深共晶溶剂聚合物包覆膜传输分离铂、钯的研究

doi:10.11949/0438-1157.20240507

摘要/Abstract

摘要：

铂族金属（platinum group metal，PGM）元素中的铂（platinum）、钯（palladium）是一类具有高经济价值的稀有金属元素，广泛应用于工业、科学、医疗和高科技等领域。由于PGM的矿产供应量无法满足不断增长的市场需求。废旧汽车催化剂、电子废弃物等二次资源的回收成为缓解PGM供需矛盾的重要途径。本研究模拟实际废旧汽车催化剂浸出液，构建分离回收Pt（Ⅳ）、Pd（Ⅱ）的深共晶溶剂聚合物包覆膜电渗析集成体系。系统探究了体系中各工艺参数对模拟浸出液中铂族金属传输与分离的影响。结果表明，摩尔比为1∶1的TOPO/Thy对Pt、Pd传输性能最好，Pt、Pd的萃取效率均为99.90%，反萃取效率分别为65.96%、77.93%。而0.05 mol·L^-1 KSCN作为反萃液对Pt、Pd有良好的分离效果，对Pt、Pd的反萃效率分别为62.54%、89.19%。本研究可为废旧催化剂的处理提供一种高效绿色环保的技术思路与理论依据。

关键词: 分离, 膜, 萃取, 聚合物包覆膜, 深共晶溶剂, 电渗析, 铂族金属

Abstract:

Platinum group metal (PGM) elements of Pt (platinum), Pd (palladium) is a kind of rare metal elements with high economic value, widely used in industrial, scientific, medical and high-tech fields. Because the mineral supply of PGM cannot meet the growing market demand. The recycling of secondary resources such as waste automobile catalysts and electronic waste has become an important way to alleviate the contradiction between supply and demand of PGM. In this paper, a deep eutectic solvent polymer inclusion membrane electrodialysis integrated system for one-step separation and recovery of Pt(Ⅳ) and Pd(Ⅱ) was constructed by simulating the actual leaching solution of spent automobile catalysts. The effects of various process parameters in the system on the separation of platinum group metals in the leaching solution of spent automobile catalysts were systematically investigated. The results showed that the TOPO/thymol with a molar ratio of 1∶1 had the best transport performance for Pt and Pd. The extraction efficiency of Pt and Pd were 99.90%, and the stripping efficiency were 65.96% and 77.93%, respectively. The 0.05 mol·L^-1 KSCN as the stripping solution had a good separation effect on Pt and Pd, and the stripping efficiency of Pt and Pd were 62.54% and 89.19%, respectively. This study is of great significance for the efficient separation and recovery of Pt(Ⅳ) and Pd(Ⅱ) in spent automobile catalysts.

Key words: separation, membrane, extraction, polymer inclusion membrane, deep eutectic solvent, electrodialysis, platinum group metal

中图分类号:

TQ 028

谢慧慧, 姜佳鑫, 王鑫, 李正, 郭鑫, 吕欣然, 王凌云, 刘杨. 深共晶溶剂聚合物包覆膜传输分离铂、钯的研究[J]. 化工学报, 2024, 75(S1): 235-243.

Huihui XIE, Jiaxin JIANG, Xin WANG, Zheng LI, Xin GUO, Xinran LYU, Lingyun WANG, Yang LIU. Study on transport separation of platinum and palladium by deep eutectic solvent polymer inclusion membrane[J]. CIESC Journal, 2024, 75(S1): 235-243.

图/表 9

图1 DES组分的结构

Fig.1 The structure of DES component

表1 制备DES的组成与比例

Table 1 Composition and proportion of prepared DES

缩写	氢键供体	氢键受体	受供体摩尔比	室温下的存在形式
TOPO/Thy	TOPO	Thy	1∶2	均匀透明液体
TOPO/Thy			1∶1	均匀透明液体
TOPO/Thy			2∶1	均匀透明液体
Lid/Thy	Lid	Thy	1∶2	凝胶体
Lid/Thy			1∶1	均匀透明液体
Lid/Thy			2∶1	凝胶体
TOAB/HA	TOAB	HA	1∶2	均匀透明液体
TOAB/HA			1∶1	凝胶体
TOAB/HA			2∶1	凝胶体

图2 DES-PIMED装置构型图

Fig.2 DES-PIMED device configuration diagram

图3 不同DES的黏度（1 cP=10-3 Pa·s）

Fig.3 Viscosity of different DESs

图4 不同DES-PIM对Pt、Pd传输与分离的影响

Fig.4 The effect of different DES-PIMs on the transport and separation of Pt and Pd

图5 不同氢键受体和供体比例对Pt、Pd传输与分离的影响

Fig.5 The effect of different hydrogen bond acceptor and donor ratios on the transport and separation of Pt and Pd

图6 不同载体的PIM对Pt、Pd传输与分离的影响

Fig.6 The effect of PIM of different carriers on the transport and separation of Pt and Pd

图7 不同反萃液对Pt、Pd传输与分离的影响

Fig.7 The effect of different stripping solutions on the transport and separation of Pt and Pd

图8 DES-PIM以及成膜组分的红外光谱分析

Fig.8 The infrared spectrum analysis of DES-PIM and membrane-forming components

参考文献 31

1	Tang N, Liu L L, Yin C, et al. Environmentally benign hydrophobic deep eutectic solvents for palladium(Ⅱ) extraction from hydrochloric acid solution[J]. Journal of the Taiwan Institute of Chemical Engineers, 2021, 121: 92-100.
2	Karim S, Ting Y P. Recycling pathways for platinum group metals from spent automotive catalyst: a review on conventional approaches and bio-processes[J]. Resources, Conservation and Recycling, 2021, 170: 105588.
3	Yakoumis I, Panou M, Moschovi A M, et al. Recovery of platinum group metals from spent automotive catalysts: a review[J]. Cleaner Engineering and Technology, 2021, 3: 100112.
4	Islam A, Swaraz A M, Teo S H, et al. Advances in physiochemical and biotechnological approaches for sustainable metal recovery from e-waste: a critical review[J]. Journal of Cleaner Production, 2021, 323: 129015.
5	聂瑶, 丁炜, 魏子栋. 质子交换膜燃料电池非铂电催化剂研究进展[J]. 化工学报, 2015, 66(9): 3305-3318.
	Nie Y, Ding W, Wei Z D. Recent advancements of Pt-free catalysts for polymer electrolyte membrane fuel cells[J]. CIESC Journal, 2015, 66(9): 3305-3318.
6	王培灿, 万磊, 徐子昂. 碱性膜电解水制氢技术现状与展望[J]. 化工学报, 2021, 72(12): 6161-6175.
	Wang P C, Wan L, Xu Z A, et al. Hydrogen production based-on anion exchange membrane water electrolysis: a critical review and perspective[J]. CIESC Journal, 2021, 72(12): 6161-6175.
7	Izatt R M, Izatt S R, Izatt N E, et al. 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): 2236-2245.
8	Ilyas S, Srivastava R R, Kim H, et al. Hydrometallurgical recycling of palladium and platinum from exhausted diesel oxidation catalysts[J]. Separation and Purification Technology, 2020, 248: 117029.
9	Yoshida W, Kubota F, Kono R, et al. Selective separation and recovery of Pt(Ⅳ) from Pd(Ⅱ) through an imidazolium-ionic-liquid-based supported liquid membrane[J]. Analytical Sciences: the International Journal of the Japan Society for Analytical Chemistry, 2019, 35(3): 343-346.
10	Yamada M, Rajiv Gandhi M, Kaneta Y, et al. Thiodiphenol-based n-dialkylamino extractants for selective platinum group metal separation from automotive catalysts[J]. Industrial & Engineering Chemistry Research, 2018, 57(5): 1361-1369.
11	Keskin B, Zeytuncu-Gökoğlu B, Koyuncu I. Polymer inclusion membrane applications for transport of metal ions: a critical review[J]. Chemosphere, 2021, 279: 130604.
12	Wang D, Hu J G, Li Y, et al. Evidence on the 2-nitrophenyl octyl ether (NPOE) facilitating copper(Ⅱ) transport through polymer inclusion membranes[J]. Journal of Membrane Science, 2016, 501: 228-235.
13	Wang B Y, Wang Y M, Xu T W. Recent advances in the selective transport and recovery of metal ions using polymer inclusion membranes[J]. Advanced Materials Technologies, 2023, 8(22): 2300829.
14	Nghiem L D, Mornane P, Potter I D, et al. Extraction and transport of metal ions and small organic compounds using polymer inclusion membranes (PIMs)[J]. Journal of Membrane Science, 2006, 281(1/2): 7-41.
15	Zhao S F, Samadi A, Wang Z, et al. Ionic liquid-based polymer inclusion membranes for metal ions extraction and recovery: fundamentals, considerations, and prospects[J]. Chemical Engineering Journal, 2024, 481: 148792.
16	Fajar A T N, Hanada T, Goto M. Recovery of platinum group metals from a spent automotive catalyst using polymer inclusion membranes containing an ionic liquid carrier[J]. Journal of Membrane Science, 2021, 629: 119296.
17	Fajar A T N, Hanada T, Firmansyah M L, et al. Selective separation of platinum group metals via sequential transport through polymer inclusion membranes containing an ionic liquid carrier[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(30): 11283-11291.
18	Shahrezaei F, Shamsipur M, Gholivand M B, et al. A highly selective green supported liquid membrane by using a hydrophobic deep eutectic solvent for carrier-less transport of silver ions[J]. Analytical Methods, 2020, 12(38): 4682-4690.
19	Abbott A P, Capper G, Davies D L, et al. Novel solvent properties of choline chloride/urea mixtures[J]. Chemical Communications, 2003(1): 70-71.
20	Sapir L, Harries D. Restructuring a deep eutectic solvent by water: the nanostructure of hydrated choline chloride/urea[J]. Journal of Chemical Theory and Computation, 2020, 16(5): 3335-3342.
21	Yang T X, Zhao L Q, Wang J, et al. Improving whole-cell biocatalysis by addition of deep eutectic solvents and natural deep eutectic solvents[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(7): 5713-5722.
22	Ali R A. Review on extraction of phenolic compounds from natural sources using green deep eutectic solvents[J]. Journal of Agricultural and Food Chemistry, 2021, 69(3): 878-912.
23	Tomé L C, Mecerreyes D. Emerging ionic soft materials based on deep eutectic solvents[J]. The Journal of Physical Chemistry. B, 2020, 124(39): 8465-8478.
24	Mokhodoeva O, Maksimova V, Shishov A, et al. Separation of platinum group metals using deep eutectic solvents based on quaternary ammonium salts[J]. Separation and Purification Technology, 2023, 305: 122427.
25	Li Z Y, Liu Y, Wang B Y, et al. Insights into the facilitated transport mechanisms of Cr(Ⅵ) in ionic liquid-based polymer inclusion membrane-electrodialysis (PIM-ED) process[J]. Chemical Engineering Journal, 2020, 397: 125324.
26	Qin Z H, Wang Y Z, Sun L, et al. Vanadium recovery by electrodialysis using polymer inclusion membranes[J]. Journal of Hazardous Materials, 2022, 436: 129315.
27	Wang B Y, Li Z Y, Lang Q L, et al. A comprehensive investigation on the components in ionic liquid-based polymer inclusion membrane for Cr(Ⅵ) transport during electrodialysis[J]. Journal of Membrane Science, 2020, 604: 118016.
28	Wang Y Z, Wang P F, Xie H H, et al. Mechanistic investigation of intensified separation of molybdenum(Ⅵ) and vanadium(Ⅴ) using polymer inclusion membrane electrodialysis[J]. Journal of Hazardous Materials, 2023, 456: 131671.
29	Wang B Y, Liu F, Zhang F, et al. Efficient separation and recovery of cobalt(Ⅱ) and lithium(Ⅰ) from spent lithium ion batteries (LIBs) by polymer inclusion membrane electrodialysis (PIMED)[J]. Chemical Engineering Journal, 2022, 430: 132924.
30	Liu R H, Geng Y Q, Tian Z J, et al. Extraction of platinum(Ⅳ) by hydrophobic deep eutectic solvents based on trioctylphosphine oxide[J]. Hydrometallurgy, 2021, 199: 105521.
31	Liu L L, Zhu G P, Huang Q L, et al. Efficient recovery of Au(Ⅲ) through PVDF-based polymer inclusion membranes containing hydrophobic deep eutectic solvent[J]. Journal of Molecular Liquids, 2021, 343: 117670.

编辑推荐 0

Metrics

阅读次数

全文

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
0	0	4	0	0	25

来源	本网站	其他网站

次数	15	14
比例	52%	48%

摘要

最新录用	在线预览	正式出版

0	0	66

来源	本网站	其他网站

次数	14	52
比例	21%	79%

[1]	陈森洋, 靳蒲航, 谭志明, 谢公南. 质子交换膜燃料电池中蛇形流道液滴运动数值仿真研究[J]. 化工学报, 2024, 75(S1): 183-194.
[2]	李匡奚, 于佩潜, 王江云, 魏浩然, 郑志刚, 冯留海. 微气泡旋流气浮装置内流动分析与结构优化[J]. 化工学报, 2024, 75(S1): 223-234.
[3]	邱知, 谭明. 聚离子液体膜的制备及其在低钠高钾健康酱油中的应用[J]. 化工学报, 2024, 75(S1): 244-250.
[4]	刘律, 刘洁茹, 范亮亮, 赵亮. 基于层流效应的被动式颗粒分离微流控方法研究[J]. 化工学报, 2024, 75(S1): 67-75.
[5]	张丽萍, 孟晓荣, 宋锦峰, 杜金晶. VO₂@KH550/570@PS复合薄膜的制备及其热致相变性能[J]. 化工学报, 2024, 75(9): 3348-3359.
[6]	唐昊, 胡定华, 李强, 张轩畅, 韩俊杰. 抗加速度双切线弧流道内气泡动力学行为数值与可视化研究[J]. 化工学报, 2024, 75(9): 3074-3082.
[7]	陈引, 赵霄, 杜王芳, 杨竹强, 李凯, 赵建福. 喷雾冷却液膜流动特性测试方案优化及传热规律分析[J]. 化工学报, 2024, 75(8): 2734-2743.
[8]	王皓宇, 杨杨, 荆文婕, 杨斌, 唐雨, 刘毅. 不同旋流器作用下气液螺旋环状流动特性研究[J]. 化工学报, 2024, 75(8): 2744-2755.
[9]	王倩倩, 李冰, 郑伟波, 崔国民, 赵兵涛, 明平文. 氢燃料电池局部动态特征三维模型[J]. 化工学报, 2024, 75(8): 2812-2820.
[10]	李彦熹, 王晔春, 谢向东, 王进芝, 王江, 周煜, 潘盈秀, 丁文涛, 郭烈锦. 蜗壳式多通道气液旋流分离器结构优化及分离特性研究[J]. 化工学报, 2024, 75(8): 2875-2885.
[11]	胡军勇, 胡亚丽, 谭学诣, 黄佳欣, 张乐炜, 曾俊立, 刘晓奕, 陶源. 基于LiCl-NH₄Cl水溶液多级逆电渗析性能的实验研究[J]. 化工学报, 2024, 75(7): 2670-2679.
[12]	罗小平, 侯云天, 范一杰. 逆流相分离结构微细通道流动沸腾传热与均温性[J]. 化工学报, 2024, 75(7): 2474-2485.
[13]	张颂红, 赵欣怡, 楼小玲, 沈绍传, 贠军贤. 阳离子交换纳晶胶分离乳过氧化物酶的研究[J]. 化工学报, 2024, 75(7): 2574-2582.
[14]	白炳林, 杜燊, 李明佳, 张传琪. 基于水相剥离的单壁碳纳米管薄膜透光和导电特性[J]. 化工学报, 2024, 75(7): 2680-2687.
[15]	秦晓巧, 谭宏博, 温娜. 储能式低温空分系统热力学与经济性分析[J]. 化工学报, 2024, 75(7): 2409-2421.