零价铁和赤铁矿去除污染水体中U（Ⅵ）的试验研究
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摘要
核工业生产中产生的高、中、低放废物对环境构成的威胁越来越受到重视,它们与医疗、科研、国防事业的核废物一起成为越来越严重的环境问题,尤其是铀矿冶中产生的U(Ⅵ)对地下水的污染。我国南方某大型铀尾矿库经30多年的运营,其中的放射性核素已对周围的地表水和地下水造成了不同程度的污染。本文采用零价铁法研究零价铁对溶液中的U(Ⅵ)在各种条件下的去除情况及其去除机理,并研究了其在反应过程中的主要副产物对溶液中的U(Ⅵ)去除效果。
本文研究了零价铁粉在不同pH、反应时间、温度等条件下对溶液中U(Ⅵ)的还原沉淀。结果表明,在酸性条件下,零价铁对溶液中U(Ⅵ)的固定效果较好,随着溶液pH的升高,相应的去除率也随之降低。在溶液初始pH=3时,反应2h,铁粉用量为2g时,去除率可达到98%以上。并探讨了温度对化学反应的影响,得出温度对化学反应速率的影响不大,其反应符合一级动力学反应方程。得出溶液中U(Ⅵ)的去除机理为零价铁对U(Ⅵ)的还原沉淀和零价铁腐蚀物对溶液中U(Ⅵ)的吸附沉淀共同作用。
研究了合成赤铁矿对U(Ⅵ)的吸附规律,考察了pH、平衡时间、温度以及共存的钙、镁离子等因素对吸附效果的影响。结果表明,合成赤铁矿对U(Ⅵ)的吸附在6h基本达到平衡,吸附量随着pH值增大而显著增大,当pH值达到7～8时,吸附效果最佳,吸附效果随温度的升高增加不明显。共存钙、镁离子几乎不影响U(Ⅵ)的吸附去除效果。赤铁矿对U(Ⅵ)的吸附符合Langmuir吸附等温式。温度从293K上升到318K时,饱和吸附量qm从3.36 mg·g~(-1)上升到3.54 mg·g~(-1)。U(Ⅵ)的吸附反应的?G0为负值,说明该吸附过程是自发的反应过程。利用准一级动力学方程、准二级动力学方程以及粒子扩散方程的数学模型检验了吸附过程的动力学性质,表明赤铁矿对U(Ⅵ)的吸附过程符合准二级反应动力学模型,计算给出了温度为293K时三个动力学方程的吸附速率常数K值。
Great attention has been paid to the threat of the highly radioactive and the low-level radioactive waste from nuclear industry and the radioactive waste has become a more and more serious problem with the waste from medical industry and research institutions. The uranium(Ⅵ) from uranium minings has caused the pollution of groundwater around. For example,the radioactive radionuclides have polluted the surface water and groundwater to varying degrees after thirty years’business of the large uranium mining in south china.This paper studied the removal effect of uranium(Ⅵ) in solution and its removal mechanism and also studied the removal effect of uranium(Ⅵ) in solution by the byproduct hemallite.
The removal rates of uranium(Ⅵ) in solution by zero-valent iron at different pH、reaction time and different temperatures are studied.The experiment results indicated that the removal effect is better when the pH of the solution is bellow 7 and the removal rate rised with the increase of the pH of the solution.The effect of temperature on the chemical reaction was also studied and the conclusion is the impact of temperature is weak.The reaction fitted pseudo-first-order kinetic model well. The removal mechanism of uranium(Ⅵ) was discussed and the immobilization of uranium(Ⅵ) was the reductive precipitation and adsorptive precipitation by the byproduct.
Hematite, a type of inorganic sorptive medium, was used for the removal of uranium(Ⅵ) from aqueous solutions. Variables of the batch experiments including solution pH, contact time, initial concentration, temperature ,Ca and Mg ions were studied. The adsorption capacities are strongly affected by solution pH, contact time and initial concentration. Higher pH favors higher uranium(Ⅵ) removal. It was also affected by temperature and Ca and Mg ions and the effect is weak. A two-stage kinetic behavior is observed in the adsorption of uranium(Ⅵ): very rapid initial adsorption in a few minutes, followed by a long period of a slower uptake. It is noted that an increase in temperature results in a higher uranium(Ⅵ) loading per unit weight of the sorbent.. The results indicated that adsorption of uranium by hematite had good efficiency, and the equilibrium time of adsorbing uranium(Ⅵ) was 6h.; The maximum adsorption capacity (qm) only increased from 3.36 mg·g~(-1) to 3.54 mg·g~(-1) when the temperature increased from 293K to 318K. The isothermal data are well fitted with both Langmuir and Freundlich equations, but the Langmuir isotherm fitted better than that of Freundlich. The pseudo-first-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were used to describe the kinetic data. The thermodynamic parameter, ?G0 were calculated. The negative ?G0 values of uranium(Ⅵ) at different temperatures confirmed the adsorption processes were spontaneous.
本文研究了零价铁粉在不同pH、反应时间、温度等条件下对溶液中U(Ⅵ)的还原沉淀。结果表明,在酸性条件下,零价铁对溶液中U(Ⅵ)的固定效果较好,随着溶液pH的升高,相应的去除率也随之降低。在溶液初始pH=3时,反应2h,铁粉用量为2g时,去除率可达到98%以上。并探讨了温度对化学反应的影响,得出温度对化学反应速率的影响不大,其反应符合一级动力学反应方程。得出溶液中U(Ⅵ)的去除机理为零价铁对U(Ⅵ)的还原沉淀和零价铁腐蚀物对溶液中U(Ⅵ)的吸附沉淀共同作用。
研究了合成赤铁矿对U(Ⅵ)的吸附规律,考察了pH、平衡时间、温度以及共存的钙、镁离子等因素对吸附效果的影响。结果表明,合成赤铁矿对U(Ⅵ)的吸附在6h基本达到平衡,吸附量随着pH值增大而显著增大,当pH值达到7～8时,吸附效果最佳,吸附效果随温度的升高增加不明显。共存钙、镁离子几乎不影响U(Ⅵ)的吸附去除效果。赤铁矿对U(Ⅵ)的吸附符合Langmuir吸附等温式。温度从293K上升到318K时,饱和吸附量qm从3.36 mg·g~(-1)上升到3.54 mg·g~(-1)。U(Ⅵ)的吸附反应的?G0为负值,说明该吸附过程是自发的反应过程。利用准一级动力学方程、准二级动力学方程以及粒子扩散方程的数学模型检验了吸附过程的动力学性质,表明赤铁矿对U(Ⅵ)的吸附过程符合准二级反应动力学模型,计算给出了温度为293K时三个动力学方程的吸附速率常数K值。
Great attention has been paid to the threat of the highly radioactive and the low-level radioactive waste from nuclear industry and the radioactive waste has become a more and more serious problem with the waste from medical industry and research institutions. The uranium(Ⅵ) from uranium minings has caused the pollution of groundwater around. For example,the radioactive radionuclides have polluted the surface water and groundwater to varying degrees after thirty years’business of the large uranium mining in south china.This paper studied the removal effect of uranium(Ⅵ) in solution and its removal mechanism and also studied the removal effect of uranium(Ⅵ) in solution by the byproduct hemallite.
The removal rates of uranium(Ⅵ) in solution by zero-valent iron at different pH、reaction time and different temperatures are studied.The experiment results indicated that the removal effect is better when the pH of the solution is bellow 7 and the removal rate rised with the increase of the pH of the solution.The effect of temperature on the chemical reaction was also studied and the conclusion is the impact of temperature is weak.The reaction fitted pseudo-first-order kinetic model well. The removal mechanism of uranium(Ⅵ) was discussed and the immobilization of uranium(Ⅵ) was the reductive precipitation and adsorptive precipitation by the byproduct.
Hematite, a type of inorganic sorptive medium, was used for the removal of uranium(Ⅵ) from aqueous solutions. Variables of the batch experiments including solution pH, contact time, initial concentration, temperature ,Ca and Mg ions were studied. The adsorption capacities are strongly affected by solution pH, contact time and initial concentration. Higher pH favors higher uranium(Ⅵ) removal. It was also affected by temperature and Ca and Mg ions and the effect is weak. A two-stage kinetic behavior is observed in the adsorption of uranium(Ⅵ): very rapid initial adsorption in a few minutes, followed by a long period of a slower uptake. It is noted that an increase in temperature results in a higher uranium(Ⅵ) loading per unit weight of the sorbent.. The results indicated that adsorption of uranium by hematite had good efficiency, and the equilibrium time of adsorbing uranium(Ⅵ) was 6h.; The maximum adsorption capacity (qm) only increased from 3.36 mg·g~(-1) to 3.54 mg·g~(-1) when the temperature increased from 293K to 318K. The isothermal data are well fitted with both Langmuir and Freundlich equations, but the Langmuir isotherm fitted better than that of Freundlich. The pseudo-first-order kinetic model, pseudo-second-order kinetic model and intraparticle diffusion model were used to describe the kinetic data. The thermodynamic parameter, ?G0 were calculated. The negative ?G0 values of uranium(Ⅵ) at different temperatures confirmed the adsorption processes were spontaneous.
引文
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