酸性蚀刻废液超临界水热制备纳米铜和氧化铜

doi:10.16183/j.cnki.jsjtu.2023.618

摘要/Abstract

摘要：

以酸性蚀刻废液为原料,采用超临界水热合成法制备出稳定性好的纳米铜和氧化铜粉体.考察不同加碱量对纳米氧化铜粉体制备效果的影响,通过试验验证了除杂效果,探讨了氧化铜形貌控制机理,并分析了腐蚀对产物纯度的影响.结果表明,在优化后参数下,以除杂后酸性蚀刻废液为前驱物制备的纳米铜和纳米氧化铜的平均粒径分别为82和52 nm,纯度分别为99.41%和99.2%.建立了酸性蚀刻废液预处理的工艺流程,并开发出一种以酸性蚀刻废液为前驱物的高纯纳米铜和纳米氧化铜合成工艺.最后,基于处理量480 L/h的中试规模连续式装置,进行了技术经济性评估.

关键词: 酸性蚀刻废液, 超临界水热合成, 纳米铜粉, 纳米氧化铜, 合成工艺

Abstract:

Stable copper and copper oxide nanoparticles are prepared by supercritical hydrothermal synthesis using acidic etching waste solution as the raw material. The effect of different alkali additions on the preparation of copper oxide nanoparticles is investigated, and verification test of the effect of impurity removal is conducted. The control mechanism of copper oxide morphology is obtained, and the effect of corrosion on the purity of final products is analyzed. The results show that under optimized parameters, copper and copper oxide nanoparticles prepared from acidic etching waste liquid have average particle sizes of 82 nm and 52 nm, respectively, with purities of 99.41% and 99.2%, after the removal of impurities. The technological process for the pre-treatment of acidic etching waste is established, and the synthesis process of high-purity nano copper and nano-copper oxide using acidic etching waste as precursor is developed. Finally, the technical economy is accounted based on a pilot-scale continuous plant with a treatment capacity of 480 L/h.

Key words: acidic etching waste solution, supercritical hydrothermal synthesis, copper nanoparticles, copper oxide nanoparticles, synthesis process

中图分类号:

刘慧, 王树众, 杨健乔, 王进龙, 李艳辉. 酸性蚀刻废液超临界水热制备纳米铜和氧化铜[J]. 上海交通大学学报, 2025, 59(12): 1942-1951.

LIU Hui, WANG Shuzhong, YANG Jianqiao, WANG Jinlong, LI Yanhui. Supercritical Hydrothermal Preparation of Copper and Copper Oxide Nanoparticles from Acidic Etching Waste Solution[J]. Journal of Shanghai Jiao Tong University, 2025, 59(12): 1942-1951.

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元素	质量分数/%	元素	质量分数/%
Cu	9.16	Ni	39.18×10^-4
Fe	75.15×10^-4	Pb	18.03×10^-4
Zn	82.84×10^-4	Cl	30
Al	23.19×10^-4

元素	质量浓度/(μg·mL^-1)		去除率/%
元素	除杂前	除杂后	去除率/%
Cu	14179	13800	2.7
Zn	12.824	0.553	95.7
Ni	6.065	0.328	94.6
Fe	11.633	< 0.01	100.0
Al	3.590	0.379	89.4
Pb	2.791	0.004	99.8
Cl	37107	113.4	99.7

参数	取值
温度/℃	400
压力/MPa	25
Cu²⁺浓度/(mol·L^-1)	0.2
加碱比例	2∶1
反应时间/s	0.54

成分	w/%	成分	w/%
CuO	99.2	Zn	0.09
Zr	0.27	Al	0.02
Si	0.22	Ni	0.01
S	0.14	-	-

参数	取值
温度/℃	400
压力/MPa	25
Cu²⁺浓度/(mol·L^-1)	0.05
还原剂种类	甲酸
还原剂比例	8∶1
PVP比例	3∶1
反应时间/s	0.54