氢氧化钠-磷酸盐浸出白钨矿精矿动力学（英文）
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摘要
以低品位白钨精矿为研究对象,在高压反应釜体系中研究白钨精矿在氢氧化钠-磷酸盐溶液中的反应动力学,考察搅拌速度(300～600r/min)、反应温度(353～383K)、氢氧化钠浓度(1.69～6.76mol/L)和磷酸盐浓度(0.68～1.69 mol/L)对WO_3浸出率的影响。结果表明,WO_3浸出率与搅拌速度无关,但随着反应温度、氢氧化钠浓度和磷酸盐浓度的增加而升高。实验结果遵循收缩核模型,即浸出速率由原料和产物的表面化学反应控制。浸出反应的表观活化能为49.56kJ/mol,氢氧化钠浓度和磷酸盐浓度的反应级数分别为0.27和0.67。该浸出过程动力学方程可以根据相关结果和数据建立。
The reaction kinetics for the leaching of low-grade scheelite concentrate was investigated in an autoclave with sodium hydroxide in the presence of phosphate. The effects of stirring speed(300-600 r/min), reaction temperature(353-383 K), sodium hydroxide concentration(1.69-6.76 mol/L) and phosphate concentration(0.68-1.69 mol/L) on the WO_3 dissolution ratio were studied. The results showed that the WO_3 dissolution ratio was practically independent of stirring speed, while it increased with increasing the reaction temperature, and the concentrations of sodium hydroxide and phosphate. The experimental data were consistent with the shrinking core model, with a surface chemical reaction as the leaching rate-determining step. The apparent activation energy was calculated as 49.56 kJ/mol, and the reaction orders with respect to the concentrations of sodium hydroxide and phosphate were determined as 0.27 and 0.67, respectively. The kinetics equation of the leaching process was established.
The reaction kinetics for the leaching of low-grade scheelite concentrate was investigated in an autoclave with sodium hydroxide in the presence of phosphate. The effects of stirring speed(300-600 r/min), reaction temperature(353-383 K), sodium hydroxide concentration(1.69-6.76 mol/L) and phosphate concentration(0.68-1.69 mol/L) on the WO_3 dissolution ratio were studied. The results showed that the WO_3 dissolution ratio was practically independent of stirring speed, while it increased with increasing the reaction temperature, and the concentrations of sodium hydroxide and phosphate. The experimental data were consistent with the shrinking core model, with a surface chemical reaction as the leaching rate-determining step. The apparent activation energy was calculated as 49.56 kJ/mol, and the reaction orders with respect to the concentrations of sodium hydroxide and phosphate were determined as 0.27 and 0.67, respectively. The kinetics equation of the leaching process was established.
引文
[1]BOHLOULI A,AFSHAR M R,ABOUTALEBI M R,SEYEDEIN SH.Optimization of tungsten leaching from low manganese wolframite concentrate using response surface methodology(RSM)[J].International Journal of Refractory Metals&Hard Materials,2016,61:107-114.
[2]MARTINS J I.Leaching systems of wolframite and scheelite:Athermodynamic approach[J].Mineral Processing&Extractive Metallurgy Review,2014,35:23-43.
[3]SRINIVAS K,SREENIVAS T,NATARAJAN R,PADMANABHANN P H.Studies on the recovery of tungsten from a composite wolframite-scheelite concentrate[J].Hydrometallurgy,2000,58:43-50.
[4]WANG Lin-sheng,HUANG Xiao-jing,DENG Deng-fei,LIHong-chao,CHEN Yao-ming.Synthesis of scheelite from sodium tungstate solution by calcium hydroxide addition[J].Hydrometallurgy,2015,154:17-19.
[5]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.
[6]ZHAO Zhong-wei,LIANG Yong,LIU Xue-heng,CHEN Ai-liang,LI Hong-gui.Sodium hydroxide digestion of scheelite by reactive extrusion[J].International Journal of Refractory Metals&Hard Materials,2011,29:739-742.
[7]HE Gui-xiang,ZHAO Zhong-wei,WANG Xiao-bo,LI Jiang-tao,CHEN Xing-yu,HE Li-hua,LIU Xu-heng.Leaching kinetics of scheelite in hydrochloric acid solution containing hydrogen peroxide as complexing agent[J].Hydrometallurgy,2014,144:140-147.
[8]ZHAO Z W,DING W T,LIU X H,LIANG Y.Effect of ultrasound on kinetics of scheelite leaching in sodium hydroxide[J].Canadian Metallurgical Quarterly,2013,52:138-145.
[9]GüRMEN S,TIMUR S,ARSLAN C,DUMAN I.Acidic leaching of scheelite concentrate and production of hetero-poly-tungstate salt[J].Hydrometallurgy,1999,51:227-238.
[10]LI Xiao-bin,SHEN Lei-ting,ZHOU Qiu-sheng,PENG Zhi-hong,LIU Gui-hua,QI Tian-gui.Scheelite conversion in sulfuric acid together with tungsten extraction by ammonium carbonate solution[J].Hydrometallurgy,2017,171:106-115.
[11]MARTINS J I.Leaching of synthetic scheelite by nitric acid without the formation of tungstic acid[J].Hydrometallurgy,2003,70:131-141.
[12]PAULINO J F,AFONSO J C,MANTOVANO J L,VIANNA C A.Recovery of tungsten by liquid-liquid extraction from a wolframite concentrate after fusion with sodium hydroxide[J].Hydrometallurgy,2012,127-128:121-124.
[13]LI Hong-gui.Production of high purity APT from scheelite and complex tungsten raw material with high Mo content[J].Transactions of Nonferrous Metals Society of China,2004,14:366-369.
[14]LIU Liang,XUE Ji-lai,LIU Kang,ZHU Jun,WANG Zeng-jie.Complex leaching process of scheelite in hydrochloric and phosphoric solutions[J].JOM,2016,68:1-8.
[15]ZHANG Wen-juan,LI Jiang-tao,ZHAO Zhong-wei,HUANGShao-bo,CHEN Ying-xue,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]KAHRUMAN C,YUSUFOGLU I.Leaching kinetics of synthetic Ca WO4 in HCl solutions containing H3PO4 as chelating agent[J].Hydrometallurgy,2006,81:182-189.
[17]ZHAO Zhong-wei,LI Jiang-tao,WANG Shi-bo,LI Hong-gui,LIUMao-sheng,SUN Pei-mei,LI Yun-jiao.Extracting tungsten from scheelite concentrate with caustic soda by autoclaving process[J].Hydrometallurgy,2011,108:152-156.
[18]ILHAN S,KALPAKLI A,KAHRUMAN C,YUSUFOGLU I.The investigation of dissolution behavior of gangue materials during the dissolution of scheelite concentrate in oxalic acid solution[J].Hydrometallurgy,2013,136:15-26.
[19]ZHANG Wen-juan,LI Jiang-tao,ZHAO Zhong-wei.Leaching kinetics of scheelite with nitric acid and phosphoric acid[J].International Journal of Refractory Metals&Hard Materials,2015,52:78-84.
[20]ZHAO Zhong-wei,LI Hong-gui.Thermodynamics for leaching of scheelite-pseudo-ternary-system phase diagram and its application[J].Metallurgical&Materials Transactions B,2008,39:519-523.
[21]ZHAO Zhong-wei,CAO Cai-fang,LI Hong-gui.Thermodynamics on soda decomposition of scheelite[J].The Chinese Journal of Nonferrous Metals,2008,18:356-360.(in Chinese)
[22]WANG Shi-bo,ZHAO Zhong-wei,LI Hong-gui.Thermodynamic analysis on phosphate decomposition of scheelite[J].Rare Metals&Cemented Carbides,2005,1:1-4(in Chinese).
[23]MARTINS J P.Kinetics of soda ash leaching of low-grade scheelite concentrates[J].Hydrometallurgy,1996,42:221-236.
[24]ASHRAF M,ZAFAR Z I,ANSARI T M.Selective leaching kinetics and upgrading of low-grade calcareous phosphate rock in succinic acid[J].Hydrometallurgy,2005,80:286-292.
[2]MARTINS J I.Leaching systems of wolframite and scheelite:Athermodynamic approach[J].Mineral Processing&Extractive Metallurgy Review,2014,35:23-43.
[3]SRINIVAS K,SREENIVAS T,NATARAJAN R,PADMANABHANN P H.Studies on the recovery of tungsten from a composite wolframite-scheelite concentrate[J].Hydrometallurgy,2000,58:43-50.
[4]WANG Lin-sheng,HUANG Xiao-jing,DENG Deng-fei,LIHong-chao,CHEN Yao-ming.Synthesis of scheelite from sodium tungstate solution by calcium hydroxide addition[J].Hydrometallurgy,2015,154:17-19.
[5]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.
[6]ZHAO Zhong-wei,LIANG Yong,LIU Xue-heng,CHEN Ai-liang,LI Hong-gui.Sodium hydroxide digestion of scheelite by reactive extrusion[J].International Journal of Refractory Metals&Hard Materials,2011,29:739-742.
[7]HE Gui-xiang,ZHAO Zhong-wei,WANG Xiao-bo,LI Jiang-tao,CHEN Xing-yu,HE Li-hua,LIU Xu-heng.Leaching kinetics of scheelite in hydrochloric acid solution containing hydrogen peroxide as complexing agent[J].Hydrometallurgy,2014,144:140-147.
[8]ZHAO Z W,DING W T,LIU X H,LIANG Y.Effect of ultrasound on kinetics of scheelite leaching in sodium hydroxide[J].Canadian Metallurgical Quarterly,2013,52:138-145.
[9]GüRMEN S,TIMUR S,ARSLAN C,DUMAN I.Acidic leaching of scheelite concentrate and production of hetero-poly-tungstate salt[J].Hydrometallurgy,1999,51:227-238.
[10]LI Xiao-bin,SHEN Lei-ting,ZHOU Qiu-sheng,PENG Zhi-hong,LIU Gui-hua,QI Tian-gui.Scheelite conversion in sulfuric acid together with tungsten extraction by ammonium carbonate solution[J].Hydrometallurgy,2017,171:106-115.
[11]MARTINS J I.Leaching of synthetic scheelite by nitric acid without the formation of tungstic acid[J].Hydrometallurgy,2003,70:131-141.
[12]PAULINO J F,AFONSO J C,MANTOVANO J L,VIANNA C A.Recovery of tungsten by liquid-liquid extraction from a wolframite concentrate after fusion with sodium hydroxide[J].Hydrometallurgy,2012,127-128:121-124.
[13]LI Hong-gui.Production of high purity APT from scheelite and complex tungsten raw material with high Mo content[J].Transactions of Nonferrous Metals Society of China,2004,14:366-369.
[14]LIU Liang,XUE Ji-lai,LIU Kang,ZHU Jun,WANG Zeng-jie.Complex leaching process of scheelite in hydrochloric and phosphoric solutions[J].JOM,2016,68:1-8.
[15]ZHANG Wen-juan,LI Jiang-tao,ZHAO Zhong-wei,HUANGShao-bo,CHEN Ying-xue,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]KAHRUMAN C,YUSUFOGLU I.Leaching kinetics of synthetic Ca WO4 in HCl solutions containing H3PO4 as chelating agent[J].Hydrometallurgy,2006,81:182-189.
[17]ZHAO Zhong-wei,LI Jiang-tao,WANG Shi-bo,LI Hong-gui,LIUMao-sheng,SUN Pei-mei,LI Yun-jiao.Extracting tungsten from scheelite concentrate with caustic soda by autoclaving process[J].Hydrometallurgy,2011,108:152-156.
[18]ILHAN S,KALPAKLI A,KAHRUMAN C,YUSUFOGLU I.The investigation of dissolution behavior of gangue materials during the dissolution of scheelite concentrate in oxalic acid solution[J].Hydrometallurgy,2013,136:15-26.
[19]ZHANG Wen-juan,LI Jiang-tao,ZHAO Zhong-wei.Leaching kinetics of scheelite with nitric acid and phosphoric acid[J].International Journal of Refractory Metals&Hard Materials,2015,52:78-84.
[20]ZHAO Zhong-wei,LI Hong-gui.Thermodynamics for leaching of scheelite-pseudo-ternary-system phase diagram and its application[J].Metallurgical&Materials Transactions B,2008,39:519-523.
[21]ZHAO Zhong-wei,CAO Cai-fang,LI Hong-gui.Thermodynamics on soda decomposition of scheelite[J].The Chinese Journal of Nonferrous Metals,2008,18:356-360.(in Chinese)
[22]WANG Shi-bo,ZHAO Zhong-wei,LI Hong-gui.Thermodynamic analysis on phosphate decomposition of scheelite[J].Rare Metals&Cemented Carbides,2005,1:1-4(in Chinese).
[23]MARTINS J P.Kinetics of soda ash leaching of low-grade scheelite concentrates[J].Hydrometallurgy,1996,42:221-236.
[24]ASHRAF M,ZAFAR Z I,ANSARI T M.Selective leaching kinetics and upgrading of low-grade calcareous phosphate rock in succinic acid[J].Hydrometallurgy,2005,80:286-292.