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有色金属(冶炼部分):2025,(6):146-153
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铜捕集回收废汽车尾气净化催化剂中铂族金属
张帆1,王海北2,张金池1,刘贵清1,王芳1,李拓夫2
(1.江苏北矿金属循环利用科技有限公司,江苏 徐州 221121;2.矿冶科技集团有限公司,北京 100160)
Copper Trapping Recycling of Platinum Group Metals from Spent Automotive Exhaust Purification Catalysts
ZHANG Fan1, WANG Haibei2, ZHANG Jinchi1, LIU Guiqing1, WANG Fang1, LI Tuofu2
(1. Jiangsu BGRIMM Metal Recycling Science & Technology Co., Ltd., Xuzhou 221121, Jiangsu, China; 2. BGRIMM Technology Group, Beijing 100160, China)
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投稿时间:2024-11-27    
中文摘要: 废汽车尾气净化催化剂是重要的铂族金属二次资源之一,其高效回收是行业的重要课题。以CuO为捕集剂,选取CaO-SiO2-Al2O3-B2O3-MgO渣型,对废汽车尾气净化催化剂中铂族金属进行捕集回收,从热力学角度分析了铜捕集铂族金属的可行性,系统探究了熔炼温度、熔炼时间、碱度、石英砂与硼砂质量比和捕集剂用量等因素对Pt、Pd、Rh回收率的影响。研究表明,在熔炼温度1 400 ℃、熔炼时间6 h、碱度1.1、石英砂与硼砂质量比1︰2和捕集剂用量占原料质量16%的最优条件下,熔炼渣中Pt、Pd、Rh的平均品位分别为1.4、6.5、1.0 g/t,Pt、Pd、Rh回收率分别达到99.18%、99.41%、98.62%。
Abstract:With the continuous increase in the number of motor vehicles and the tightening of environmental policies, the requirement for automotive exhaust purification catalysts is constantly increasing. When a large number of cars are scrapped, how to dispose of the spent automotive exhaust purification catalysts reasonably is a major social problem. Spent automotive exhaust purification catalysts contain a large amount of platinum group metals (PGMs) with high-value, which are important secondary resources of PGMs. In the current situation of scarce PGMs resources and long-term dependence on foreign imports, efficient recovery of PGMs from spent automotive exhaust purification catalysts plays an important role in the recycling of resources and alleviating the supply-demand contradiction of PGMs in China. Using pyrometallurgical technology and copper trapping method, efficient separation between base metal carriers and PGMs can be achieved. Using spent automotive exhaust purification catalysts as experimental materials and CuO as the trapping agent, CaO-SiO2-Al2O3-B2O3-MgO slag type was selected to conduct research on the pyrometallurgical technology and copper trapping of PGMs in spent automotive exhaust purification catalysts. The feasibility of copper trapping PGMs was analyzed from a thermodynamic perspective. In the process of copper trapping, using coke as a reducing agent, it is necessary to focus on analyzing the thermodynamic behavior of various metal oxides during carbon reduction process. The effects of melting temperature, melting time, basicity, the mass ratio of quartz sand and borax, and trapping agent dosage on the recovery rates of Pt, Pd, and Rh were systematically studied. The main chemical components of the experimental materials and products were analyzed using inductively coupled plasma optical emission spectrometer (ICP-OES) and spectrophotometer. The phase composition of the experimental materials and copper alloy were analyzed using X-ray diffractometer (XRD). The microstructure and energy spectrum of the copper alloy characterized by field emission scanning electron microscope and energy dispersive spectrometer (SEM-EDS). The thermodynamic research results indicate that the copper oxide and platinum group metal oxides can be reduced to their corresponding metals at high temperatures. Then, the PGMs generated by reduction were trapped and enriched in the copper alloy by the new ecological copper liquid, forming corresponding continuous solid solutions. The experimental research results show that when the temperature of reduction melting is continuously increased from 1 350 ℃ to 1 400 ℃, all the recovery rate of Pt, Pd, and Rh is improved. The recovery rate of Pt, Pd, and Rh gradually increases with the extension of the reduction smelting time, and then tend to stabilize. After six hours of smelting reaction, the copper trapping reaction basically reaches dynamic equilibrium. As the basicity increases, the recovery of PGMs rises firstly and then decreases. With the increase of borax dosage, the recovery of Pt, Pd, and Rh increases firstly and then decreases. Determining the appropriate amount of borax is crucial. After increasing the amount of trapping agent, the recovery rate of Pt, Pd, and Rh is gradually improved. Select an appropriate amount of capture agent based on production costs and recovery rate. Under the optimal conditions of melting temperature of 1 400 ℃, melting time of 6 h, basicity of 1.1, the mass ratio of quartz sand to borax of 1:2, and trapping agent dosage accounting of 16% of mass fraction of the raw material, the results of three parallel verification experiment indicate that the average grade of Pt, Pd and Rh in the melting slag is 1.4, 6.5 and 1.0 g/t, respectively, while the recovery rate of Pt, Pd and Rh reaches to 99.18%, 99.41% and 98.62%, respectively. The main component of the alloy product is Cu, with a grade of 92.84%. The grade of Pt, Pd, and Rh in copper alloy is 0.27%, 1.88% and 0.13%, respectively, indicating that they have been highly enriched. XRD patterns show that PGMs form phases such as Cu3Pt, CuPd, and CuRh in copper alloys, respectively. The results of energy dispersive spectroscopy analysis show that the non-precious metal elements in copper alloys are mainly composed of Cu, C, and O, and the Pt, Pd and Rh is unevenly distributed on Cu.
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基金项目:山东省重点研发计划项目(2023CXGC010903)
引用文本:
张帆,王海北,张金池,刘贵清,王芳,李拓夫.铜捕集回收废汽车尾气净化催化剂中铂族金属[J].有色金属(冶炼部分),2025(6):146-153.
ZHANG Fan,WANG Haibei,ZHANG Jinchi,LIU Guiqing,WANG Fang,LI Tuofu.Copper Trapping Recycling of Platinum Group Metals from Spent Automotive Exhaust Purification Catalysts[J].Nonferrous Metals (Extractive Metallurgy),2025(6):146-153.

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