D201离子交换树脂分离钒、磷、硅的应用基础研究
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摘要
钒是一种稀有高熔点金属,溶于酸或碱。浸出液中的钒常以五价的钒酸根阴离子形式存在,可与树脂上的阴离子交换基团相互交换,而与其它杂质分离。本文采用D201树脂吸附钒、磷、硅,并对其吸附性能和机理进行了研究。研究内容与研究结果如下:
单一元素水溶液体系中,D201树脂对钒、磷、硅的交换吸附受pH值、树脂用量、时间、温度因素的影响。pH=1.9-2.1时,树脂对钒的吸附最好,与其在溶液中的赋存状态有关,吸附平衡时间为11h;磷在pH=6.9-7.1时,吸附最好,吸附平衡时间30min;硅则是在pH=11.4-11.6时吸附最好,吸附平衡时间40min。升温对树脂吸附钒、磷有利,低温对吸附硅有利。
多元素混合模拟水溶液体系中,磷和硅对树脂吸附钒的影响不大,因此不需要预先除杂。在pH=1.9-2.1时,钒磷和钒硅的分离系数分别为48.33和106.77。
实际体系中动态吸附解吸试验表明,吸附时料液流速应≤2BV/h,解吸时流速应控制在2-3BV/h之间,5%NaOH+10%NaCl做解吸剂,能将D201树脂上的钒、磷、硅基本完全解吸。
热力学研究表明D201树脂对钒、磷、硅的吸附行为可用Langmuir或Freundlich等温方程描述。D201树脂对钒、磷、硅的吸附过程是自发过程(△G<0),熵变为正值(△S>0)。D201树脂吸附钒、磷是吸热过程(△H>0),吸附硅是放热过程(△H<0)。
动力学研究表明D201树脂对钒、磷、硅的吸附交换过程符合二级吸附交换动力学过程。动边界模型模拟及搅拌速度、树脂粒径试验表明D201树脂对钒、磷的吸附受微球扩散控制,对硅的吸附受微球扩散和大孔扩散联合控制。
Vanadium is a kind of rare and high melting point metal which can be dissolved in sour or alkali solution. In lixivium, vanadium is the form of vanadium radical which can be adsorbed and exchanged by the anion group in the resin and be separated with impurities. The paper was studied the adsorption behavior and mechanism of D201 resin for vanadium (V), phosphorus, silicon. Main conclusions were obtained as following:
In singular element system, effects of pH, resin amount, temperature and time on adsorption behavior were investigated. The best adsorption effect on vanadium could be obtained when pH was 1.9-2.1, since it's related with the condition of vanadium in solution. The best adsorption effect on phosphorus could be obtained when pH was 6.9-7.1 while silicon was pH11.4-11.6. The equilibrium time of vanadium was about 11h, phosphorus was 30min and silicon was 40min. Higher temperature were beneficial for the adsorption of vanadium and phosphorus while lower temperature was good for silicon.
There was little effect of phosphorus or silicon on the adsorption of vanadium in multi element system. The separation coefficient of vanadium and phosphorus was 48.33 and the separation coefficient of vanadium and silicon was 106.77 when pH was 1.9-2.1.
The results of the column dynamic adsorption experiments showed that the flow rate should be lower than 2BV/h. The suitable conditions for the desorption were 5%NaOH+10%NaCl as the eluent and 2-3BV/h flow rate.
Langmuir and Freundlich isotherms were both suitable for describing the adsorption process. The thermodynamic study showed that the adsorption of vanadium, phosphorus and silicon was spontaneous and the entropy was positive. The adsorption of vanadium, phosphorus was endothermal but silicon was exothermic.
A sencond-order adsorption-ion exchange kinetic equation was developed for the process, and the equation parameters were estimated, results indicated that the adsorption of vanadium and phosphorus were controlled by the diffusion through micro ball of macroporous resin and silicon was controlled by the diffusion through micro ball and macropore of macroporous resin.
单一元素水溶液体系中,D201树脂对钒、磷、硅的交换吸附受pH值、树脂用量、时间、温度因素的影响。pH=1.9-2.1时,树脂对钒的吸附最好,与其在溶液中的赋存状态有关,吸附平衡时间为11h;磷在pH=6.9-7.1时,吸附最好,吸附平衡时间30min;硅则是在pH=11.4-11.6时吸附最好,吸附平衡时间40min。升温对树脂吸附钒、磷有利,低温对吸附硅有利。
多元素混合模拟水溶液体系中,磷和硅对树脂吸附钒的影响不大,因此不需要预先除杂。在pH=1.9-2.1时,钒磷和钒硅的分离系数分别为48.33和106.77。
实际体系中动态吸附解吸试验表明,吸附时料液流速应≤2BV/h,解吸时流速应控制在2-3BV/h之间,5%NaOH+10%NaCl做解吸剂,能将D201树脂上的钒、磷、硅基本完全解吸。
热力学研究表明D201树脂对钒、磷、硅的吸附行为可用Langmuir或Freundlich等温方程描述。D201树脂对钒、磷、硅的吸附过程是自发过程(△G<0),熵变为正值(△S>0)。D201树脂吸附钒、磷是吸热过程(△H>0),吸附硅是放热过程(△H<0)。
动力学研究表明D201树脂对钒、磷、硅的吸附交换过程符合二级吸附交换动力学过程。动边界模型模拟及搅拌速度、树脂粒径试验表明D201树脂对钒、磷的吸附受微球扩散控制,对硅的吸附受微球扩散和大孔扩散联合控制。
Vanadium is a kind of rare and high melting point metal which can be dissolved in sour or alkali solution. In lixivium, vanadium is the form of vanadium radical which can be adsorbed and exchanged by the anion group in the resin and be separated with impurities. The paper was studied the adsorption behavior and mechanism of D201 resin for vanadium (V), phosphorus, silicon. Main conclusions were obtained as following:
In singular element system, effects of pH, resin amount, temperature and time on adsorption behavior were investigated. The best adsorption effect on vanadium could be obtained when pH was 1.9-2.1, since it's related with the condition of vanadium in solution. The best adsorption effect on phosphorus could be obtained when pH was 6.9-7.1 while silicon was pH11.4-11.6. The equilibrium time of vanadium was about 11h, phosphorus was 30min and silicon was 40min. Higher temperature were beneficial for the adsorption of vanadium and phosphorus while lower temperature was good for silicon.
There was little effect of phosphorus or silicon on the adsorption of vanadium in multi element system. The separation coefficient of vanadium and phosphorus was 48.33 and the separation coefficient of vanadium and silicon was 106.77 when pH was 1.9-2.1.
The results of the column dynamic adsorption experiments showed that the flow rate should be lower than 2BV/h. The suitable conditions for the desorption were 5%NaOH+10%NaCl as the eluent and 2-3BV/h flow rate.
Langmuir and Freundlich isotherms were both suitable for describing the adsorption process. The thermodynamic study showed that the adsorption of vanadium, phosphorus and silicon was spontaneous and the entropy was positive. The adsorption of vanadium, phosphorus was endothermal but silicon was exothermic.
A sencond-order adsorption-ion exchange kinetic equation was developed for the process, and the equation parameters were estimated, results indicated that the adsorption of vanadium and phosphorus were controlled by the diffusion through micro ball of macroporous resin and silicon was controlled by the diffusion through micro ball and macropore of macroporous resin.
引文
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