尾矿重金属淋溶污染及其抑制技术研究
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摘要
广东大宝山尾矿造成的重金属污染严重影响了矿区周围的生态环境,目前对矿区的重金属污染还未采取有效地控制方法。本文以大宝山尾矿为研究对象,对其进行分析,并在模拟酸雨条件下进行淋溶实验,研究了尾矿释放重金属的规律及动力学。此外,本文以三乙烯四胺、蒙脱石及二者制备成的复合体作为抑制剂,研究其对尾矿重金属释放的抑制作用。通过对抑制剂及抑制剂-重金属复合体的表征研究抑制剂的作用机理。论文的主要结论如下:
1.大宝山尾矿主要元素是Fe、Si、Al,S含量很少;主要矿物是石英、铅矾、铁矾和三水铝石;尾矿重金属含量很高;重金属主要以残渣态及硫化物态存在;尾矿的pH值很低。
2.模拟酸雨淋溶尾矿的淋滤液pH值维持在2.35~2.58范围,电导率很高且逐渐减小;Cu、Zn、Cd及Mn的释放过程均可分为快速释放及慢速释放两个阶段,Pb在释放过程中释放速率变化不大。重金属累计释放量大小为Mn>Cu>Zn> Cd> Pb。随着酸雨pH值的降低,淋滤液pH值降低,电导率升高,重金属释放量增大。5种重金属的释放量受酸雨pH值影响的程度为Pb>Mn> Zn> Cd >Cu,重金属的淋溶强度为Mn>Cu > Cd > Zn >Pb。Cu、Zn、Cd及Mn的释放可用准二级动力学方程及Elovich方程很好的拟合,准二级动力学方程更优;Pb的释放可用双常数方程和零级动力学方程很好的拟合。
3.三乙烯四胺/蒙脱石复合体的表征显示,三乙烯四胺插层到了蒙脱石的层间。抑制剂对5种重金属释放的抑制效果相比较,三乙烯四胺/蒙脱石复合体的效果均最好。在pH 3.0或40℃条件下,复合体也可保持较高的抑制率。随抑制剂用量的增加,重金属的抑制率升高。三乙烯四胺/蒙脱石复合体及蒙脱石对重金属的吸附很迅速,除了Mn在复合体上的吸附。复合体上重金属的解吸率普遍低于蒙脱石上的解吸率,除了Cu。
4.三乙烯四胺/蒙脱石复合体对5种重金属的吸附均可用Langmuir方程很好的拟合,蒙脱石对Cu和Pb的吸附,用Langmuir方程拟合较好,而对Zn、Cd及Mn的吸附,用Freundlich方程拟合较好。三乙烯四胺/蒙脱石复合体及蒙脱石对5种重金属的吸附均可用准一级动力学方程及准二级动力学方程很好的拟合,而准二级动力学方程拟合效果最好。抑制剂-重金属复合体的表征显示抑制剂与重金属发生了吸附作用,而复合体与重金属除了吸附作用,还发生了配位作用。三乙烯四胺/蒙脱石复合体作为抑制剂,汲取了三乙烯四胺及蒙脱石的优点,达到了最好的抑制效果。
Ecosystem has been badly contaminated by heavy metals from tailings near Dabaoshan mine, Guang dong province. There has been no effective control method for heavy metal pollution in the mining area currently. In this paper, the tailings collected from Da Baoshan Mine are as research objects. Analysis of their composition and leaching expriments were conducted to study the release properties and kinetics of heavy metals. And in this paper, Triethylenetetramine, Montmorillonite and Triethylenetetramine-montmorillonite complexes are as inhibitors to inactivate heavy metals in the tailings. The impact of inhibitors on heavy metals was studied. The inhibitors and inhibitor-heavy metal complexes were tested by X-ray diffraction, infrared spectrum, thermo gravimetry, specific surface area analyzer and scaning electron microscope. And the reaction mechanism of the inhibitors was also researched in this paper. The conclusions are as follows:
1. The tailings mainly have the elements of Fe, Si and Al. The content of S is very low. The main minerals in the tailings are quartz, lead alum, iron alum and gibbsite. The content of heavy metals in the tailings is high,which exist mainly in residue and sulfide. The tailings have a very low pH level.
2. The pH of the leachates by leaching tailings with simulated acid rain ranged from 2.35~2.58, the conductivities of the leachates were high in the initial leaching stage and decreased gradually. Cu, Zn, Cd and Mn were similar in release progress, which could be divided into two stages, namely a fast leaching stage and a slow leaching stage. The release rate of Pb in the whole progress was relatively stable. The accumulative amount of heavy metals in the decreasing order was of Mn>Cu>Zn> Cd> Pb. With the pH of simulated acid rain decreasing, the pH of the leachates decreased, the conductivities of the leachates and the accumulative amount of heavy metals increased. The effect of the pH of simulated acid rain on the release of heavy metals in the decreasing order was of Pb>Mn> Zn> Cd >Cu. The leaching intensity of heavy metals in the decreasing order was of Mn >Cu > Cd > Zn > Pb . The kinetics of Cu, Zn, Cd and Mn could be properly described by Pseudo-second-order kinetic equation and Elovich equation, but the former was better. The kinetics of Pb could be properly described both by Two-constant equation and Pseudo-zero-order kinetic equation.
3. Several tests of Triethylenetetramine-montmorillonite complexes indicated that Triethylenetetramine had inserted into the interlayer of montmorillonite. The suppression of Triethylenetetramine-montmorillonite complexes on the release of heavy metals was the best of three inhibitors. Triethylenetetramine-montmorillonite complexes could keep the ?suppression ratio of heavy metals high even if at pH3.0 or at the temperature of 40℃. The suppression ratio of heavy metals increased with the dosage of treatments increasing. The sorption of heavy metals on Triethylenetetramine-montmorillonite complexes and montmorillonite was rapid except the adsorption of Mn on Triethylenetetramine-montmorillonite complexes. The desorption amount of heavy metals on Triethylenetetramine-montmorillonite complexes was mostly lower than the desorption amount of heavy metals on montmorillonite except Cu.
4. The adsorption of heavy metals on Triethylenetetramine-montmorillonite complexes fits Langmuir adsorption isotherm. The adsorption of Cu and Pb on montmorillonite fits Langmuir adsorption isotherm, but the adsorption of Zn, Cd and Mn fits Freundlich adsorption isotherm. The kinetics of the adsorption of heavy metals on Triethylenetetramine-montmorillonite complexes and montmorillonite can be properly described by Pseudo-first-order kinetic equation and Pseudo-second-order kinetic equation, but the latter is better. The tests of treatment-metal complexes indicated that adsorption happened between heavy metals and inhibitors.Besides adsorption, coordination reaction was produced by Hydroxyl or amino on the Triethylenetetramine-montmorillonite complexes and heavy metals.Triethylenetetramine-montmorillonite complexes have merits of both Triethylenetetramine and montmorillonite. Its suppression achieves the best results.
1.大宝山尾矿主要元素是Fe、Si、Al,S含量很少;主要矿物是石英、铅矾、铁矾和三水铝石;尾矿重金属含量很高;重金属主要以残渣态及硫化物态存在;尾矿的pH值很低。
2.模拟酸雨淋溶尾矿的淋滤液pH值维持在2.35~2.58范围,电导率很高且逐渐减小;Cu、Zn、Cd及Mn的释放过程均可分为快速释放及慢速释放两个阶段,Pb在释放过程中释放速率变化不大。重金属累计释放量大小为Mn>Cu>Zn> Cd> Pb。随着酸雨pH值的降低,淋滤液pH值降低,电导率升高,重金属释放量增大。5种重金属的释放量受酸雨pH值影响的程度为Pb>Mn> Zn> Cd >Cu,重金属的淋溶强度为Mn>Cu > Cd > Zn >Pb。Cu、Zn、Cd及Mn的释放可用准二级动力学方程及Elovich方程很好的拟合,准二级动力学方程更优;Pb的释放可用双常数方程和零级动力学方程很好的拟合。
3.三乙烯四胺/蒙脱石复合体的表征显示,三乙烯四胺插层到了蒙脱石的层间。抑制剂对5种重金属释放的抑制效果相比较,三乙烯四胺/蒙脱石复合体的效果均最好。在pH 3.0或40℃条件下,复合体也可保持较高的抑制率。随抑制剂用量的增加,重金属的抑制率升高。三乙烯四胺/蒙脱石复合体及蒙脱石对重金属的吸附很迅速,除了Mn在复合体上的吸附。复合体上重金属的解吸率普遍低于蒙脱石上的解吸率,除了Cu。
4.三乙烯四胺/蒙脱石复合体对5种重金属的吸附均可用Langmuir方程很好的拟合,蒙脱石对Cu和Pb的吸附,用Langmuir方程拟合较好,而对Zn、Cd及Mn的吸附,用Freundlich方程拟合较好。三乙烯四胺/蒙脱石复合体及蒙脱石对5种重金属的吸附均可用准一级动力学方程及准二级动力学方程很好的拟合,而准二级动力学方程拟合效果最好。抑制剂-重金属复合体的表征显示抑制剂与重金属发生了吸附作用,而复合体与重金属除了吸附作用,还发生了配位作用。三乙烯四胺/蒙脱石复合体作为抑制剂,汲取了三乙烯四胺及蒙脱石的优点,达到了最好的抑制效果。
Ecosystem has been badly contaminated by heavy metals from tailings near Dabaoshan mine, Guang dong province. There has been no effective control method for heavy metal pollution in the mining area currently. In this paper, the tailings collected from Da Baoshan Mine are as research objects. Analysis of their composition and leaching expriments were conducted to study the release properties and kinetics of heavy metals. And in this paper, Triethylenetetramine, Montmorillonite and Triethylenetetramine-montmorillonite complexes are as inhibitors to inactivate heavy metals in the tailings. The impact of inhibitors on heavy metals was studied. The inhibitors and inhibitor-heavy metal complexes were tested by X-ray diffraction, infrared spectrum, thermo gravimetry, specific surface area analyzer and scaning electron microscope. And the reaction mechanism of the inhibitors was also researched in this paper. The conclusions are as follows:
1. The tailings mainly have the elements of Fe, Si and Al. The content of S is very low. The main minerals in the tailings are quartz, lead alum, iron alum and gibbsite. The content of heavy metals in the tailings is high,which exist mainly in residue and sulfide. The tailings have a very low pH level.
2. The pH of the leachates by leaching tailings with simulated acid rain ranged from 2.35~2.58, the conductivities of the leachates were high in the initial leaching stage and decreased gradually. Cu, Zn, Cd and Mn were similar in release progress, which could be divided into two stages, namely a fast leaching stage and a slow leaching stage. The release rate of Pb in the whole progress was relatively stable. The accumulative amount of heavy metals in the decreasing order was of Mn>Cu>Zn> Cd> Pb. With the pH of simulated acid rain decreasing, the pH of the leachates decreased, the conductivities of the leachates and the accumulative amount of heavy metals increased. The effect of the pH of simulated acid rain on the release of heavy metals in the decreasing order was of Pb>Mn> Zn> Cd >Cu. The leaching intensity of heavy metals in the decreasing order was of Mn >Cu > Cd > Zn > Pb . The kinetics of Cu, Zn, Cd and Mn could be properly described by Pseudo-second-order kinetic equation and Elovich equation, but the former was better. The kinetics of Pb could be properly described both by Two-constant equation and Pseudo-zero-order kinetic equation.
3. Several tests of Triethylenetetramine-montmorillonite complexes indicated that Triethylenetetramine had inserted into the interlayer of montmorillonite. The suppression of Triethylenetetramine-montmorillonite complexes on the release of heavy metals was the best of three inhibitors. Triethylenetetramine-montmorillonite complexes could keep the ?suppression ratio of heavy metals high even if at pH3.0 or at the temperature of 40℃. The suppression ratio of heavy metals increased with the dosage of treatments increasing. The sorption of heavy metals on Triethylenetetramine-montmorillonite complexes and montmorillonite was rapid except the adsorption of Mn on Triethylenetetramine-montmorillonite complexes. The desorption amount of heavy metals on Triethylenetetramine-montmorillonite complexes was mostly lower than the desorption amount of heavy metals on montmorillonite except Cu.
4. The adsorption of heavy metals on Triethylenetetramine-montmorillonite complexes fits Langmuir adsorption isotherm. The adsorption of Cu and Pb on montmorillonite fits Langmuir adsorption isotherm, but the adsorption of Zn, Cd and Mn fits Freundlich adsorption isotherm. The kinetics of the adsorption of heavy metals on Triethylenetetramine-montmorillonite complexes and montmorillonite can be properly described by Pseudo-first-order kinetic equation and Pseudo-second-order kinetic equation, but the latter is better. The tests of treatment-metal complexes indicated that adsorption happened between heavy metals and inhibitors.Besides adsorption, coordination reaction was produced by Hydroxyl or amino on the Triethylenetetramine-montmorillonite complexes and heavy metals.Triethylenetetramine-montmorillonite complexes have merits of both Triethylenetetramine and montmorillonite. Its suppression achieves the best results.
引文
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