摘要
固-液界面的吸附现象是自然界中普遍存在、最为重要的现象之一,也是环境化学领域的重要研究内容之一。因为污染物在固-液界面(如土壤-水界面)的吸附-脱附行为对污染物的形态分布、迁移转化和归宿等均具重要影响；另外,在环境治理工程中,所采用的技术也多与吸附过程有关。因此,科学认识污染物的吸附-脱附行为,是研究环境污染形成机理、探索有效防治途径的重要基础。
吸附热力学和动力学是固-液界面吸附研究中的基础内容。前期,在吸附-脱附平衡研究中,发现其吸附等温线随吸附剂浓度(Cs)增大而降低,即其平衡常数与Cs有关,这似乎与热力学平衡理论相悖,称为“固体效应”或“吸附剂浓度效应”(Cs-effect)。虽然已提出了多种吸附剂浓度效应模型,如“溶质络合模型”、“粒子间相互作用模型”、“亚稳平衡态吸附理论”、“絮凝模型”、“幂函数(Freundlich型)模型”和“四组分吸附模型”等,或因适用范围有限(只能描述个别实验结果),或因模型参数不能实验测定,目前均未被广泛认可,对Cs-effect产生的本质原因也还缺乏合理或公认的解释。另外,在吸附动力学中也存在Cs-effect,即吸附速率常数与Cs有关,目前还未见相关固体效应模型的研究报道。由于现有的理论模型不能准确地描述或预测Cs-effect,给固-液界面吸附的理论发展和技术应用带来一系列问题。其一,因对吸附现象物理过程的本质缺乏科学认识,将影响模型构建,妨碍理论的发展；其二,因模型参数的不确定性,将给环境治理工程的设计造成困难,甚至使整体方案产生缺陷。鉴于此,本文对固-液界面吸附的Cs-effect现象进行了研究,探讨了相关机理,构建了固体效应模型(包括热力学模型和动力学模型),以期加深对固-液界面吸附现象的科学认识,为环境治理(如废水处理和土壤修复等)工程的设计提供理论依据。
本论文主要研究内容及结论如下：
(1)以高岭土、层状双金属氢氧化物(LDHs)和EDTA插层LDH(EDTA-LDH)纳米杂化物等为模型吸附剂,以重金属离子Pb(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)和Hg(Ⅱ)为模型吸附质,实验研究了固-液界面的吸附热力学(等温线)和动力学,结果表明均存在明显的Cs-effect。
(2)采用传统的吸附等温方程(Langmuir和Freundlich等温式)和动力学方程(准一级和准二级方程)对吸附实验数据进行了模拟,结果表明可准确地描述给定Cs下的吸附行为,但不能描述或预测Cs-effect。或者说,所拟合得到的吸附平衡常数和速率常数皆与Cs有关,这样在给定Cs下得到的常数不能用于预测其它Cs下的吸附行为。
(3)结合文献报道和本实验结果分析,作者认为Gs-effect是一个客观存在的自然现象,缘于吸附剂颗粒间的相互作用,包括碰撞、粘附、静电力和van de Waals力作用等。为解释和描述Gs-effect,提出了“表面组分活度模型”(Surface Component Activity Model, S CA模型),假设吸附剂表面组分即吸附位和吸附质的活度系数不等于1,而分别为吸附剂浓度(Cs)和吸附量(Г)的函数。这是因为实际吸附体系中,同组分间即吸附剂颗粒之间和吸附质分子(或离子)之间均存在相互作用,使其偏离于理想吸附体系；和溶液体系一样,将热力学平衡定律应用于实际吸附体系时,应用活度代替浓度进行校正。传统吸附模型未考虑同组分间的相互作用,故不能描述或预测实际吸附体系中的Cs-effect.
(4)基于SCA模型,分别推导出了与吸附剂浓度有关的Langmuir、Freundlich等温式和分配系数方程,简记为Langmuir-SCA、Freundlich-SCA等温式和SCA-分配系数方程,相关的平衡常数皆与Cs无关；因此,在给定Cs下得到的平衡常数,可用于预测其它Cs下的吸附平衡行为。
(5)基于SCA模型,分别推导出了与吸附剂浓度有关的准一级动力学和准二级动力学方程,简记为SCA-准一级和SCA-准二级动力学方程,相关的速率常数皆与Cs无关；因此,在给定Cs下得到的速率常数,可用于预测其它Cs下的吸附动力学行为。
(6)假设并优化出表面吸附位活度系数(fH2Os)与Cs的最佳函数关系为指数形式,即fH2Os=exp(-γCsα),其中γ和α为常数；推导出了fH2Os与吸附参数间的理论关系式,即由吸附数据可拟合得到fH2Os值,为SCA模型方程的实际应用奠定了基础。
(7)利用本文所得和文献报道吸附实验数据,对SCA模型方程进行了验证,并与现有固体效应模型方程进行了对比,结果表明SCA模型方程可更好地描述Cs-effect实验结果。
The adsorption phenomenon at solid-liquid interface is one of the most universal and important behaviors occurring in nature and one of the important research contents in environmental chemistry. It is because the adsorption-desorption behaviors of the pollutants at solid-liquid interface (such as soil-liquid interface) have a major influence on distribution, migration and transformation of the pollutants. In addition, the technology used in the environmental engineering project is mostly related to the adsorption process. Therefore, scientific knowledge of the pollutants adsorption-desorption behaviors is an important foundation for the research of environmental pollution formation mechanism and the exploration of the effective pollution preventive approaches.
The adsorption thermodynamics and kinetics are the basic contents of solid-liquid interface adsorption studies. Earlier, it has been observed in the adsorption-desorption equilibrium studies that adsorption isotherms decline with the sorbent concentration (Cs) increases, i.e., the adsorption equilibrium constants vary with Cs. It was described as "solids effect" or "sorbent concentration effect"(Cs-effect). This seems to contradict the thermodynamic equilibrium theory. Many solids effect models have been proposed, such as the solute complexation model, the particle interaction model, the metastable-equilibrium adsorption theory, the flocculation model, the power function (Freundlich-like) model, and the four components adsorption model. But these models have not been widely accepted because the application scope is limited or the model parameters cannot be experimentally measured. The essential reason for Cs-effect still lacks reasonable or accepted explanation. The Cs-effect also occurs in adsorption kinetics at solid-liquid interfaces, where adsorption rate constants vary with Cs. The existing theoretical models cannot accurately describe or predict Cs-effect. This brought a series of problems in the development of solid-liquid interface adsorption theory and the technology application. First, the lack of scientific knowledge about the physical process nature of the adsorption phenomena will affect the model construction and hinder the theory development; second, the uncertainty of model parameters creates difficulties in environmental treatment project and the engineering design. In view of this, the Cs-effect phenomenon on the soil-liquid interface adsorption was studied. The related mechanism was discussed. The Cs-effect model (including thermodynamic and kinetic model) was constructed. These would enhance our scientific knowledge of the solid-liquid interface adsorption phenomena and provide the theory basis for the design of environmental treament engineering (such as wastewater treatment and soil remediation).
The main research contents and conclusions are listed as follows:
(1) The adsorption thermodynamics (isotherms) and kinetics on solid-liquid interface adsorption were studied. The model sorbents include kaolinite, the layered double hydroxides (LDHs) and EDTA intercalated nanocomposite (EDTA-LDH). The model adsorbates include Pb(II), Cu(II), Zn(II) and Hg(II). The results showed that there were obvious Cs-effect in adsorption thermodynamic and kinetic process.
(2) The adsorption data were fitted with the classical isotherm equations (Langmuir and Freundlich equation) and the kinetic equations (pseudo-first-order and pseudo-second-order kinetic equation). It was found that the classical equations could adequately describe the adsorption phenomenon for a given Cs value but could not describe or predict Cs-effect. In other words, the adsorption equilibrium constants and the rate constants vary with Cs. The constants obtained at given Cs cannot predict the adsorption behavior at other Cs.
(3) Combining with the analysis of the literature and the experimental results, the author believed that the Cs-effect was an objective phenomenon due to the sorbent particle-particle interactions (including collision, adhesion, electrostatic force and Van de Waals force etc.). In order to explain and describe the Cs-effect, a surface component activity (SCA) model was proposed. The SCA model suggests that the surface component (adsorption site or adsorbed solute) activity coefficients are not equal to unity but are the functions of Cs and the adsorption amount (Γ) respectively. This is because the interaction existed in the same component (the sorbent particles and the adsorbate molecules) makes a real adsorption system deviating from an ideal one. When the thermodynamic equilibrium law applied to the real adsorption system, it should use activity instead of concentration to correct as same as the solution system. As the classical adsorption models do not consider the same component interaction, they cannot describe or predict the Cs-effect in the real adsorption system.
(4) Based on the SCA model, the Cs-dependent Langmuir equation, the Cs-dependent Freundlich equation and the Cs-dependent partition coefficient equation, denoted as Langmuir-SCA, Freundlich-SCA and the SCA-partition coefficient equation, were derived. The related equilibrium constants are independent of Cs. Therefore, the equilibrium constants obtained at given Cs can predict the adsorption equilibrium behavior at other Cs.
(5) Based on the SCA model, the Cs-dependent first-order kinetic equation and the Cs-dependent second-order kinetic equation, denoted as SCA-first-order and SCA-second-order kinetic equation, were derived. The related rate constants are independent of Cs. Therefore, the rate constants obtained at given Cs can predict the adsorption kinetic behavior at other Cs.
(6) The best supposed and optimized function of the adsorption sites activity coefficient (fH2Os) and Cs is exponential form, i. e., fH2Os=exp(-γCsα). The theoretical relationship between fH2Os o and adsorption parameters was derived. The value of fH2Os can be obtained by adsorption data. This lays the foundation for the practical application of the SCA model equation.
(7) The SCA model equations were examined using the adsorption experimental data obtained in this paper and literature and compared with the existing Cs-effect model equations. The results showed that the SCA model equations can better describe the experimental results of Cs-effect.
引文
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