膨胀石墨的制备及其对金属离子去除性能的研究
摘要
膨胀石墨是一种多孔性材料,孔径范围广,总孔容大,在吸附方面有巨大的潜力。本文的目的主要是研究膨胀石墨对于几种代表性的金属离子的吸附性能,优化吸附条件,并且在实验数据的基础上进行数学分析和机理研究,为进一步提高膨胀石墨的吸附能力和应用范围提供理论依据和方向。此外,本文还制备了改性膨胀石墨,以提高膨胀石墨的吸附性能。
本文以青岛宏达购买的可膨胀石墨为原料采用微波膨胀法制备出膨胀石墨,通过BET方程和BJH法计算其比表面积、孔体积和孔径分布；采用扫描电子显微镜(SEM)和FT-IR红外分析仪观察了膨胀石墨的微观形貌结构以及膨胀石墨含有的官能团。
膨胀石墨吸附铅、铬、锡离子吸附实验结果表明：溶液pH是控制三种金属离子吸附过程的重要因素；当溶液呈中性或偏酸性时,铅溶液的初始浓度为300mg/L,吸附时间为300min时,膨胀石墨对含铅离子的吸附量达到63mg/g；当溶液在pH=3时,膨胀石墨对铬离子的吸附效果最好；当溶液呈偏酸性,锡溶液的初始浓度为300mg/L,吸附时间为120min时,膨胀石墨对锡离子的吸附量达到343mg/g。另外,分别采用Langmuir吸附等温线方程、Freundlich吸附等温线方程和Temkin吸附等温线方程对膨胀石墨吸附三种金属的实验数据进行拟合,结果表明Langmuir等温线方程能较好地描述三种金属离子在膨胀石墨上的吸附平衡,膨胀石墨吸附三种金属离子的Langmuir模型极限吸附容量分别为70.42mg/g,2.77mg/g,378.78mg/g。采用准一级、准二级、Elovich和Ritchie's-二阶吸附动力学模型分析了实验数据,发现准二级动力学模型能更好地描述吸附过程。
经过纳米氢氧化镁改性后的膨胀石墨对铅离子吸附的实验结果表明：对比原膨胀石墨,可以发现改性膨胀石墨能有效地吸附铅离子,其吸附量由原来的70mg/g提高到105mg/g。当初始pH值为4-6、含Pb(Ⅱ)废水初始浓度为100mg/L、改性膨胀石墨投加量为0.035g、吸附时间为120min,25℃条件下,含铅废水的去除率为98%左右。
采用Langmuir、Freundlich以及Temkin吸附等温模型对数据进行了拟合,发现Langmuir模型具有更好的线性相关性。分别采用准一级动力学模型、准二级、Elovich、Ritchie's-二阶动力学模型分析了实验数据,发现改性膨胀石墨吸附铅离子的整个过程能更好地符合准二级动力学模型。
Expanded graphite is a kind of poriferous material. It has a wide range of pore diameter and a great pore volum. So it has a great potential in practical use for a adsorption. The main objective of this research is to study the adsorption capability of expanded graphite against three kinds of metal ions and optimize the reaction condition. Based on the data aquired in experiments, some mathematical analysis is conducted and some theories are given to explain the experiment results. Furthemore, in order to improve the metal ion adsorption capability of expanded graphite, the expanded graphite is modified by applying relevant modifier.
Commercial expandable graphite (purchased from Qingdao Nanshu Hongda Graphite Co. Ltd, China) was directly placed into MicroWave oven.Then, the expanded graphite was prepared. For provide the material characterization, the BET equation and BJH method were used to calculate the specific surface area, pore volume and pore size distribution. The scan electric microscope (SEM) and FT-IR were used to investigate the morphology and chemistry structural characteristics.
The experimental results of Pb,Cr and Sn adsorption onto the expanded graphite showed that the pH value of solutions is the most important factor to the effect on the three kinds of metal ions adsorption capacity of expanded graphite.
Under the conditions of the initial pH:4-6,concentration of Pb(Ⅱ):300mg/L and the adsorption time:300min, the adsorption capacity could reach at 63mg/g. Under the condition of the initial pH of Cr(Ⅵ)=3, the expanded graphite reveals the highest adsorption capability for Cr solution. Under the conditions of the initial pH:2-3, concentration of Sn(Ⅱ):300mg/L and the adsorption time:120min, the adsorption capacity could reach at 343mg/g. Furthermore, the adsorption equilibrium data were fitted according to Langmuir, Freundlich and Temkin adsorption isotherms, respectively. The results show that the Langmuir isotherm can agree with the adsorption behavior of the three kinds of metal ions on expanded graphite. The calculated Langmuir limit adsorption capacities were 70.42mg/g,2.77mg/g and 378.78mg/g. The adsorption was analyzed using pseudo-first-order, pseudo-second-order, Elovich and Ritchie's kinetics models and the adsorption kinetics were found to follow pseudo-second-order kinetics model.
The experimental results of Pb adsorption onto the modified expanded graphite by loading Mg(OH)2 showed that the adsorption capacity increased greatly comparing the expanded graphite. The adsorption quantity could reach at 105mg/g from the original 70mg/g. Under the conditions of the initial pH:4-6,concentration of Pb(Ⅱ):300mg/L, dosage of the modified expanded graphite:0.035g and the adsorption time:120min, the removal rate could reach at 98%. The adsorption equilibrium data were fitted according to Langmuir, Freundlich and Temkin adsorption isotherms, respectively. The results show that the Langmuir isotherm can agree with the adsorption behavior of Pb on modified expanded graphite. The adsorption was analyzed using pseudo-first-order, pseudo-second-order, Elovich and Ritchie's kinetics models and the adsorption kinetics were found to follow pseudo-second-order kinetics model.
本文以青岛宏达购买的可膨胀石墨为原料采用微波膨胀法制备出膨胀石墨,通过BET方程和BJH法计算其比表面积、孔体积和孔径分布；采用扫描电子显微镜(SEM)和FT-IR红外分析仪观察了膨胀石墨的微观形貌结构以及膨胀石墨含有的官能团。
膨胀石墨吸附铅、铬、锡离子吸附实验结果表明：溶液pH是控制三种金属离子吸附过程的重要因素；当溶液呈中性或偏酸性时,铅溶液的初始浓度为300mg/L,吸附时间为300min时,膨胀石墨对含铅离子的吸附量达到63mg/g；当溶液在pH=3时,膨胀石墨对铬离子的吸附效果最好；当溶液呈偏酸性,锡溶液的初始浓度为300mg/L,吸附时间为120min时,膨胀石墨对锡离子的吸附量达到343mg/g。另外,分别采用Langmuir吸附等温线方程、Freundlich吸附等温线方程和Temkin吸附等温线方程对膨胀石墨吸附三种金属的实验数据进行拟合,结果表明Langmuir等温线方程能较好地描述三种金属离子在膨胀石墨上的吸附平衡,膨胀石墨吸附三种金属离子的Langmuir模型极限吸附容量分别为70.42mg/g,2.77mg/g,378.78mg/g。采用准一级、准二级、Elovich和Ritchie's-二阶吸附动力学模型分析了实验数据,发现准二级动力学模型能更好地描述吸附过程。
经过纳米氢氧化镁改性后的膨胀石墨对铅离子吸附的实验结果表明：对比原膨胀石墨,可以发现改性膨胀石墨能有效地吸附铅离子,其吸附量由原来的70mg/g提高到105mg/g。当初始pH值为4-6、含Pb(Ⅱ)废水初始浓度为100mg/L、改性膨胀石墨投加量为0.035g、吸附时间为120min,25℃条件下,含铅废水的去除率为98%左右。
采用Langmuir、Freundlich以及Temkin吸附等温模型对数据进行了拟合,发现Langmuir模型具有更好的线性相关性。分别采用准一级动力学模型、准二级、Elovich、Ritchie's-二阶动力学模型分析了实验数据,发现改性膨胀石墨吸附铅离子的整个过程能更好地符合准二级动力学模型。
Expanded graphite is a kind of poriferous material. It has a wide range of pore diameter and a great pore volum. So it has a great potential in practical use for a adsorption. The main objective of this research is to study the adsorption capability of expanded graphite against three kinds of metal ions and optimize the reaction condition. Based on the data aquired in experiments, some mathematical analysis is conducted and some theories are given to explain the experiment results. Furthemore, in order to improve the metal ion adsorption capability of expanded graphite, the expanded graphite is modified by applying relevant modifier.
Commercial expandable graphite (purchased from Qingdao Nanshu Hongda Graphite Co. Ltd, China) was directly placed into MicroWave oven.Then, the expanded graphite was prepared. For provide the material characterization, the BET equation and BJH method were used to calculate the specific surface area, pore volume and pore size distribution. The scan electric microscope (SEM) and FT-IR were used to investigate the morphology and chemistry structural characteristics.
The experimental results of Pb,Cr and Sn adsorption onto the expanded graphite showed that the pH value of solutions is the most important factor to the effect on the three kinds of metal ions adsorption capacity of expanded graphite.
Under the conditions of the initial pH:4-6,concentration of Pb(Ⅱ):300mg/L and the adsorption time:300min, the adsorption capacity could reach at 63mg/g. Under the condition of the initial pH of Cr(Ⅵ)=3, the expanded graphite reveals the highest adsorption capability for Cr solution. Under the conditions of the initial pH:2-3, concentration of Sn(Ⅱ):300mg/L and the adsorption time:120min, the adsorption capacity could reach at 343mg/g. Furthermore, the adsorption equilibrium data were fitted according to Langmuir, Freundlich and Temkin adsorption isotherms, respectively. The results show that the Langmuir isotherm can agree with the adsorption behavior of the three kinds of metal ions on expanded graphite. The calculated Langmuir limit adsorption capacities were 70.42mg/g,2.77mg/g and 378.78mg/g. The adsorption was analyzed using pseudo-first-order, pseudo-second-order, Elovich and Ritchie's kinetics models and the adsorption kinetics were found to follow pseudo-second-order kinetics model.
The experimental results of Pb adsorption onto the modified expanded graphite by loading Mg(OH)2 showed that the adsorption capacity increased greatly comparing the expanded graphite. The adsorption quantity could reach at 105mg/g from the original 70mg/g. Under the conditions of the initial pH:4-6,concentration of Pb(Ⅱ):300mg/L, dosage of the modified expanded graphite:0.035g and the adsorption time:120min, the removal rate could reach at 98%. The adsorption equilibrium data were fitted according to Langmuir, Freundlich and Temkin adsorption isotherms, respectively. The results show that the Langmuir isotherm can agree with the adsorption behavior of Pb on modified expanded graphite. The adsorption was analyzed using pseudo-first-order, pseudo-second-order, Elovich and Ritchie's kinetics models and the adsorption kinetics were found to follow pseudo-second-order kinetics model.
引文
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