高钙云母型含钒页岩焙烧及浸出机理研究
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摘要
含钒页岩是我国特有的含钒资源,分布广泛且储量巨大。从含钒页岩中提钒主要有传统钠化焙烧水浸、无添加剂焙烧酸浸、直接酸浸等工艺。高钙云母型含钒页岩是我国具有代表性的一类含钒页岩,由于钒在其中特殊的赋存状态,提钒难度大,采用上述工艺效果均不理想,而且对其焙烧过程及钒的浸出机理方面,如添加剂对云母类矿物晶格的破坏作用,焙烧过程中钒酸钙的形成特征,以及浸出的动力学过程等方面,都缺乏系统深入的研究。
针对以上问题,本研究在国家“十二五”科技支撑计划重点项目“典型含钒页岩高效提钒技术及示范”(编号：2011BAB05801)的资助下,选取湖北某地高钙云母型含钒页岩为原料,进行了无添加剂焙烧和添加剂焙烧研究,探讨了焙烧对白云母晶体结构的破坏,钒氧化与钒浸出等之间的关系,以及钙含量对钒水浸率的影响机理,此外,还探讨了钒浸出的动力学和热力学过程。主要结论及研究成果如下：
1、白云母纯矿物加入添加剂(NaCl、Na2SO4)焙烧后铝的浸出率均比无添加剂焙烧明显提高,同样添加剂也能促进含钒白云母结构破坏,促进钒的浸出。
2、高钙云母型含钒页岩无添加剂焙烧过程
(1)原矿直接用20%硫酸浸出3h,钒浸出率为24%；同样的浸出条件,9000C无添加剂焙烧样浸出率达到70%。无添加剂焙烧的最佳条件为焙烧温度：900℃,焙烧时间：2h。
(2)含钒白云母脱除羟基的反应在830℃以上。随着羟基脱除,八面体结构失稳,钒浸出率大幅升高,温度过高,含钒物质会被玻璃态物质包裹,浸出率急剧下降,900℃无添加剂焙烧样中仍存在白云母,因此稀酸浸出效果不好。
3、高钙云母型含钒页岩复合添加剂焙烧过程
(1)原矿采用传统NaCl焙烧工艺,钒的水浸率不到30%；采用复合添加剂可以降低NaCl用量,保证总浸率同时提高水浸率,最终采用的复合添加剂配比为6%NaCl加上10%Na2SO4,在此条件下钒的水浸率为45.01%,钒的总浸率可达77.61%。
(2)增加五价钒(V(Ⅴ))的氧化率是提高水浸率的前提,四价钒(V(Ⅳ))的氧化前段受界面化学反应过程控制,反应后段受内扩散控制,且有如下结论：1)温度是决定反应发生的重要因素；2)反应速率与颗粒粒径成反比；3)在氧气含量一定的情况下,增加气流速度对钒氧化无影响；4)复合添加剂可以明显降低反应活化能,界面化学控制阶段的表观活化能由173.230kJ/mol降至104.690kJ/mol;5)氧气的内扩散过程也十分重要,如果出现烧结必然会影响到钒的氧化。
(3)复合钠盐添加剂焙烧产物主要晶态物相为钾钠长石和石英,钒酸盐与钾钠长石伴随而生,白云母转化为钾钠长石的量越多,钒总浸率越高,只有一定的温度才能生成钾钠长石物相,但焙烧温度过高会生成玻璃态物质包裹钒而使总浸率急剧下降,因此合适的焙烧温度范围为：850℃-900℃。
(4)该矿石采用添加单一NaCl焙烧会生成大量钒酸钙,导致水浸率较低；通过纯V205和CaCO3的试验得出以下结论：1)过量CaCO3(mCaCO3:mV2O5>3)与V205反应,850℃时产物为Ca3V2O8,700℃焙烧时会有部分Ca2V2O7生成。2)在CaCO3相对V205过量(mCaCO3:mV2O5>3)的条件下,添加NaCl焙烧时并不能阻碍钒酸钙的生成。而添加Na2SO4在850℃时能使部分V205生成NaVO3,而减少难溶的钒酸钙的生成,起到提高钒水浸率的作用。
(5)氯气气氛下焙烧能加速含钒白云母晶体结构的破坏,同时对钒酸盐的生成起到催化的作用,这也是复合添加剂中NaCl的作用机理。
4、原矿及焙烧样浸出过程
对原矿,无添加剂焙烧样,复合添加剂焙烧样三种样品进行的浸出动力学研究表明：
(1)原矿酸浸(30%H2S04,以下均为体积浓度)过程钒浸出的表观活化能为48.63kJ/mol,属于化学反应控制,温度对反应速率影响显著；表观反应级数为1.2075。硫酸浓度在33%以下时,钒浸出反应处于化学控制区,提高硫酸浓度,化学反应速率增大,浸出率提高。当硫酸浓度高于33%时,反应处于内扩散控制区,继续提高硫酸浓度作用不明显。
(2)无添加剂焙烧样酸浸时,表观反应级数为1.04335,比原矿直接酸浸要低,因此从化学反应控制转变为内扩散控制所需的硫酸浓度降低。当硫酸浓度高于20%时,反应处于内扩散控制区域。
(3)复合添加剂焙烧样水浸过程满足液膜非稳态扩散模型,而水浸渣采用2%H2S04酸浸时,其过程就已属于内扩散控制,因此,添加剂焙烧能显著降低钒浸出反应级数,降低酸的用量。
Vanadium-bearing black shale is a unique vanadium resource in China, and the total reserve of vanadium-bearing black shale is abundant. It is widely distributed in many provinces of China. The typical techniques of vanadium extraction from vanadium-bearing black shale include:traditional high salt roasting-water leaching technique, direct acid leaching technique and blank oxidation roasting-acid leaching technique. High calcium mica-type vanadium-bearing black shale is a representative type of black shale in China, it is difficult to extract vanadium for the special occurrence state of vanadium in this type of balck shale. The mechanism of roasting and vanadium leaching for high calcium mica-type vanadium-bearing black shale, such as the effect of additives on the mica crystal lattice, the characteristics of the formation of calcium vanadate during roasting process, and the kinetics of leaching process of vanadium are not studied well.
In orde to resolve these problems, this work, which was financially supported by the National Key Technologies R&D Program of China (No.2011BAB05B01), investigated the non-additive roasting and additive roasting processes for high calcium mica-type vanadium-bearing black shale in Hubei. Furthermore, the change of vanadium compounds in roasting process was studied, and the effect of roasting to mica crystal lattice, vanadium oxidation to vanadium leaching and the content of calcium to water leaching rate was also discussed. By using compound additives roasting, the high leaching rate of vanadium was achieved, and the acid consumption was reduced. The main conclusions are as follows:
1. The leaching rate of aluminum from mica was higher by addtive (NaCl, Na2SO4) roasting than it by non-additive roasting. Accordingly, The additive roasting also can enhance the decompose of mica structure and improve and leaching rate of vanadium (LRV).
2. The effect of non-additive roasting on the mineral structure and the LRV
(1) The LRV was only24%when the raw black shale was leached by20%H2SO4for3h, but the LRV can reach70%after the raw ore was roasted at900℃. The optimum conditions of oxidation roasting were roasting temperature:900℃, roasting time:2h.
(2) The dehydroxylation of mica occurs when the roasting temperature is above 830℃. The LRV increases apparently along with the dehydroxylation of mica, but the LRV decreases dramatically when the roasting temperature is too high and the vanadium-bearing materials is wrapped in newly formed aluminosilicate and sintered materials, which causes vanadium is hard to leach. It is less effective for vanadium leaching with dilute acid because mica is also found in the sample roasted at900℃with non-additive.
3. The study on the compound additive roasting
(1) The water leaching rate of vanadium (WLRV) is below30%using conventional high sodium roasting. By using compound additive roasting it can reduce the salt consumption and increase WLRV at the same time. The WLRV is45.01%, and the overall leaching rate can reach77.61%by roasting with6%NaCl and10%Na2S04
(2) The premise of increasing the WLRV is increasing the content of pentavalent vanadium (V(V)), and the oxidation process of tetravalent vanadium is controlled by interface chemical reaction in the forepart, and by internal diffusion in later of the roasting process. The conclusions are as follows:1) Temperature is the key factor of the vanadium oxidation reaction.2) The reaction rate is in inverse proportion to particle size of reactant.3) When the oxygen concentration is fixed, The increase of the air velocity has no effect on vanadium oxidation.4) The compound additive can reduce activation energy barrier of interface chemical reaction, from173.230kJ/mol to104.690kJ/mol.5) The internal diffusion of oxygen is also important, the oxidation of V(IV) can be impeded if the materials is sintered.
(3) The crystal phase in roasted sample by adding compound additive are K-Na feldspar and quartz. The more K-Na feldspar in roasted sample the more the LRV is. The K-Na feldspar grow well at the conditions of enough high temperature and additive content, but the LRV decreases dramatically when the temperature is too high, because the vanadium-bearing materials is wrapped in glass-like state material. So the appropriate temperature for roasting is850～900℃.
(4) A mass of calcium vanadate will be generated when the raw ore is roasted with NaCl, and it is the reason for the lower WLRV due to calcium vanadate is insoluble in water. Through the roasting experiment using pure V2O5and CaCO3, some conclusions can be drawn as follows:1) the reaction products of excess content of CaCO3(mCaCO3:mV2O5>3) with V2O5was Ca3V2O8, and a part of Ca2V2O7will be generated at lower temperature.2) the calcium vanadate can not be impeded in the process of roasting with NaCl at the condition of excess CaCO3. The calcium vanadate can not be partly impeded in the process of roasting with Na2SO4additive, and a part of V2O5can form NaV03accordingly, hence, the Na2SO4in the compound additive can enhance the WLRV.
(5) Chlorine can promote the decomposition of vanadium-bearing mica crystal lattice and the generation of metal vanadates.
4. The study on the process of leaching vanadium from the raw ore and roasted sample
The researches of leaching kinetics of raw ore, non-additive roasted sample and additive roasted samples show:
(1) The apparent activation energy and apparent reaction order of the reaction direct acid (30%H2SO4, volume concentration) leaching vanadium from raw ore are48.63kJ/mol and1.2075, respectively. The kinetic results show that the reaction rate is controlled by chemical process. Leaching temperature affect the reaction rate apparently. When the acid concentration is below33%, the reaction rate of vanadium leaching is controlled by chemical process. Increasing the acid concentration accelerates the chemistry reaction rate. When the acid concentration is above33%, the leaching reaction is in internal diffusion control area and it is less effective to enhance leaching rate by increasing the acid concentration.
(2) The apparent reaction order of the reaction that leaching vanadium from blank oxidation roasted sample is1.04335. It is lower than of direct acid leaching reaction. Non-additive roasting can reduce acid concentration when the reaction is transfered from chemical control to internal diffusion control. As acid concentration is above20%, the reaction is controlled by internal diffusion.
(3) The process of leaching vanadium with acid from additive roasted sample is controlled by unsteady-state diffusion of liquid film. The process of leaching vanadium with acid (2%H2SO4) from water leached residue belongs to shrinking unreacted core model, and it is controlled by internal diffusion. Therefore, non-additive roasting and additive roasting both can reduce the apparent reaction order and the acid consumption.
针对以上问题,本研究在国家“十二五”科技支撑计划重点项目“典型含钒页岩高效提钒技术及示范”(编号：2011BAB05801)的资助下,选取湖北某地高钙云母型含钒页岩为原料,进行了无添加剂焙烧和添加剂焙烧研究,探讨了焙烧对白云母晶体结构的破坏,钒氧化与钒浸出等之间的关系,以及钙含量对钒水浸率的影响机理,此外,还探讨了钒浸出的动力学和热力学过程。主要结论及研究成果如下：
1、白云母纯矿物加入添加剂(NaCl、Na2SO4)焙烧后铝的浸出率均比无添加剂焙烧明显提高,同样添加剂也能促进含钒白云母结构破坏,促进钒的浸出。
2、高钙云母型含钒页岩无添加剂焙烧过程
(1)原矿直接用20%硫酸浸出3h,钒浸出率为24%；同样的浸出条件,9000C无添加剂焙烧样浸出率达到70%。无添加剂焙烧的最佳条件为焙烧温度：900℃,焙烧时间：2h。
(2)含钒白云母脱除羟基的反应在830℃以上。随着羟基脱除,八面体结构失稳,钒浸出率大幅升高,温度过高,含钒物质会被玻璃态物质包裹,浸出率急剧下降,900℃无添加剂焙烧样中仍存在白云母,因此稀酸浸出效果不好。
3、高钙云母型含钒页岩复合添加剂焙烧过程
(1)原矿采用传统NaCl焙烧工艺,钒的水浸率不到30%；采用复合添加剂可以降低NaCl用量,保证总浸率同时提高水浸率,最终采用的复合添加剂配比为6%NaCl加上10%Na2SO4,在此条件下钒的水浸率为45.01%,钒的总浸率可达77.61%。
(2)增加五价钒(V(Ⅴ))的氧化率是提高水浸率的前提,四价钒(V(Ⅳ))的氧化前段受界面化学反应过程控制,反应后段受内扩散控制,且有如下结论：1)温度是决定反应发生的重要因素；2)反应速率与颗粒粒径成反比；3)在氧气含量一定的情况下,增加气流速度对钒氧化无影响；4)复合添加剂可以明显降低反应活化能,界面化学控制阶段的表观活化能由173.230kJ/mol降至104.690kJ/mol;5)氧气的内扩散过程也十分重要,如果出现烧结必然会影响到钒的氧化。
(3)复合钠盐添加剂焙烧产物主要晶态物相为钾钠长石和石英,钒酸盐与钾钠长石伴随而生,白云母转化为钾钠长石的量越多,钒总浸率越高,只有一定的温度才能生成钾钠长石物相,但焙烧温度过高会生成玻璃态物质包裹钒而使总浸率急剧下降,因此合适的焙烧温度范围为：850℃-900℃。
(4)该矿石采用添加单一NaCl焙烧会生成大量钒酸钙,导致水浸率较低；通过纯V205和CaCO3的试验得出以下结论：1)过量CaCO3(mCaCO3:mV2O5>3)与V205反应,850℃时产物为Ca3V2O8,700℃焙烧时会有部分Ca2V2O7生成。2)在CaCO3相对V205过量(mCaCO3:mV2O5>3)的条件下,添加NaCl焙烧时并不能阻碍钒酸钙的生成。而添加Na2SO4在850℃时能使部分V205生成NaVO3,而减少难溶的钒酸钙的生成,起到提高钒水浸率的作用。
(5)氯气气氛下焙烧能加速含钒白云母晶体结构的破坏,同时对钒酸盐的生成起到催化的作用,这也是复合添加剂中NaCl的作用机理。
4、原矿及焙烧样浸出过程
对原矿,无添加剂焙烧样,复合添加剂焙烧样三种样品进行的浸出动力学研究表明：
(1)原矿酸浸(30%H2S04,以下均为体积浓度)过程钒浸出的表观活化能为48.63kJ/mol,属于化学反应控制,温度对反应速率影响显著；表观反应级数为1.2075。硫酸浓度在33%以下时,钒浸出反应处于化学控制区,提高硫酸浓度,化学反应速率增大,浸出率提高。当硫酸浓度高于33%时,反应处于内扩散控制区,继续提高硫酸浓度作用不明显。
(2)无添加剂焙烧样酸浸时,表观反应级数为1.04335,比原矿直接酸浸要低,因此从化学反应控制转变为内扩散控制所需的硫酸浓度降低。当硫酸浓度高于20%时,反应处于内扩散控制区域。
(3)复合添加剂焙烧样水浸过程满足液膜非稳态扩散模型,而水浸渣采用2%H2S04酸浸时,其过程就已属于内扩散控制,因此,添加剂焙烧能显著降低钒浸出反应级数,降低酸的用量。
Vanadium-bearing black shale is a unique vanadium resource in China, and the total reserve of vanadium-bearing black shale is abundant. It is widely distributed in many provinces of China. The typical techniques of vanadium extraction from vanadium-bearing black shale include:traditional high salt roasting-water leaching technique, direct acid leaching technique and blank oxidation roasting-acid leaching technique. High calcium mica-type vanadium-bearing black shale is a representative type of black shale in China, it is difficult to extract vanadium for the special occurrence state of vanadium in this type of balck shale. The mechanism of roasting and vanadium leaching for high calcium mica-type vanadium-bearing black shale, such as the effect of additives on the mica crystal lattice, the characteristics of the formation of calcium vanadate during roasting process, and the kinetics of leaching process of vanadium are not studied well.
In orde to resolve these problems, this work, which was financially supported by the National Key Technologies R&D Program of China (No.2011BAB05B01), investigated the non-additive roasting and additive roasting processes for high calcium mica-type vanadium-bearing black shale in Hubei. Furthermore, the change of vanadium compounds in roasting process was studied, and the effect of roasting to mica crystal lattice, vanadium oxidation to vanadium leaching and the content of calcium to water leaching rate was also discussed. By using compound additives roasting, the high leaching rate of vanadium was achieved, and the acid consumption was reduced. The main conclusions are as follows:
1. The leaching rate of aluminum from mica was higher by addtive (NaCl, Na2SO4) roasting than it by non-additive roasting. Accordingly, The additive roasting also can enhance the decompose of mica structure and improve and leaching rate of vanadium (LRV).
2. The effect of non-additive roasting on the mineral structure and the LRV
(1) The LRV was only24%when the raw black shale was leached by20%H2SO4for3h, but the LRV can reach70%after the raw ore was roasted at900℃. The optimum conditions of oxidation roasting were roasting temperature:900℃, roasting time:2h.
(2) The dehydroxylation of mica occurs when the roasting temperature is above 830℃. The LRV increases apparently along with the dehydroxylation of mica, but the LRV decreases dramatically when the roasting temperature is too high and the vanadium-bearing materials is wrapped in newly formed aluminosilicate and sintered materials, which causes vanadium is hard to leach. It is less effective for vanadium leaching with dilute acid because mica is also found in the sample roasted at900℃with non-additive.
3. The study on the compound additive roasting
(1) The water leaching rate of vanadium (WLRV) is below30%using conventional high sodium roasting. By using compound additive roasting it can reduce the salt consumption and increase WLRV at the same time. The WLRV is45.01%, and the overall leaching rate can reach77.61%by roasting with6%NaCl and10%Na2S04
(2) The premise of increasing the WLRV is increasing the content of pentavalent vanadium (V(V)), and the oxidation process of tetravalent vanadium is controlled by interface chemical reaction in the forepart, and by internal diffusion in later of the roasting process. The conclusions are as follows:1) Temperature is the key factor of the vanadium oxidation reaction.2) The reaction rate is in inverse proportion to particle size of reactant.3) When the oxygen concentration is fixed, The increase of the air velocity has no effect on vanadium oxidation.4) The compound additive can reduce activation energy barrier of interface chemical reaction, from173.230kJ/mol to104.690kJ/mol.5) The internal diffusion of oxygen is also important, the oxidation of V(IV) can be impeded if the materials is sintered.
(3) The crystal phase in roasted sample by adding compound additive are K-Na feldspar and quartz. The more K-Na feldspar in roasted sample the more the LRV is. The K-Na feldspar grow well at the conditions of enough high temperature and additive content, but the LRV decreases dramatically when the temperature is too high, because the vanadium-bearing materials is wrapped in glass-like state material. So the appropriate temperature for roasting is850～900℃.
(4) A mass of calcium vanadate will be generated when the raw ore is roasted with NaCl, and it is the reason for the lower WLRV due to calcium vanadate is insoluble in water. Through the roasting experiment using pure V2O5and CaCO3, some conclusions can be drawn as follows:1) the reaction products of excess content of CaCO3(mCaCO3:mV2O5>3) with V2O5was Ca3V2O8, and a part of Ca2V2O7will be generated at lower temperature.2) the calcium vanadate can not be impeded in the process of roasting with NaCl at the condition of excess CaCO3. The calcium vanadate can not be partly impeded in the process of roasting with Na2SO4additive, and a part of V2O5can form NaV03accordingly, hence, the Na2SO4in the compound additive can enhance the WLRV.
(5) Chlorine can promote the decomposition of vanadium-bearing mica crystal lattice and the generation of metal vanadates.
4. The study on the process of leaching vanadium from the raw ore and roasted sample
The researches of leaching kinetics of raw ore, non-additive roasted sample and additive roasted samples show:
(1) The apparent activation energy and apparent reaction order of the reaction direct acid (30%H2SO4, volume concentration) leaching vanadium from raw ore are48.63kJ/mol and1.2075, respectively. The kinetic results show that the reaction rate is controlled by chemical process. Leaching temperature affect the reaction rate apparently. When the acid concentration is below33%, the reaction rate of vanadium leaching is controlled by chemical process. Increasing the acid concentration accelerates the chemistry reaction rate. When the acid concentration is above33%, the leaching reaction is in internal diffusion control area and it is less effective to enhance leaching rate by increasing the acid concentration.
(2) The apparent reaction order of the reaction that leaching vanadium from blank oxidation roasted sample is1.04335. It is lower than of direct acid leaching reaction. Non-additive roasting can reduce acid concentration when the reaction is transfered from chemical control to internal diffusion control. As acid concentration is above20%, the reaction is controlled by internal diffusion.
(3) The process of leaching vanadium with acid from additive roasted sample is controlled by unsteady-state diffusion of liquid film. The process of leaching vanadium with acid (2%H2SO4) from water leached residue belongs to shrinking unreacted core model, and it is controlled by internal diffusion. Therefore, non-additive roasting and additive roasting both can reduce the apparent reaction order and the acid consumption.
引文
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