-11-3.
[12]WANG Ming-shuang,WEI Chang,FAN Gang,DENG Zhi-gan,WANG Si-fu,WU Jun.Molybdenum recovery from oxygen pressure water leaching residue of Ni-Mo ore[J].Rare Metals,2013,32(2):208-212.
[13]NGUYEN T H,LEE M S.Development of a hydrometallurgical process for the recovery of calcium molybdate and cobalt oxalate powders from spent hydrodesulphurization(HDS)catalyst[J].Journal of Cleaner Production,2015,90:388-396.
[14]ILHAN S,KALPAKLI A O,KAHRUMAN C,YUSUFOGLU I.The use of Langmuir-Hinshelwood mechanism to explain the kinetics of calcium molybdate leaching in oxalic acid solution[J].Hydrometallurgy,2012,127:91-98.
[15]ZHANG Wen-juan,LI Jiang-tao,ZHAO Zhong-wei,HUANGShao-bo,CHEN Xing-yu,HU Kai-long.Recovery and separation of W and Mo from high-molybdenum synthetic scheelite in HCl solutions containing H2O2[J].Hydrometallurgy,2015,155:1-5.
[16]XIA Wen-tang,ZHAO Zhong-wei,LI Hong-Gui.Thermodynamic analysis on sodium carbonate decomposition of calcium molybdenum[J].Transactions of Nonferrous Metals Society of China,2007,17(3):622-625.
[17]PAN Mao-sen,ZHU Yun.Experimental study on leaching molybdenum at high-pressure from calcium molybdate[J].China Molybdenum Industry,2005,29(6):19-21.(in Chinese)
[18]ZHANG Wen-juan,YANG Jin-hong,ZHAO Zhong-wei,WANGWen-qiang,LI Jiang-tao.Coordination leaching of tungsten from scheelite concentrate with phosphorus in nitric acid[J].Journal of Central South University,2016,23(6):1312-1317.
[19]XUIN G H,YU D Y,SU Y F.Leaching of scheelite by hydrochloric acid in the presence of phosphate[J].Hydrometallurgy,1986,16(1):27-40.
[20]LI Jiang-tao,ZHAO Zhong-wei.Kinetics of scheelite concentrate digestion with sulfuric acid in the presence of phosphoric acid[J].Hydrometallurgy,2016,163:55-60.
[21]KAHRUMAN C,YUSUFOGLU I.Leaching kinetics of synthetic Ca WO4 in HCl solutions containing H3PO4 as chelating agent[J].Hydrometallurgy,2006,81(3-4):182-189.
[22]PETTERSSON L,ANDERSSON I,?HMAN L O.Multicomponent polyanions.35.A 31P NMR study of aqueous molybdophosphates[J].Acta Chem Scand,1985,39:53-58.
[23]PETTERSSON L,ANDERSSON I,?HMAN L O.Multicomponent polyanions.39.Speciation in the aqueous H+-MoO42--HPO42-system as deduced from a combined Emf-phosphorus-31P NMR study[J].Inorganic Chemistry,1986,25(26):4726-4733.
[24]SPEIGHT J G.Lange’s handbook of chemistry[M].New York:McGraw-Hill,2005.
[25]YANG Jin-hong,HE Li-hua,LIU Xu-heng,DING Wen-tao,SONGYun-feng,ZHAO Zhong-wei.Comparative kinetic analysis of conventional and ultrasound-assisted leaching of scheelite by sodium carbonate[J].Transactions of Nonferrous Metals Society of China,2018,28(4):775-782.
[26]YANG Hong-ying,LI Xue-jiao,TONG Lin-lin,JIN Zhe-nan,YINLu,CHEN Guo-bao.Leaching kinetics of selenium from copper anode slimes by nitric acid-sulfuric acid mixture[J].Transactions of Nonferrous Metals Society of China,2018,28(1):186-192.
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