废锌基脱硫剂与铜锌基催化剂协同真空碳热提取锌

doi:10.16085/j.issn.1000-6613.2023-1428

摘要/Abstract

摘要：

针对废锌基脱硫剂及铜锌基催化剂中金属提取工艺流程长、污染物产生量大的问题，提出了利用真空碳热还原方法将两种物料中铜和锌实现高效、清洁协同分离利用的技术思路。在对废脱硫剂、铜锌基催化剂化学成分及主要物相检测的基础上进行了真空碳热协同提取分离铜和锌的实验研究，通过调整加热温度、保温时间、配料比等获得了较优的锌挥发工艺条件，并深入分析了工艺机理。研究结果表明，以ZnS为主要物相的废脱硫剂和以CuO和ZnO为主要物相的废铜锌基催化剂协同在真空碳热还原时可有效地将两种物料中的锌充分还原挥发。铜锌基催化剂、脱硫剂及碳以C∶(ZnO+CuO)=1∶1（摩尔比）、CuO∶ZnS=2∶1（摩尔比）的配料组成混合物料，加热至1100℃保温60min，锌的还原挥发率可达到99.56%，还原渣中铜品位可达到59.46%，还原渣中铜主要为Cu_1.96S，可作为冰铜吹炼原料使用。

关键词: 锌基脱硫剂, 铜锌基催化剂, 真空碳热还原, 协同利用, 回收, 相平衡, 催化剂

Abstract:

To solve the problems of long process and large amount of pollutants in metal extraction of waste zinc-based desulfurizer and copper-zinc-based catalyst, a technical method of efficient and clean synergistic separation and utilization of the copper and zinc in the two materials by vacuum carbothermal reduction method was proposed. On the basis of the characterizations of the chemical composition and main phase of the waste desulfurizer and copper-zinc-based catalyst, the experimental study of vacuum carbothermal synergistic extraction and separation of copper and zinc was carried out. The optimum zinc volatilization process conditions were obtained by adjusting the heating temperature, holding time and batch ratio, and the process mechanism was analyzed in depth. The results showed that the waste desulfurizer with ZnS as the main phase and the scrap copper-zinc-based catalyst with CuO and ZnO as the main phase could effectively reduce and volatilize the zinc in the two materials during vacuum carbothermal reduction. The mixture of copper-zinc-based catalyst, desulfurizer, and carbon with C∶ (ZnO + CuO) as 1∶1 (molar ratio) and CuO∶ZnS as 2∶1 (molar ratio) was heated to 1100℃ for 60min, the reduction and volatilization rate of zinc reached 99.56%, and the copper grade in the reduced slag was 59.46% with the copper existing mainly as Cu_1.96S, which could be used as ice copper blowing raw materials.

Key words: zinc-based desulfurizer, copper-zinc-based catalyst, vacuum carbothermal reduction, synergistic utilization, recovery, phase equilibria, catalyst

中图分类号:

TF813

马红周, 党煜博, 王耀宁, 曾劲阳, 赵小军, 史建伟. 废锌基脱硫剂与铜锌基催化剂协同真空碳热提取锌[J]. 化工进展, 2024, 43(9): 5275-5281.

MA Hongzhou, DANG Yubo, WANG Yaoning, ZENG Jinyang, ZHAO Xiaojun, SHI Jianwei. Zinc-based desulfurizer scrap and copper-zinc-based catalyst synergistic vacuum carbothermal extraction of zinc[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 5275-5281.

图/表 11

表1 X荧光检测结果（质量分数） (%)

物料	MgO	Al₂O₃	SiO₂	SO₃	Cl	K₂O	CaO	TiO₂	Fe₂O₃	NiO	ZnO	CuO
废脱硫剂	0.21	0.41	0.44	41.87	0.69	0.04	0.35	0.02	0.05	0.05	55.88	—
铜锌基催化剂	0.22	10.53	0.9	0.84	0.15	0.02	0.54	0.01	0.32	0.03	33.22	53.13

图1 废脱硫剂及铜锌基催化剂主要物相

表2 兰炭粉工业成分分析结果（质量分数）单位：%

灰分	挥发分	固定碳	Al₂O₃	CaO
7.6	3.73	75	2.18	2.29

表3 可能发生的反应及其起始反应温度

反应式	起始反应温度/℃	编号
CuO+C $̿$ Cu+CO_(g)	<200	(2)
2CuO+C $̿$ 2Cu+CO_2(g)	<200	(3)
ZnO+C $̿$ Zn_(g)+CO_(g)	500	(4)
2ZnO+C $̿$ 2Zn_(g)+CO_2(g)	550	(5)
ZnS+2Cu $̿$ Cu₂S+Zn_(g)	750	(6)
2ZnS+C $̿$ 2Zn_(g)+CS_2(g)	900	(7)
ZnS+Cu $̿$ CuS+Zn_(g)	1050	(8)

表3 可能发生的反应及其起始反应温度

反应式	起始反应温度/℃	编号
CuO+C $̿$ Cu+CO_(g)	<200	(2)
2CuO+C $̿$ 2Cu+CO_2(g)	<200	(3)
ZnO+C $̿$ Zn_(g)+CO_(g)	500	(4)
2ZnO+C $̿$ 2Zn_(g)+CO_2(g)	550	(5)
ZnS+2Cu $̿$ Cu₂S+Zn_(g)	750	(6)
2ZnS+C $̿$ 2Zn_(g)+CS_2(g)	900	(7)
ZnS+Cu $̿$ CuS+Zn_(g)	1050	(8)

图2 各反应的ΔG-T关系图

表4 真空碳热还原起始反应物、产物的名称及数量

名称	物质的量/mol
起始反应物
ZnO	1
CuO	2
ZnS	1
C	4
产物
Zn	0
Cu	0
Cu₂S	0
Zn_(g)	0
CO	0
CO₂	0

图3 混合物料反应过程计算结果

图4 加热温度对锌挥发率的影响

图5 铜锌基催化剂的保温时间对锌提取的影响

图6 铜锌基催化剂和脱硫剂催化剂协同焙烧

图7 还原渣物相

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