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过程工程学报 ›› 2022, Vol. 22 ›› Issue (5): 689-698.DOI: 10.12034/j.issn.1009-606X.221085

• 研究论文 • 上一篇    

MOCVD生产废料中镓、铟提取工艺及其动力学研究

饶富1,2， 郑晓洪1,3， 张西华2*， 陶天一1， 曹宏斌1， 吕伟光1， 孙峙1,2*   

  1. 1. 中国科学院过程工程研究所环境技术与工程研究部，绿色过程与工程重点实验室，北京市过程污染控制工程技术研究中心，北京 100190 2. 上海第二工业大学电子废弃物研究中心，资源循环科学与工程中心，上海电子废弃物资源化协同创新中心，上海 201209 3. 中国地质大学(北京)材料科学与工程学院，北京非金属矿物与固体废物材料利用重点实验室，矿物材料国家重点实验室，北京 100083
  • 收稿日期:2021-03-14 修回日期:2021-06-03 出版日期:2022-05-28 发布日期:2022-05-27
  • 通讯作者: 孙峙 sunzhi@ipe.ac.cn
  • 作者简介:饶富(1994-)，男，江西省赣州市人，硕士研究生，环境工程专业；通讯联系人，张西华，E-mail: zhangxh@sspu.edu.cn；孙峙，E-mail: sunzhi@ipe.ac.cn.
  • 基金资助:
    国家科技部重点专项;国家科技部重点专项;国家自然科学基金;国家自然科学基金青年科学基金项目

Research on recovery process and kinetics of gallium and indium from MOCVD production waste

Fu RAO1,2,  Xiaohong ZHENG1,3,  Xihua ZHANG2*,  Tianyi TAO1,  Hongbin CAO1,  #br# Weiguang LÜ1,  Zhi SUN1,2*   

  1. 1. Beijing Engineering Research Center of Process Pollution Control, Key Laboratory of Green Process and Engineering, Division of Environment Technology and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China 2. WEEE Research Center, Research Center of Resource Recycling Science and Engineering, Shanghai Polytechnic University, Shanghai Collaborative Innovation Center for WEEE Recycling, Shanghai 201209, China 3. Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences (Beijing), Beijing 100083, China
  • Received:2021-03-14 Revised:2021-06-03 Online:2022-05-28 Published:2022-05-27

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摘要： 近年来，LED以其节能及环境友好等特性被广泛运用于各类照明领域。作为LED产品关键部件，采用金属有机气相沉积(MOCVD)生产外延片过程产生大量的生产废料。随着LED行业的快速发展，绿色、清洁回收MOCVD生产废料备受关注。本研究以硫酸为浸出剂，重点研究了MOCVD生产废料中Ga和In元素的浸出行为和浸出动力学。通过对浸出试剂种类、H2SO4浓度、固液比、浸出温度和浸出时间等参数的过程优化，在H2SO4浓度3 mol/L、固液比50 g/L、温度80℃、反应2 h的最佳工艺条件下，Ga和In的浸出率仅为67.50%和91.46%。动力学研究表明，在293.15~333.15 K温度范围内，Ga和In的浸出动力学符合收缩核模型，浸出过程受表面化学反应和外扩散混合控制。同时，XRD和SEM-EDS结果也印证了符合收缩核模型。在293.15~333.15 K温度范围内，Ga和In的浸出活化能分别为25.7和21.7 kJ/mol。基于对Ga和In浸出行为的动力学分析，提出并验证了MOCVD生产废料强化焙烧-浸出工艺的可行性。研究结果表明，强化焙烧-酸浸工艺可以使Ga和In的浸出率分别由67.50%和91.46%提升至88.27%和98.32%，并得到了氧化镓副产品。本研究结果有望为MOCVD生产废料的工业化资源循环提供基础数据支撑和新路径选择。

关键词: MOCVD, 浸出, 镓, 铟, 动力学

Abstract: In recent years, LED has been widely used in various lighting fields because of its energy-saving and environment-friendly characteristics. As a key part of LED products, epitaxial wafers are produced by metal-organic vapor deposition (MOCVD). With the rapid development of the LED industry, green and clean recycling of MOCVD production waste has attracted much attention. In this study, the leaching behavior and kinetics of Ga and In elements from MOCVD production waste were studied with sulfuric acid as a leaching agent. The effects of different types of leaching agents, H2SO4 concentration, solid-liquid ratio, leaching temperature and leaching time on the leaching efficiencies of Ga and In were systemically investigated. It was found that the leaching efficiencies of Ga and In can reach 67.50% and 91.46% under the optimal conditions of H2SO4 concentration of 3 mol/L, the solid-liquid ratio of 50 g/L, the temperature of 80℃, and the reaction of 120 min. The kinetics study showed that the leaching kinetics of Ga and In in the temperature range of 293.15~333.15 K was by the shrinkage core model, and the leaching process was controlled by surface chemical reaction and external diffusion mixing. At the same time, the results of XRD and SEM-EDS also confirmed the agreement with the shrinkage kernel model. The activation energies of Ga and In are 25.7 and 21.7 kJ/mol, respectively, when the leaching temperature was ranged from 293.15 K to 333.15 K. Based on the kinetics behavior of Ga and In leaching, the feasibility of enhanced roasting-acid leaching process was proposed and verified. It was found that the leaching efficiencies of Ga and In can be increased from 67.50% and 91.46% to 88.27% and 98.32%, respectively, under the enhanced roasting-acid leaching process. And gallium oxide byproducts were obtained. The findings from this research are expected to provide technical support and alternative for industrial recycling of critical metals from MOCVD production waste.

Key words: MOCVD, leaching, gallium, indium, kinetics