Kinetic and Thermodynamic Studies on Adsorption of Platinum Group Metals by Molecular Recognition Materials AITranslate

［1］（余建民，毕向光，李权. 汽车失效催化剂之铂族金属分离方法［J］.稀有金属，2013，37（3）：485.）

J M Yu，X G Bi，Q Li. Review of separation methods of platinum group metals from spent auto-catalysts［J］.Chinese Journal of Rare Metals，2013，37（3）：485.

［2］（李卫民. 分子识别技术在铜工业应用中的最新进展［J］.中国有色冶金，2007，（4）：1.）

W M Li. Recent advances in the application of molecular recognition technology （MRT） in the copper industry［J］.China Nonferrous Metallurgy，2007，（4）：1.

［3］（王建军，庄宇凯，徐剑瑛，王绍娟，曹全苹. 电感耦合等离子体光谱法测定贵金属合金电镀废水中贵金属［J］.黄金，2023，44（10）：106.）

J J Wang，Y K Zhuang，J Y Xu，S J Wang，Q P Cao. Determination of precious metals in precious metal alloy electroplating wastewater by ICP［J］.Gold，2023，44（10）：106.

［4］（余德和，左川，高勇，周世平，卢军，刘锋. 电解水析氢贵金属电催化剂的研究进展［J］.稀有金属，2023，47（11）：1573.）

D H Yu，C Zuo，Y Gao，S P Zhou，J Lu，F Liu. Research progress on electrolysis of hydrogen-deposited noble metal electrocatalysts［J］.Chinese Journal of Rare Metals，2023，47（11）：1573.

［5］（李耀威，杨明珠，王芝元. 分子识别技术在金属分离回收中的应用研究进展［J］.安全与环境学报，2013，13（3）：93.）

Y W Li，M Z Yang，Z Y Wang. Progress in the application of molecular recognition technology to the metal separation and recovery［J］.Journal of Safety and Environment，2013，13（3）：93.

［6］（白雪莲，邓文叶，刘育育，薛燕，赵鹏君，常爱民，谢永新.微波辅助回收废旧三元锂电池中的有价金属［J］.有色金属工程，2023，13（9）：79.）

X L Bai，W Y Deng，Y Y Liu，Y Xue，P J Zhao，A M Chang，Y X Xie. Microwave assisted recovery of valuable metals from waste ternary lithium batteries［J］.Nonferrous Metals Engineering，2023，13（9）：79.

［7］（范兴祥，董海刚，付光强，陈家林，吴跃东，赵家春. 还原-磨选法从汽车尾气失效催化剂中富集铂族金属［J］.稀有金属，2014，38（2）：262.）

X X Fan，H G Dong，G Q Fu，J L Chen，Y D Wu，J C Zhao. Enrichment of PGMs by reduction grinding-separation method from spent automobile catalyst［J］.Chinese Journal of Rare Metals，2014，38（2）：262.

［8］（王亚军，李晓征. 汽车尾气净化催化剂贵金属回收技术 ［J］.稀有金属，2013，37（6）：1004.）

Y J Wang，X Z Li. Progress in recycling of precious metals in automobile catalysts［J］.Chinese Journal of Rare Metals，2013，37（6）：1004.

［9］（王露，冯天意，崔鹏媛，沈庆峰，林艳，俞小花. 废旧锂离子电池正极材料中有价金属离子分离回收技术的研究现状［J］.有色金属科学与工程，2023，14（6）：791.）

L Wang，T Y Feng，P Y Cui，Q F Shen，Y Lin，X H Yu.Status of technological research on the separation and recovery of valuable metal ions in cathode materials from spent lithium-ion battery［J］.Nonferrous Metals Science and Engineering，2023，14（6）：791.

［10］（房孟钊. 从金还原后液中回收贵金属的试验研究［J］.铜业工程，2023，（1）：157.）

M Z Fang. Recovery of precious metals from gold reduction liquid［J］.Copper Engineering，2023，（1）：157.

［11］Izatt R M，Izatt S R，Izatt N E，Krakowiak K E，Bruening R L，Navarro L. Industrial applications of molecular recognition technology to separations of platinum group metals and selective removal of metal impurities from process streams［J］.Green chemistry，2015，17（4）：2236.

［12］（李卫民. 分子识别技术在铋的脱除和回收中的新应用 ［J］.中国有色冶金，2008，（2）：1.）

W M Li. A new MRT application for bismuth removal and recovery［J］.China Nonferrous Metallurgy，2008，（2）：1.

［13］Wright C，Bruening R L. The new SuperligTM resins：report on the first commercial precious metals refinery application，precious metals recovery and refining［A］. Proceedings of a seminar of the international precious metals institute ［C］. Scottsdale，Arizona，USA，1989. 95.

［14］Bruening R L，Izatt S R，Griffin L D. Separation of Rhand/or Ir form concentrated precious and base metals matrices using SuperligTM1［A］. Precious Metals1990.Proceedings of the 14th international precious metals conference and exhibition ［C］. San Diego，California，USA，1990.1.

［15］Black W H，Izatt S R，Dale J B，Bruening R L. The application of molecular recognition technology （MRT） in the palladium refining process at Impala and other selected applications［A］. In 30th Annual Conference，International Precious Metals Institute ［C］. Pensacola，FL，USA，2006. 1.

［16］（郝海光，秦红伟，赵周明，侯致福. 分子识别技术应用于废弃SCR脱硝催化剂中钒和钨的回收研究［J］.山东化工，2020，49（13）：244.）

H G Hao，H W Qin，Z M Zhao，Z F Hou. Study on the recovery of the vanadium，tungsten from waste SCR catalyst by molecular recognition technology［J］.Shandong Chemical Industry，2020，49（13）：244.

［17］Ichiishi S，Izatt S R，Bruening R L. A commercial MRT process for recovery and purification of rhodium from a refinery feed stream containing platinum group metals and base metal contaminants［A］. Proceedings of the 24th International Precious Metals Conference and Exhibition ［C］. Willianmsburg，Virginia，USA，2000.11.

［18］Ichiishi S，Izatt S R，Bruening R L，Izatt N E，Dale J B. A commercial MRT process for the recovery and purification of rhodium from a refinery feed stream containing platinum group metals （PGMs） and base metal contaminants［A］. Precious Metals 2000：24th International Precious Metals Conference ［C］. Williamsburg，Virginia，USA，2000. 11.

［19］Izatt S R，Dale J B，Bruening R L. The application of molecular recognition technology （MRT） to refining of platinum and ruthenium［A］. International Precious Metals Institute，31st Annual Conference ［C］. Miami，FL，USA，2007. 9.

［20］Izatt S R，Mansur D M. Environmentally friendly recovery of precious metals from spent catalysts［A］. International Precious Metals Institute Petroleum Seminar ［C］. Houston，Texas，USA，2006. 13.

［21］（贺小塘，韩守礼，吴喜龙，王欢，王咏梅. 分子识别技术在铂族金属分离提纯中的应用［J］.贵金属，2010，31（1）：53.）

X T He，S L Han，X L Wu，H Wang，Y M Wang. Application of molecular recognition technology in platinum group metals refining process［J］.Precious Metals，2010，31（1）：53.

［22］（杨桂生，王欢，赵雨，李勇，陈明军，贺小塘，吴喜龙. 从硝酸工业过滤器回收铂族金属的工艺研究［J］.贵金属，2019，40（3）：39.）

G S Yang，H Wang，Y Zhao，Y Li，M J Chen，X T He，X L Wu. Studying on recovering of platinum metals from recovery filter in nitric acid industry［J］.Precious Metals，2019，40（3）：39.

［23］（赵天逸，宁正福，曾彦. 页岩与煤岩等温吸附模型对比分析［J］.新疆石油地质，2014，35（3）：319.）

T Y Zhao，Z F Ning，Y Zeng. Comparative analysis of isothermal adsorption models for shales and coals［J］.Xinjiang Petroleum Geology，2014，35（3）：319.

Basic Information:

DOI：10.13373/j.cnki.cjrm.XY23030037

Chinese Library Classification Number:TF803.21

Citation Information:

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 PdCl₄²⁻ by M1 material，PtCl₆²⁻ by M2 material，and RhCl₆³⁻ 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 PdCl₄²⁻ by M1 material，PtCl₄²⁻ by M2 material，and RhCl₆³⁻ 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 ν_Pd>ν_Pt>ν_Rh，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.