摘要
硅藻土作为一种粘土矿物,具备吸附能力强、来源丰富、价格合理等特点,是重金属离子的良好吸附材料,但硅藻土存在一定的理化构造缺陷,严重限制了其吸附性能的发挥。因此有必要对硅藻土实施深度物化改性,改善其理化特性,提高其应用水平。柱撑作为一种先进改性技术能够有效提高层状结构物质的层间距、稳定性、比表面积及表面活性等特性,但将柱撑改性技术应用于硅藻土改性的研究尚未见报道,故研究硅藻土柱撑改性具有非常重要的意义。本论文采用聚羟基铝对硅藻土实施了深度化学改性,并将改性前后的硅藻土用于吸附重金属离子Pb2+、Cd2+,研究了硅藻土聚羟基铝柱撑改性工艺及条件,分析了改性前后硅藻土吸附性能的变化,探究了硅藻土聚羟基铝柱撑改性机理。主要研究结果如下：
(1)通过静态吸附实验研究发现,离子初始浓度、硅藻土投加量、pH值、温度、震荡时间是硅藻土吸附性能主要影响因素；硅藻土对Pb2+、Cd2+的吸附量随着离子初始浓度的提高而增大,随着硅藻土投加量的增加而先增大后减小,随着pH值的提高而增大,随着震荡时间的延长而先增大后趋于平衡,随着温度的升高而先增大后减小；各因素对硅藻土吸附Pb2+、Cd2+的影响程度排序分别为：初始浓度>pH值>投加量>温度>震荡时间、初始浓度>投加量>pH值>震荡时间>温度。
(2)通过吸附条件优化实验发现,聚羟基铝改性硅藻土对Cd2+、Pb2+的最优吸附条件均为：离子初始浓度为1500mg/L,硅藻土投加量为50g/L, pH值为8,温度为25℃,震荡时间120min。
(3)通过柱撑改性实验研究发现,针对吸附模拟废水中的Cd2+,硅藻土聚羟基铝柱撑最佳改性条件为：柱化液浓度为0.2mol/L、[Al]/土摩尔比为10mmol/g、反应温度为60℃、反应时间为120min、活化温度为105℃、活化时间为16h；针对吸附模拟废水中的Pb2+,硅藻土聚羟基铝柱撑最佳改性条件为：柱化液浓度为0.1mol/L、[Al]/土摩尔比为10mmol/g、反应温度为60℃、反应时间为120min、活化温度为105℃、活化时间为16h。
(4)通过吸附性能比较研究发现,在最优吸附条件下,硅藻土原土对Cd2+的饱和吸附量为6.9mg/g,去除率为34.5%,柱撑改性土对Cd2+的饱和吸附量为10.05mg/g,去除率为50.3%,改性土与原土相比饱和吸附量与去除效率分别提高了39.9%和15.8%,改性效果明显(P<0.05)；硅藻土原土对Pb2+的饱和吸附量为10.39mg/g,去除率为52.0%,柱撑改性土对Pb2+的饱和吸附量为13.62mg/g,去除率为67.9%,改性土与原土相比饱和吸附量与去除效率分别提高了31.1%和15.9%,改性效果相比对Cd2+的吸附要差。
(5)通过电子扫描电镜(SEM)研究发现,改性土与原土相比,表面要光滑,杂质较少；聚羟基铝改性硅藻土以分子插入硅藻土的层间距中,改善了硅藻土的结构,提高了聚羟基铝改性硅藻土在重金属废水处理中的去除效果。通过改性机理研究发现,硅藻土吸附性能的提高主要是由于经聚羟基铝改性后,聚羟基铝颗粒进入硅藻土层间,与硅藻土层间的可交换性阳离子进行交换,为重金属离子Cd2+、Pb2+提供更多的吸附位点。
Diatomite is a nature soil mineral with many excellent advantages, such as high adsorption ability, wide source and reasonable price, so it is widely used to adsorb heavy metal ions. But its adsorption ability is limited by some physical and chemical structure. In order to improve its physicochemical properties and application level, it is necessary to do research in modification of diatomite. Pillared agent, as an advanced modification technology, is a new tool which can improve the lamellar spacing, stability, special surface area and surface activity of layered materials. It is of importance to modify diatomite with pillared agent. In this article, we adopt poly-hydroxyl aluminum as pillared agent to do this chemical modification experiment. After adsorbing Pb2+, Cd2with diatomite and modified diatomite respectively, modification mechanism and technological conditions are studied in this paper. Conclusions can be got as following:
(1) Static adsorption experiments reveal that the adsorption ability of diatomite depends closely upon initial concentration of heavy metal ion, the dosage of diatomite, temperature, and adsorption time. Diatomite adsorption amount is increased with the increase of initial concentration of heavy metal ion, adsorption time and pH. While the adsorption amount increase at first and then reduce with the ascension of temperature and the dosage of diatomite. The importance of adsorption factors are shown as follows: initial concentration of heavy metal ion> pH> the dosage of diatomite>temperature> adsorption time.
(2) The experiment of optimum modification conditions reveals that when the initial concentration of Cd2+is1500mg/L, the dosage of diatomite is50g/L, pH is8, temperature is25℃and adsorption time is120min, both the adsorption of Cd2+and Pb2+get the optimum condition.
(3) Pillared modification experiments reveal:when to adsorb Cd2+, the optimum modified conditions of diatomite is that the concentration of pillared liquid is0.2mol/L, molar ratio of [Al]/soil islOmmol/g, reaction temperature is60℃, reaction time is120min, activation temperature is105℃and activation time is16h. When to adsorb Pb2+, the optimum modified conditions of diatomite is that the concentration of pillared liquid is0.1mol/L, molar ratio of [Al]/soil islOmmol/g, reaction temperature is60℃, reaction time is120min, activation temperature is105℃and activation time is16h.
(4) Through comparing the adsorption performance before and after modification, the study found that: when to adsorb Cd2+, the saturation absorptive capacity of diatomite is6.9mg/g and the removal rate is34.5%, while the saturation absorptive capacity of modified diatomite is10.05mg/g and the removal rate is50.3%, so the saturation absorptive capacity and removal rate of modified diatomite is greater than diatomite. When to adsorb Pb2+, the saturation absorptive capacity of diatomite is10.39mg/g and the removal rate is67.9%, while the saturation absorptive capacity of modified diatomite is13.62mg/g and the removal rate is67.9%, so the saturation absorptive capacity and removal rate of modified diatomite is greater than diatomite.
(5) SEM experiments reveal that: compared with original diatomite, modified diatomite has more smooth surface and less impurity. In order to provide more adsorption sites for Cd2+and Pb2+, the poly-hydroxyl aluminum particles enter into layers of diatomite and then exchange with exchangeable cations. That is why the adsorption ability of diatomite is improved after modifying with poly-hydroxyl aluminum.
引文
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