反应挤出法碱分解钨矿基础理论及新工艺
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摘要
钨矿是我国重要的优势战略资源,经济、高效地从钨矿中提取钨一直是钨冶炼工业中的一个重要课题。
本文围绕钨矿碱分解的理论和新工艺进行了研究,主要内容如下：
(1)系统研究了氢氧化钠分解白钨矿的动力学过程。研究结果表明：在反应温度为60～100℃的条件下,白钨矿的碱分解过程属表面化学反应控制,增大碱浓度、升高反应温度和减小矿物粒度均有利反应的进行。基于溶液活度的条件下研究过程动力学,测得的反应表观活化能和反应级数分别为82.0kJ·mol-1和0.68,建立的动力学方程为：1-(1-x)1/3=54.08a0.68r0exp(8.314T/82000)t;而以浓度代替活度时,则得到反应表观活化能和反应级数分别为64.9kJ·mol-1和1.74,建立的动力学方程为：1-(1-x)3/1=20.12×10-3[NaOH]1.74r0-1exp(8.314T/64900)t。两种情况下测得的动力学参数有较大的偏差,说明在浸出剂浓度较高、活度条件变化较大时,不能简单以浓度代替活度进行动力学研究。
在此基础上,还分别考察了机械活化对碱分解白钨精矿和黑钨精矿动力学的影响。实验结果表明：机械活化能明显降低钨矿碱浸过程的表观活化能,降低钨矿碱分解过程对温度的依赖程度,强化钨矿的浸出。白钨精矿浸出反应的表观活化能由未活化时的78.1kJ·mol-1下降至机械活化10min后的27.9kJ·mor-1;而黑钨精矿的浸出过程相应也未活化时76.2kJ·mor-1下降至机械活化20min后的34.3kJ·mor-1。
(2)考虑到反应挤出技术能有效地解决高浓高粘物料体系的传质问题,同时也可为物料提供强烈的机械活化作用,因而可借用于高碱、高粘度钨矿浸出新工艺的开发。鉴于反应挤出技术从未应用于湿法冶金领域,因此,本文首次对实验所用反应挤出设备(双螺杆挤出机)的反应工程学进行了研究。
研究结果表明,流体在反应器内的平均停留时间t随着螺杆转速的增大而缩短,随着温度的升高而增长；按槽列模型计算所得虚拟槽数均随着螺杆转速的增大和温度升高而减少；螺杆转速对平均停留时间t和虚拟槽数N的影响较温度更显著；流体的轴向混合强度均随着螺杆转速的增大和温度的升高而增大。
综上,双螺杆挤出机类似管式反应器,可看成由多个串联的全混槽组合而成,其反应效率优于间歇式全混槽(如压煮反应器)。(3)在以上研究基础上,开发了反应挤出法碱分解钨矿的新工艺,考察了反应温度、浸出时间、螺杆转速和碱用量对白钨精矿和黑钨精矿的碱分解效果的影响。研究结果表明：反应挤出法碱分解钨矿新工艺可以高效、连续地分解白钨精矿和黑钨精矿。
处理白钨精矿时,在矿水质量比高达2.67：1、分解时间为3.5h、螺杆转速为160rpm和碱用量为理论量的2.2倍的条件下,分解温度仅为120℃(比传统碱分解工艺反应温度低了30～60℃),白钨精矿分解率可达99.18%。处理黑钨精矿时,以相同的矿水比并控制分解时间为2.5h、螺杆转速为180rpm和碱用量为理论量1.5倍时,反应温度也只需120℃,黑钨精矿分解率便可达99.13%。
在此基础上,考察了该工艺对其他钨矿的适应能力,结果表明,采用新工艺处理各钨矿时分解率均高于99%,新工艺对钨矿原料的适应性较强。
与传统碱法工艺相比,新工艺在碱用量相当、水用量少、温度较低的条件下,实现了钨矿常压碱分解,降低了能耗,节约了生产成本。
Tungsten ores is one of the important strategic resources in China. Up to now, tungsten extraction from the tungsten ores economically and efficiently is widely researched in the tungsten smelting industry.
The basic theory and novel process were investigated in this paper and the main research contents were as follows:
(1) The kinetics of sodium hydroxide leaching of scheelite was investigated systematically. The research results indicated that the leaching rate was controlled by the surface chemical reaction from60to100℃. Increasing of alkali concentration, temperature and the decreasing the particle size of the mineral can improve the reaction rate remarkably. Based on the solution activity, the apparent activation energy and the reaction order of the process were respectively determined as82.0kJ·mol-1and0.68. And the kinetics equation was established as1-(1-x)1/3=54.08a0.68r0-1exp(8.314T/82000)t. However, when the activity was replaced by concentration, the apparent activation energy and the reaction order of the process were determined as64.9kJ·mol-1and1.74, respectively. And the corresponding kinetics equation of the process was established as1-(1-x)3/1=20.12×10-3[NaOH]1.74r0-1exp(8.314T/64900)t. The determined kinetics parameters had obvious deviations with that determined based on the solution activity. This indicated that the activity of solution cannot be replaced directly with concentration to research the kinetics when the solution concentration was high, because its activity was affected by the concentration of solution and temperature.
Based on the above study, the effects of mechanical activation on the apparent activation energy of sodium hydroxide leaching of scheelite concentrates and wolframite concentrates were investigated. The results indicated that mechanical activation effect can remarkably decrease the apparent activation energy of sodium hydroxide leaching of tungsten ores, which means that the tungsten ore can be digested with sodium hydroxide under a lower temperature. The leaching process was strengthened by mechanical activation. For scheelite concentrates, the apparent activation of the process was decreased from78.1kJ·mol-1to27.9kJ·mol-1by the mechanical activation after10min and for wolframite concentrates, the apparent activation of the process was also decreased from76.2kJ·mol-1to34.3kJ·mol-1by the mechanical activation after20min.
(2) Reactive extrusion technology was widely used to treat the materials with high viscosity. By the technology, mass transfer of material with high viscosity can be solved and mechanical activation effect can be provided for the material. So, it is considerable to apply this technology to develop a novel process of sodium hydroxide digestion of highly viscous scheelite slurry. In view of reactive extrusion technology used in hydrometallurgy field for the first time, reaction engineering about the equipment used for developing novel process (twin screw extruder) was investigated in the paper.
The research results indicated that the average residence time of flow in the reactor decreased with the rotating speed of screws increased, and increased with the temperature increased; the quantity of virtual slot calculated by tank column model decreased as the rotating speed of screws and temperature increased; the effect of the rotating speed of screws on the average residence time and the quantity of virtual slot was more significant than the temperature; the axial mixing intensity of fluid increased with the rotating speed of screws and temperature increased.
Therefore, twin screw extruder is similar with a tubular reactor which is equivalent of numbers of full-mixed tank reactors in series. The equipment is more efficient than single full-mixed tank reactor (such as autoclave reactor).
(3) Based on the above study, a novel technology of sodium hydroxide digestion of tungsten ores by reactive extrusion was developed. The effect of leaching temperature, screw rotating speed, reaction time and NaOH dosage on the decomposition of scheelite concentrates and wolframite concentrates were investigated. The experiments results showed that scheelite concentrate and wolframite can be digested efficiently and continuously by the novel process of reactive extrusion method.
For scheelite concentrate, on the digestion conditions of the mass ratio of ores/water2.67:1, the dosage of NaOH2.2times to stoichiometry, the screw rotating speed160rpm and the reaction time3.5h and the temperature just120℃(which was30～60℃lower than that of the traditional processes), the WO3extraction can reach99.18%; While for wolframite concentrate, under the conditions of the mass ratio of ores/water2.67:1, the reaction time3.5h, the screw rotating speed160rpm and the dosage of NaOH2.2times to stoichiometry and the temperature just120℃, the WO3extraction can reached99.13%. Both scheelite concentrate and wolframite concentrate can be decomposed completely by the novel process.
Besides, the adaptation of novel process to other tungsten ore had been investigated. The results showed that the novel process can deal with other tungsten ore well with all the WO3extraction more than99%, which meant that the novel process was adaptable rifely to tungsten ores.
Compared with the traditional NaOH leaching process, tungsten ors can be decomposed completely by this novel process which is conducted on the conditions of atmospheric pressure, less water dosage, lower temperature and considerable dosage of NaOH.
本文围绕钨矿碱分解的理论和新工艺进行了研究,主要内容如下：
(1)系统研究了氢氧化钠分解白钨矿的动力学过程。研究结果表明：在反应温度为60～100℃的条件下,白钨矿的碱分解过程属表面化学反应控制,增大碱浓度、升高反应温度和减小矿物粒度均有利反应的进行。基于溶液活度的条件下研究过程动力学,测得的反应表观活化能和反应级数分别为82.0kJ·mol-1和0.68,建立的动力学方程为：1-(1-x)1/3=54.08a0.68r0exp(8.314T/82000)t;而以浓度代替活度时,则得到反应表观活化能和反应级数分别为64.9kJ·mol-1和1.74,建立的动力学方程为：1-(1-x)3/1=20.12×10-3[NaOH]1.74r0-1exp(8.314T/64900)t。两种情况下测得的动力学参数有较大的偏差,说明在浸出剂浓度较高、活度条件变化较大时,不能简单以浓度代替活度进行动力学研究。
在此基础上,还分别考察了机械活化对碱分解白钨精矿和黑钨精矿动力学的影响。实验结果表明：机械活化能明显降低钨矿碱浸过程的表观活化能,降低钨矿碱分解过程对温度的依赖程度,强化钨矿的浸出。白钨精矿浸出反应的表观活化能由未活化时的78.1kJ·mol-1下降至机械活化10min后的27.9kJ·mor-1;而黑钨精矿的浸出过程相应也未活化时76.2kJ·mor-1下降至机械活化20min后的34.3kJ·mor-1。
(2)考虑到反应挤出技术能有效地解决高浓高粘物料体系的传质问题,同时也可为物料提供强烈的机械活化作用,因而可借用于高碱、高粘度钨矿浸出新工艺的开发。鉴于反应挤出技术从未应用于湿法冶金领域,因此,本文首次对实验所用反应挤出设备(双螺杆挤出机)的反应工程学进行了研究。
研究结果表明,流体在反应器内的平均停留时间t随着螺杆转速的增大而缩短,随着温度的升高而增长；按槽列模型计算所得虚拟槽数均随着螺杆转速的增大和温度升高而减少；螺杆转速对平均停留时间t和虚拟槽数N的影响较温度更显著；流体的轴向混合强度均随着螺杆转速的增大和温度的升高而增大。
综上,双螺杆挤出机类似管式反应器,可看成由多个串联的全混槽组合而成,其反应效率优于间歇式全混槽(如压煮反应器)。(3)在以上研究基础上,开发了反应挤出法碱分解钨矿的新工艺,考察了反应温度、浸出时间、螺杆转速和碱用量对白钨精矿和黑钨精矿的碱分解效果的影响。研究结果表明：反应挤出法碱分解钨矿新工艺可以高效、连续地分解白钨精矿和黑钨精矿。
处理白钨精矿时,在矿水质量比高达2.67：1、分解时间为3.5h、螺杆转速为160rpm和碱用量为理论量的2.2倍的条件下,分解温度仅为120℃(比传统碱分解工艺反应温度低了30～60℃),白钨精矿分解率可达99.18%。处理黑钨精矿时,以相同的矿水比并控制分解时间为2.5h、螺杆转速为180rpm和碱用量为理论量1.5倍时,反应温度也只需120℃,黑钨精矿分解率便可达99.13%。
在此基础上,考察了该工艺对其他钨矿的适应能力,结果表明,采用新工艺处理各钨矿时分解率均高于99%,新工艺对钨矿原料的适应性较强。
与传统碱法工艺相比,新工艺在碱用量相当、水用量少、温度较低的条件下,实现了钨矿常压碱分解,降低了能耗,节约了生产成本。
Tungsten ores is one of the important strategic resources in China. Up to now, tungsten extraction from the tungsten ores economically and efficiently is widely researched in the tungsten smelting industry.
The basic theory and novel process were investigated in this paper and the main research contents were as follows:
(1) The kinetics of sodium hydroxide leaching of scheelite was investigated systematically. The research results indicated that the leaching rate was controlled by the surface chemical reaction from60to100℃. Increasing of alkali concentration, temperature and the decreasing the particle size of the mineral can improve the reaction rate remarkably. Based on the solution activity, the apparent activation energy and the reaction order of the process were respectively determined as82.0kJ·mol-1and0.68. And the kinetics equation was established as1-(1-x)1/3=54.08a0.68r0-1exp(8.314T/82000)t. However, when the activity was replaced by concentration, the apparent activation energy and the reaction order of the process were determined as64.9kJ·mol-1and1.74, respectively. And the corresponding kinetics equation of the process was established as1-(1-x)3/1=20.12×10-3[NaOH]1.74r0-1exp(8.314T/64900)t. The determined kinetics parameters had obvious deviations with that determined based on the solution activity. This indicated that the activity of solution cannot be replaced directly with concentration to research the kinetics when the solution concentration was high, because its activity was affected by the concentration of solution and temperature.
Based on the above study, the effects of mechanical activation on the apparent activation energy of sodium hydroxide leaching of scheelite concentrates and wolframite concentrates were investigated. The results indicated that mechanical activation effect can remarkably decrease the apparent activation energy of sodium hydroxide leaching of tungsten ores, which means that the tungsten ore can be digested with sodium hydroxide under a lower temperature. The leaching process was strengthened by mechanical activation. For scheelite concentrates, the apparent activation of the process was decreased from78.1kJ·mol-1to27.9kJ·mol-1by the mechanical activation after10min and for wolframite concentrates, the apparent activation of the process was also decreased from76.2kJ·mol-1to34.3kJ·mol-1by the mechanical activation after20min.
(2) Reactive extrusion technology was widely used to treat the materials with high viscosity. By the technology, mass transfer of material with high viscosity can be solved and mechanical activation effect can be provided for the material. So, it is considerable to apply this technology to develop a novel process of sodium hydroxide digestion of highly viscous scheelite slurry. In view of reactive extrusion technology used in hydrometallurgy field for the first time, reaction engineering about the equipment used for developing novel process (twin screw extruder) was investigated in the paper.
The research results indicated that the average residence time of flow in the reactor decreased with the rotating speed of screws increased, and increased with the temperature increased; the quantity of virtual slot calculated by tank column model decreased as the rotating speed of screws and temperature increased; the effect of the rotating speed of screws on the average residence time and the quantity of virtual slot was more significant than the temperature; the axial mixing intensity of fluid increased with the rotating speed of screws and temperature increased.
Therefore, twin screw extruder is similar with a tubular reactor which is equivalent of numbers of full-mixed tank reactors in series. The equipment is more efficient than single full-mixed tank reactor (such as autoclave reactor).
(3) Based on the above study, a novel technology of sodium hydroxide digestion of tungsten ores by reactive extrusion was developed. The effect of leaching temperature, screw rotating speed, reaction time and NaOH dosage on the decomposition of scheelite concentrates and wolframite concentrates were investigated. The experiments results showed that scheelite concentrate and wolframite can be digested efficiently and continuously by the novel process of reactive extrusion method.
For scheelite concentrate, on the digestion conditions of the mass ratio of ores/water2.67:1, the dosage of NaOH2.2times to stoichiometry, the screw rotating speed160rpm and the reaction time3.5h and the temperature just120℃(which was30～60℃lower than that of the traditional processes), the WO3extraction can reach99.18%; While for wolframite concentrate, under the conditions of the mass ratio of ores/water2.67:1, the reaction time3.5h, the screw rotating speed160rpm and the dosage of NaOH2.2times to stoichiometry and the temperature just120℃, the WO3extraction can reached99.13%. Both scheelite concentrate and wolframite concentrate can be decomposed completely by the novel process.
Besides, the adaptation of novel process to other tungsten ore had been investigated. The results showed that the novel process can deal with other tungsten ore well with all the WO3extraction more than99%, which meant that the novel process was adaptable rifely to tungsten ores.
Compared with the traditional NaOH leaching process, tungsten ors can be decomposed completely by this novel process which is conducted on the conditions of atmospheric pressure, less water dosage, lower temperature and considerable dosage of NaOH.
引文
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