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《中国工程科学》 >> 2024年 第26卷 第3期 doi: 10.15302/J-SSCAE-2024.03.012

铂族金属循环利用技术开发现状及展望

1. 南昌大学物理与材料学院,南昌 330031
2. 北京科技大学新材料技术研究院,北京 100083

收稿日期: 2024-05-16 修回日期: 2024-06-12

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摘要

铂族金属(PGMs)是汽车、石化、能源、国防装备等领域不可或缺的战略性金属资源,但PGMs矿产资源极度匮乏,供需矛盾突出;开展PGMs循环利用是保障PGMs安全供应、支撑关联产业高质量发展的重要举措。本文分析了PGMs的供给和应用情况,明确了当前PGMs市场的供需态势;全面梳理了PGMs湿法回收(含氰化法、盐酸+氧化剂工艺),火法回收(含铅捕集、铜捕集、锍捕集、铁捕集工艺)的技术特征与应用情况;着重从焙烧 ‒ 浸出、铁捕集 ‒ 酸浸、低温铁捕集 ‒ 电解 ‒ 离心萃取工艺等方面阐述了PGMs火法 ‒ 湿法联合回收技术的研发与应用进展。其中,低温铁捕集 ‒ 电解 ‒ 离心萃取成套工艺延续了低温铁捕集研究思路,通过低熔点渣型设计将铁捕集温度由1800 ℃以上降至约1400 ℃,富集得到Fe-PGMs合金后经电解进一步富集PGMs,再经离心萃取提纯依次得到Pd、Pt、Rh,实现了短流程分离提纯PGMs,具有绿色、高效、低成本的诸多优点。着眼PGMs循环利用产业高质量发展,建议围绕“PGMs富集、分离提纯、污染防控”全流程开展基础研究和技术攻关,加快建设PGMs循环利用全链条标准体系和绿色低碳的产业生态环境,全面开展业务流程的“互联网+”能力建设以实现“回收 ‒ 处理 ‒ 再利用”全流程的智能化。

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参考文献

[ 1 ] Tong X, Dai H C, Lu P T, et al. Saving global platinum demand while achieving carbon neutrality in the passenger transport sector: Linking material flow analysis with integrated assessment model [J]. Resources, Conservation and Recycling, 2022, 179: 106110.

[ 2 ] 崔祖霞. 我国战略性矿产资源保供形势分析与思考 [J]. 中国矿业, 2023, 32(7): 10‒14.
Cui Z X. Analysis and reflection on the situation of strategic mineral resources conservation in China [J]. China Mining Magazine, 2023, 32(7): 10‒14.

[ 3 ] 裴忠冶, 王政华, 冯亚平, 等. 铂族金属火法冶炼技术研究进展 [J]. 中国有色冶金, 2023, 52(6): 16‒25.
Pei Z Y, Wang Z H, Feng Y P, et al. Research progress of platinum group metals pyrometallurgy technology [J]. China Nonferrous Metallurgy, 2023, 52(6): 16‒25.

[ 4 ] 曹礼梅, 邱兆富, 张巍, 等. 化工废催化剂污染特征及资源化途径 [J]. 化工进展, 2021, 40(10): 5293‒5301.
Cao L M, Qiu Z F, Zhang W, et al. Pollution and utilization of chemical industry spent catalysts [J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5293‒5301.

[ 5 ] Cowley A. PGM market report 2024 [R]. London: Johnson Matthey, 2024.

[ 6 ] 辛宝平, 王佳. 涉重危废概念的提出及其资源化利用 [J]. 环境工程学报, 2022, 16(1): 1‒9.
Xin B P, Wang J. Scientific definition of hazardous wastes containing heavy metals and their resource utilization [J]. Chinese Journal of Environmental Engineering, 2022, 16(1): 1‒9.

[ 7 ] The U.S. Geological Survey. Mineral commodity summaries 2023 [R]. Reston: National Minerals Information Center, 2023.

[ 8 ] Cowley A. PGM market report 2023 [R]. London: Johnson Matthey, 2023.

[ 9 ] 全球铂族金属年鉴2022 [R]. 伦敦: 金属聚焦公司, 2023.
Global platinum-group metals yearbook 2022 [R]. London: Metal Focus, 2023.

[10] 胡龙, 李骞, 董海刚, 等. 废Pd/Al2O3催化剂中钯的湿法回收工艺研究进展 [J]. 贵金属, 2016, 37(S1): 110‒114.
Hu L, Li Q, Dong H G, et al. Research on hydrometallurgical processes for recovery of palladium from spent Pd/Al2O3 catalysts [J]. Precious Metals, 2016, 37(S1): 110‒114.

[11] 丁云集, 张深根. 废催化剂中铂族金属回收现状与研究进展 [J]. 工程科学学报, 2020, 42(3): 257‒269.
Ding Y J, Zhang S G. Status and research progress on recovery of platinum group metals from spent catalysts [J]. Chinese Journal of Engineering, 2020, 42(3): 257‒269.

[12] 钱兴坤, 陆如泉, 罗良才, 等. 2023年国内外油气行业发展及2024年展望 [J]. 国际石油经济, 2024, 32(2): 1‒13.
Qian X K, Lu R Q, Luo L C, et al. Global oil and gas industry in 2023 and outlook for 2024 [J]. International Petroleum Economics, 2024, 32(2): 1‒13.

[13] Liu Y, Zhang L G, Song Q M, et al. Recovery of palladium as nanoparticles from waste multilayer ceramic capacitors by potential-controlled electrodeposition [J]. Journal of Cleaner Production, 2020, 257: 120370.

[14] 邓瑞, 闻明, 陈家林, 等. 钌粉提纯和钌靶制备的研究进展 [J]. 贵金属, 2019, 40(1): 82‒87.
Deng R, Wen M, Chen J L, et al. Progress in refining of ruthenium powder and preparation of ruthenium target [J]. Precious Metals, 2019, 40(1): 82‒87.

[15] 雷云涛, 孙丰龙, 赵中伟. 地球化学与提取冶金的学科借鉴——以铂族金属和金为例 [J]. 中国有色金属学报, 2023, 33(9): 2957‒2974.
Lei Y T, Sun F L, Zhao Z W. Interdisciplinarity of geochemistry and extractive metallurgy—Taking platinum group metals and gold as examples [J]. The Chinese Journal of Nonferrous Metals, 2023, 33(9): 2957‒2974.

[16] Kinas S, Jermakowicz-Bartkowiak D, Pohl P, et al. On the path of recovering platinum-group metals and rhenium: A review on the recent advances in secondary-source and waste materials processing [J]. Hydrometallurgy, 2024, 223: 106222.

[17] 黄昆, 陈景, 陈奕然, 等. 加压碱浸处理 ‒ 氰化浸出法回收汽车废催化剂中的贵金属 [J]. 中国有色金属学报, 2006, 16(2): 363‒369.
Huang K, Chen J, Chen Y R, et al. Recovery of precious metals from spent auto-catalysts by method of pressure alkaline treatment-cyanide leaching [J]. The Chinese Journal of Nonferrous Metals, 2006, 16(2): 363‒369.

[18] Snyders C A, Bradshaw S M, Akdogan G, et al. The effect of temperature, cyanide and base metals on the adsorption of Pt, Pd and Au onto activated carbon [J]. Hydrometallurgy, 2014, 149: 132‒142.

[19] Shams K, Beiggy M R, Gholamipour S A. Platinum recovery from a spent industrial dehydrogenation catalyst using cyanide leaching followed by ion exchange [J]. Applied Catalysis A: General, 2004, 258(2): 227‒234.

[20] Dari J A. Extraction of platinum from spent catalyst as Pt/Al2O3 in aqua regia [J]. Diyala Journal of Engineering Sciences, 2019, 12(3): 8‒14.

[21] 黄继承. 从废载体催化剂中回收提炼高纯铂 [J]. 再生资源研究, 2000 (3): 24‒25.
Huang J C. Recovering and refining high purity platinum from waste carrier catalyst [J]. Recycling Research, 2000 (3): 24‒25.

[22] Baghalha M, Khosravian G H, Mortaheb H R. Kinetics of platinum extraction from spent reforming catalysts in aqua-regia solutions [J]. Hydrometallurgy, 2009, 95(3/4): 247‒253.

[23] 李骞, 胡龙, 杨永斌, 等. 从失效催化剂中回收钯的试验研究 [J]. 湿法冶金, 2017, 36(1): 41‒45.
Li Q, Hu L, Yang Y B, et al. Research on recovery of palladium from spent catalyst [J]. Hydrometallurgy of China, 2017, 36(1): 41‒45.

[24] 李耀威, 戚锡堆. 废汽车催化剂中铂族金属的浸出研究 [J]. 华南师范大学学报(自然科学版), 2008, 40(2): 84‒87.
Li Y W, Qi X D. Study on leaching of platinum-group metals from spent auto-catalysts [J]. Journal of South China Normal University (Natural Science Edition), 2008, 40(2): 84‒87.

[25] 张朝宏, 张立, 李国栋, 等. 废汽车三元催化剂湿法回收铂族金属研究 [J]. 再生资源与循环经济, 2023, 16(10): 26‒31.
Zhang C H, Zhang L, Li G D, et al. Study on wet recovery of platinum group metals from ternary catalyst of waste automobile [J]. Recyclable Resources and Circular Economy, 2023, 16(10): 26‒31.

[26] Trucillo P, Lancia A, Di Natale F. Recovery of platinum from diesel catalysts by combined use of H2O2/HCl leaching and adsorption [J]. Journal of Environmental Chemical Engineering, 2022, 10(3): 107730.

[27] Ding Y J, Zheng H D, Li J Y, et al. Recovery of platinum from spent petroleum catalysts: Optimization using response surface methodology [J]. Metals, 2019, 9(3): 354.

[28] Ding Y J, Zhang S G, Liu B, et al. Recovery of precious metals from electronic waste and spent catalysts: A review [J]. Resources, Conservation and Recycling, 2019, 141: 284‒298.

[29] 管有祥, 徐光, 王应进, 等. 用金作保护剂铅试金富集汽车尾气净化催化剂中铂钯铑的研究 [J]. 贵金属, 2011, 32(2): 67‒71.
Guan Y X, Xu G, Wang Y J, et al. Study on gold as protective reagent for enrichment Pt, Pd and Rh by lead assaying for automobile exhaust-purifying catalysts [J]. Precious Metals, 2011, 32(2): 67‒71.

[30] 张腾, 张善辉, 姜学利, 等. PbO高温还原法捕集铂族金属的试验研究 [J]. 铜业工程, 2022 (5): 62‒66.
Zhang T, Zhang S H, Jiang X L, et al. Experimental study on platinum group metals capture by PbO high-temperature reduction method [J]. Copper Engineering, 2022 (5): 62‒66.

[31] 赵家春, 崔浩, 保思敏, 等. 铜捕集法回收铂族金属的理论及实验研究 [J]. 中国有色金属学报, 2019, 29(12): 2819‒2825.
Zhao J C, Cui H, Bao S M, et al. Theory and practice on recovery of platinum group metals from spent auto catalysts by reduction-smelting copper trapping method [J]. The Chinese Journal of Nonferrous Metals, 2019, 29(12): 2819‒2825.

[32] Zhang L G, Song Q M, Liu Y, et al. Novel approach for recovery of palladium in spent catalyst from automobile by a capture technology of eutectic copper [J]. Journal of Cleaner Production, 2019, 239: 118093.

[33] Kolliopoulos G, Balomenos E, Giannopoulou I, et al. Behavior of platinum group during their pyrometallurgical recovery from spent automotive catalysts [J]. OALib, 2014, 1(5): 1‒9.

[34] 陈景. 火法冶金中贱金属及锍捕集贵金属原理的讨论 [J]. 中国工程科学, 2007, 9(5): 11‒16.
Chen J. Discussion on the micro-mechanism of precious metals trapped in pyro-metallurgical processes by base metals and matte phase [J]. Strategic Study of CAE, 2007, 9(5): 11‒16.

[35] Tang H M, Peng Z W, Li Z Z, et al. Recovery of platinum-group metals from spent catalysts by microwave smelting [J]. Journal of Cleaner Production, 2021, 318: 128266.

[36] Morcali M H. A new approach to recover platinum-group metals from spent catalytic converters via iron matte [J]. Resources, Conservation and Recycling, 2020, 159: 104891.

[37] Sun L D, Jiang Y, Huang M Y, et al. Recovery and enrichment of platinum from spent Al2O3 carrier catalysts by matte smelting-acid leaching process [J]. Advances in Materials Science and Engineering, 2022, 2022: 8473452.

[38] 贺小塘, 李勇, 吴喜龙, 等. 等离子熔炼技术富集铂族金属工艺初探 [J]. 贵金属, 2016, 37(1): 1‒5.
He X T, Li Y, Wu X L, et al. Study on the process of enrichment platinum group metals by plasma melting technology [J]. Precious Metals, 2016, 37(1): 1‒5.

[39] Kasuya R, Miki T, Morikawa H, et al. Dissolution of platinum in catalyst materials using hydrochloric acid: A new method based on the use of complex oxides [J]. Minerals Engineering, 2016, 87: 25‒31.

[40] Ikhmayies S J, Li B W, Carpenter J S, et al. Characterization of minerals, metals, and materials 2016 [M]. Cham: Springer, 2016.

[41] 董海刚, 赵家春, 杨海琼, 等. 铵盐焙烧 ‒ 酸浸法从石油重整废催化剂中富集回收铂的研究 [J]. 贵金属, 2014, 35(S1): 23‒27, 30.
Dong H G, Zhao J C, Yang H Q, et al. Enrichment and recovery of Pt from spent petroleum reforming catalyst by ammonium salt roasting-acid leaching process [J]. Precious Metals, 2014, 35(S1): 23‒27, 30.

[42] 吴喜龙, 贺小塘, 李红梅, 等. 含铂钯铑的铁合金富集物溶解试验研究 [J]. 有色金属(冶炼部分), 2016 (3): 52‒54, 67.
Wu X L, He X T, Li H M, et al. Dissolution research of platinum, palladium and rhodium enriched ferroalloy [J]. Nonferrous Metals (Extractive Metallurgy), 2016 (3): 52‒54, 67.

[43] 陈景, 陈奕然, 谢明进. 从熔炼捕集料中回收铂族金属的方法: CN101575674A [P]. 2009-11-11.
Chen J, Chen Y R, Xie M J. Methods for the recovery of platinum group metals from smelting traps: CN101575674A [P]. 2009-11-11.

[44] 童伟锋, 董海刚, 吴晓峰, 等. 两段逆流浸出从铁捕集物中富集铂族金属的研究 [J]. 贵金属, 2015, 36(1): 21‒24.
Tong W F, Dong H G, Wu X F, et al. Study on enrichment of platinum group metals in iron-trapping material using two-stage countercurrent leaching [J]. Precious Metals, 2015, 36(1): 21‒24.

[45] 丁云集, 崔言杰, 张深根. 铁捕集铂族金属富集物的锌碎化-酸解原理及工艺研究 [J]. 稀有金属, 2022, 46(1): 57‒66.
Ding Y J, Cui Y J, Zhang S G. Mechanism and process of zinc fragmentation-acid leaching of platinum group metals concentrates from iron capture method [J]. Chinese Journal of Rare Metals, 2022, 46(1): 57‒66.

[46] Ding Y J, Zheng H D, Zhang S G, et al. Highly efficient recovery of platinum, palladium, and rhodium from spent automotive catalysts via iron melting collection [J]. Resources, Conservation and Recycling, 2020, 155: 104644.

[47] Zheng H D, Ding Y J, Wen Q, et al. Slag design and iron capture mechanism for recovering low-grade Pt, Pd, and Rh from leaching residue of spent auto-exhaust catalysts [J]. Science of the Total Environment, 2022, 802: 149830.

[48] He X F, Yin X P, Ding Y J, et al. Slag design and optimization for iron capturing platinum group metals from alumina-based spent catalysts [J]. Rare Metals, 2023, 42(6): 2093‒2103.

[49] Wen Q, Ding Y J, Zheng H D, et al. Process and mechanism of electrolytic enrichment of PGMs from Fe-PGMs alloy [J]. Journal of Cleaner Production, 2020, 271: 122829.

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