【摘要】 分子识别技术（MRT）是当今先进的分离技术，MRT分离铂族金属具有工艺流程短、回收率高、周期短等优点，越来越备受关注。本文对3种MRT材料（SuperLig?2,SuperLig?95和SuperLig?190；分别简称为M1,M2和M3）吸附铂族金属动力学及热力学进行了研究，结果表明，M1材料吸附PdCl₄^2-，M2材料吸附PtCl₄^2-，M3材料吸附RhCl₆^2-均符合准二级动力学模型，Pd,Pt和Rh的吸附均符合Langmuir模型；3种材料吸附速率大小顺序为ν_Pd>ν_Pt>ν_Rh，饱和吸附容量为Q_Rh>Q_Pd>Q_Pt;Pd,Pt和Rh的吸附焓变（ΔH）分别为31.33,10.75和19.50 kJ·mol^-1，表明吸附过程不存在强化学键作用力，主要是离子交换、氢键及疏水键作用；吉布斯自由能变（ΔG）<0表明吸附过程均能自发进行，且属于物理吸附过程；熵变（ΔS）>0表明铂族金属离子在吸附力作用下，整个体系混乱度增加，但温度对ΔS影响较小。更多还原

【Abstract】 Molecular recognition technology（MRT） is one of the most advanced separation technologies today. MRT separation technology of platinum group metals（PGMs） has attracted increasing attention due to its advantages such as short process flow, high recovery, and short cycle time. The principle of molecular recognition technology is to use specially designed macrocyclic compounds or ligands to selectively adsorb target ions from the solution without other ions being adsorbed, achieving the separation of target ions.At the same time, the adsorbed target ions can be desorbed by changing conditions. Due to its high selectivity and excellent adsorption performance of recognition materials, the target ions can be effectively separated and enriched. Molecular recognition technology, similar to ion exchange method, is a liquid-solid extraction technology that has developed rapidly in recent years. Due to its higher selectivity and shorter technological process, it has received high attention in the platinum group metal refining industry. In this paper, the material structure, kinetics, and thermodynamics of adsorption of platinum group metals（Pd, Pt and Rh） onto MRT materials were studied. For the structure of their recognition materials, particle size analyzer, specific surface area analyzer, pore volume tester, X-ray fluorescence analyzer, scanning electron microscope（SEM） and Fourier transform infrared spectrometer（FT-TR） were used to conduct physical characterization and structural analysis of three recognition materials（M1, M2 and M3）. The role of materials in separating precious metals from a structural perspective was analyzed and identified. And the adsorption kinetics and thermodynamics experiments on three recognition materials（M1, M2 and M3） were conducted. During the adsorption kinetics experiment, the recognition materials were added to three chloride solutions of Pd, Pt, and Rh to oscillate at constant temperature, take regular samples, and determine the concentration in the solution using inductively coupled plasma-atomic emission spectrometry. Studying the adsorption kinetics model could predict the possible reaction mechanism and predict the reaction rate, and establish a quasi-first order kinetic model or a quasi-second order kinetic model. When conducting thermodynamic experiments, the adsorption equilibria were performed at 303, 308, 313, 318, and 323 K, and the concentrations of Pd, Pt, and Rh in the solution were measured. The thermodynamic study of the adsorption of platinum group metals by MRT materials began with adsorption isotherm models, adsorption equilibrium studies, and thermodynamic parameters. In order to better understand the adsorption mechanism of the three materials for platinum group metals（Pd, Pt, and Rh）, two classical adsorption models, Langmuir model and Freundlich model, were used to fit the experimental data. Through data processing and theoretical analysis, model parameters were established for the adsorption of PdCl₄^2-by M1 material, PtCl₆^2-by M2 material, and RhCl₆^3-by M3 material, and the thermodynamic linear relationship diagrams for the adsorption of Pd, Pt, and Rh by MRT material were fitted. The results showed that the adsorption of PdCl₄^2-by M1 material, PtCl₄^2-by M2 material, and RhCl₆^3-by M3 material conformed to a quasi-second order kinetic model, the adsorption of Pd, Pt, and Rh all conformed to Langmuir model. The order of adsorption rates of the three materials was νPd>νPt>νRh, and the saturated adsorption capacity was Q_Rh>Q_Pd>Q_Pt. The adsorption enthalpy change （ΔH） values for Pd, Pt, and Rh were 31.33, 10.75 and, 19.50 kJ·mol^-1, respectively, indicating that there was no enhanced bonding force during the adsorption process, mainly due to ion exchange, hydrogen bonding, and hydrophobic bonding. On the one hand, Gibbs free energy change （ΔG）<0 in the adsorption process of the three recognition materials indicated that the process of adsorption of platinum group metals could occur spontaneously and belonged to a physical adsorption process; on the other hand, the result of entropy change （ΔS）>0 indicated that the disorder degree of the entire system increases due to the adsorption of platinum group metal ions. However, temperature has little effect on ΔS. At the same time, after repeated adsorption and elution, the adsorption performance of MRT material had basically not changed, indicating that the resin materials used for the separation of platinum group metals（Pd, Pt, and Rh） had good regenerative adsorption performance and excellent stability, and then could be reused. Compared to traditional separation methods, molecular recognition technology had significant separation advantages and had become an indispensable separation technology in the metallurgical field.更多还原