用树脂吸附从铜电解液中去除锑铋实验

夏栋; 蒋晓云; 刘雅倩; 杨兴海

doi:10.3969/j.issn.1000-6532.2023.01.030

用树脂吸附从铜电解液中去除锑铋实验

长沙华时捷环保科技发展股份有限公司，湖南　长沙　410000

详细信息

作者简介: 夏栋（1988-），男，工程师，从事湿法冶金、废水处理及资源回收

通讯作者: 蒋晓云（1978-），女，博士，正高级工程师，从事污染防治与资源综合利用

中图分类号: TD98

收稿日期: 2021-01-18

刊出日期: 2023-02-25

Removal of Antimony and Bismuth in Copper Electrolyte by Resin Adsorption

Changsha Hasky Environmental Protection Science and Technology Development Co., Ltd., Changsha, Hunan, China

More Information

Corresponding author: Jiang Xiaoyun, 18973113478@163.com

Received Date: 18 January 2021

Publish Date: 25 February 2023

摘要

摘要:
研究采用树脂吸附法从铜电解液中去除锑、铋杂质，考查树脂对锑、铋的吸附能力，溶液流速和温度对锑、铋吸附的影响，以及洗脱剂类型、温度和添加剂等因素对锑、铋洗脱的影响。结果表明：树脂对锑、铋的吸附能力相同；降低溶液流速和提高温度均可提升锑、铋的吸附率；动态吸附实验中，树脂对铜电解液中的Sb、Bi、Pb和Fe有吸附效果，平均吸附率分别为94.4%、97.3%、75.9%和28.3%；锑的洗脱效果主要受酸度和Cl^-浓度影响，铋的洗脱效果主要受Cl^-浓度影响；一定温度下，在高浓度盐酸溶液中加入少量硫脲有利于Sb（V）的洗脱。
- 铜电解液 /
- Sb /
- Bi /
- 吸附 /
- 净化
Abstract:
Resin Adsorption was adopted for removal of Sb and Bi in copper electrolyte. A series of investigations were done respectively on: adsorption capacity of resin for Sb and Bi, affects of solution flow rate and temperature for the adsorption of Sb and Bi, affects of eluent types, temperature and additives for the elution efficiency of Sb and Bi. The experimental results showed that, the resin has the same adsorption capacity for Sb and Bi, the adsorption could be improved by the solution flow rate reducing and the temperature increasing. In the dynamic adsorption test, the resin has adsorption effect on Sb, Bi, Pb and Fe in copper electrolyte, and the average adsorption rates are 94.4%, 97.3%, 75.9% and 28.3%, respectively. The elution of Sb was mainly influenced by the concentrations of H⁺ and Cl^-. The elution of Bi was mainly influenced by the concentrations of Cl^-. It was beneficial for the elution of Sb (V) by adding thiourea in high concentration HCl solution at a certain temperature.
- Copper electrolyte /
- Sb /
- Bi /
- Adsorption /
- Purification

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图 1 树脂吸附结构

Figure 1.

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图 2 长时间动态吸附曲线

Figure 2.

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图 3 不同流速吸附曲线

Figure 3.

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图 4 不同温度吸附曲线

Figure 4.

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图 5 不同洗脱剂溶液洗脱曲线

Figure 5.

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图 6 温度和添加剂对锑、铋洗脱的影响

Figure 6.

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图 7 不同负载量实验的洗脱后液质量浓度和洗脱曲线

Figure 7.

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图 8 不同[Cl^-]浓度下lg[Sb³⁺]_T、lg[Bi³⁺]_T与[H⁺]浓度关系

Figure 8.

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表 1 铜电解液原液组成/（g·L^-1）

Table 1. Composition of copper electrolyte stock solution

Cu	As	Sb	Bi	Ni	Fe	H₂SO₄
45.54	12.71	0.18	0.26	12.61	0.21	178

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表 2 静态吸附实验结果

Table 2. Experimental results of static adsorption

元素	实验	C₀/ （mmol·L^-1）	C_e/ （mmol·L^-1）	E	Q/ （mmol·g^-1）	D
Sb	1	1.36	1.03	24.2%	0.263	256
	2	1.36	0.81	40.0%	0.217	267
	3	1.36	0.60	55.8%	0.151	252
	4	1.36	0.27	80.0%	0.108	400
	5	0.80	0.53	34.0%	0.108	206
Bi	1	1.34	1.04	22.5%	0.241	232
	2	1.34	0.83	37.9%	0.203	244
	3	1.34	0.61	54.6%	0.146	241
	4	1.34	0.27	79.6%	0.107	391
	5	0.89	0.58	34.6%	0.122	212

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表 3 铜电解液吸附前后成分/（g·L^-1）

Table 3. Composition of copper electrolyte before and after adsorption

成分	Cu	As	Sb	Bi	Ni	Fe	Pb	Zn
原液	45.54	12.71	0.18	0.26	12.61	0.21	0.029	0.206
吸附后液1	45.23	12.56	0.011	0.008	12.55	0.147	0.007	0.204
吸附后液2	45.64	12.63	0.009	0.006	12.60	0.154	0.007	0.199

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表 4 不同清洗剂条件下所得洗脱后液成分/（g·L^-1）

Table 4. Composition of the eluate obtained under different cleaning agent conditions

清洗剂类型	Sb	Bi	Cu	As	Fe
水	2.97	5.45	0.21	0.83	0.18
稀硫酸	3.10	5.31	0.02	0.21	0.11

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表 5 不同负载量实验的Sb和Bi树脂负载量/( mg·g^-1)

Table 5. Sb and Bi resin loadings of different loading experiments

实验	Sb树脂负载量	Bi树脂负载量
1	14.4	24.5
2	8.7	14.2

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表 6 Sb³⁺、Bi³⁺与Cl^-的配合平衡常数

Table 6. Coordination equilibrium constants of Sb³⁺、Bi³⁺ and Cl^-

平衡常数	lgβ₁	lgβ₂	lgβ₃	lgβ₄	lgβ₅	lgβ₆
Sb-Cl	2.26	3.49	4.18	4.72	4.70	4.10
Bi-Cl	2.35	4.40	5.45	6.65	7.29	7.09

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参考文献(13)

[1]	朱祖泽, 贺家齐. 现代铜冶金学[M]. 北京: 科学出版社, 2003. ZHU Z Z, HE J Q. Modern Copper Metallurgy [M]. Beijing: Science Press, 2003.
[2]	陈白珍, 仇勇海, 梅显芝, 等. 电积法脱铜脱砷的现状与进展[J]. 有色金属(冶炼部分), 1998(3):30-32. CHEN B Z, QIU Y H, MEI X Z, et al. Status and progress of copper and arsenic removal by electrowinning[J]. Nonferrous Metals (Extractive Metallurgy), 1998(3):30-32.
[3]	郑雅杰, 周文科, 彭映林, 等. 砷锑价态对铜电解液中砷锑铋脱除率的影响[J]. 中南大学学报(自然科学版), 2012, 43(3):821-826. ZHENG Y J, ZHOU W K, PENG Y L, et al. Influence of arsenic-antimony valence state on the removal rate of arsenic, antimony and bismuth in copper electrolyte[J]. Journal of Central South University(Natural Science Edition), 2012, 43(3):821-826.
[4]	李俊标, 李敬忠, 苏峰, 等. 萃取法回收铜电解液中锑铋研究与实践[J]. 铜业工程, 2017(6):47-51+7. LI J B, LI J Z, SU F, et al. Research and practice on recovery of antimony and bismuth from copper electrolyte by extraction method[J]. Copper Industry Engineering, 2017(6):47-51+7. doi: 10.3969/j.issn.1009-3842.2017.06.015
[5]	SALARI K, HASHEMIAN S, BAEI M T. 采用不同吸附剂从铜电解液中除锑(英文)[J]. Transactions of Nonferrous Metals Society of China, 2017, 27(2):440-449. SALARI K, HASHEMIAN S, BAEI M T. Antimony removal from copper electrolytes using different adsorbents (English)[J]. Transactions of Nonferrous Metals Society of China, 2017, 27(2):440-449. doi: 10.1016/S1003-6326(17)60050-5
[6]	何万年, 赵旺盛, 何思郏. 交换吸附法净化铜电解液中的锑和铋研究[J]. 有色金属(冶炼部分), 1998(3):27-29+36. HE W N, ZHAO W S, HE S J. Study on purification of antimony and bismuth in copper electrolyte by exchange adsorption method[J]. Nonferrous Metals (Extractive Metallurgy), 1998(3):27-29+36.
[7]	程霞霞. 树脂除杂技术在铜电解工业化应用研究[J]. 有色金属(冶炼部分), 2018(2):46-49. CHENG X X. Research on industrial application of resin impurity removal technology in copper electrolysis[J]. Nonferrous Metals (Extractive Metallurgy), 2018(2):46-49.
[8]	张子悦. 用氨基膦酸树脂从铜电解液中除锑[J]. 湿法冶金, 2011, 30(1):63. ZHANG Z Y. Antimony removal from copper electrolyte with aminophosphonic acid resin[J]. Hydrometallurgy, 2011, 30(1):63. doi: 10.13355/j.cnki.sfyj.2011.01.020
[9]	唐谟堂. 三氯化铋水解体系的热力学研究[J]. 中南矿冶学院学报, 1993(1):45-51. TANG M T. Thermodynamic study on the hydrolysis system of bismuth trichloride[J]. Journal of Zhongnan Institute of Mining and Metallurgy, 1993(1):45-51.
[10]	廖婷. 铜转炉白烟灰湿法提取铋的工艺研究[D]. 长沙: 中南大学, 2013. LIAO T. Research on wet extraction of bismuth from copper converter white soot[D]. Changsha: Central South University, 2013.
[11]	杜新玲. Sb~(³⁺)-Cl^--H₂O体系中三氯化锑水解平衡的研究[J]. 中国有色冶金, 2012, 41(5):75-79. DU X L. Study on hydrolysis equilibrium of antimony trichloride in Sb~(³⁺)-Cl^--H₂O system[J]. China Nonferrous Metals, 2012, 41(5):75-79. doi: 10.3969/j.issn.1672-6103.2012.05.020
[12]	徐振鑫. 铜阳极泥复合酸浸砷锑铋工艺及锑铋水解机理研究[D]. 赣州: 江西理工大学, 2020. XU Z X. Research on the composite acid leaching of arsenic, antimony and bismuth of copper anode slime and the hydrolysis mechanism of antimony and bismuth[D]. Ganzhou: Jiangxi University of Science and Technology, 2020.
[13]	鲁道荣, 李学良, 林建新. 砷锑铋对阴极铜沉积过程的影响[J]. 应用化学, 1998(2):59-62. LU D R, LI X L, LIN J X. Influence of arsenic, antimony and bismuth on cathode copper deposition process[J]. Applied Chemistry, 1998(2):59-62.