机械活化强化锌焙砂中锌的浸出

doi:10.16085/j.issn.1000-6613.2022-0991

摘要/Abstract

摘要：

锌精矿焙烧阶段产生的铁酸锌（ZnFe₂O₄）是一类具有尖晶石结构的复合氧化物，性质稳定，不溶于稀酸和碱，在常规浸出条件下，仍有20%的锌以铁酸锌的形式存在于锌浸渣中，导致锌精矿焙烧产物的锌浸出率不高，一般为80%左右。机械活化具有使矿物晶格产生缺陷，降低反应对温度、酸浓度等条件依赖程度的优点。因此，本文采用机械活化对锌焙砂进行预处理，以硫酸为浸出剂，研究了机械活化时间、球料比、硫酸浓度、液固比、温度对锌的浸出率及其他杂质离子的影响规律。结果表明：锌的浸出率随机械活化时间的延长呈现出先增大后降低的趋势。机械活化（H₂C₂O₄·2H₂O与锌焙砂的质量比为3.60%，球料比为2∶1，球磨时间10min）-酸浸（70g/L H₂SO₄，液固比为10∶1，温度为35℃）工艺结果表明，锌的浸出率为87.61%，与未机械活化时相比（82.59%），锌的浸出率提高5个百分点。机理分析表明，机械活化使锌焙砂颗粒粒径变小，产生晶格畸变和局部破坏，锌焙砂中铁酸锌的结晶度从47.90%降至34.50%，使得浸出剂更易渗透到锌焙砂颗粒内部从而促进锌的浸出。

关键词: 浸取, 活化, 锌焙砂, 强化浸出, 锌

Abstract:

Zinc ferrite (ZnFe₂O₄) produced in the roasting stage of zinc concentrate is a group of complex oxides with spinel structure, stable in nature and insoluble in dilute acids and bases. Under conventional leaching conditions, 20% of zinc still exists in zinc leaching residue in the form of zinc ferrite, resulting in low zinc leaching rate of zinc concentrate roasting products, generally about 80%. Mechanical activation has the advantage of creating defects in the mineral lattice and reducing the dependence of reaction conditions such as temperature and acid concentration. Therefore, Mechanical activation was used to pretreat zinc calcine using sulfuric acid as the leaching agent. The effects of mechanical activation time, ball-to-material ratio, sulfuric acid concentration, liquid-to-solid ratio and temperature on zinc leaching efficiency and other impurity ions were investigated. The results showed that zinc leaching efficiency increased with increasing mechanical activation time. The leaching results using the mechanical activation (3.60% mass ratio of H₂C₂O₄·2H₂O to zinc calcine, 2∶1 ball-to-material ratio, 10min ball milling time)-acid leaching process indicated that the zinc leaching rate reached 87.61% with 70g/L H₂SO₄ and 10∶1 liquid to solid ratio at 35°C, which was 5% higher compared to that without mechanical activation (82.59%). Mechanistic analysis showed that mechanical activation reduced zinc calcine particle size, resulting in lattice distortion and localized damage. After mechanical activation, the crystallinity of zinc ferrite in zinc calcine decreased from 47.90% to 34.50%, thus the leaching agent penetrate into the zinc calcine particles more easily, promoting zinc leaching. The findings of this paper would provide a new approach to the green and low-carbon development of the electro-zinc industry.

Key words: leaching, activation, zinc calcine, enhanced leaching, zinc

中图分类号:

TF813

陈绍勤, 胡玲, 雷天涯, 王蓉, 舒建成, 陈梦君. 机械活化强化锌焙砂中锌的浸出[J]. 化工进展, 2023, 42(3): 1649-1658.

CHEN Shaoqin, HU Ling, LEI Tianya, WANG Rong, SHU Jiancheng, CHEN Mengjun. Mechanical activation for zinc enhanced leaching from zinc calcine[J]. Chemical Industry and Engineering Progress, 2023, 42(3): 1649-1658.

图/表 17

表1 锌焙砂的XRF化学组成

成分	质量分数/%
ZnO	64.23
Fe₂O₃	13.62
SO₃	9.55
SiO₂	5.00
PbO	2.08
CaO	1.56
CuO	1.09
Al₂O₃	0.68
MgO	0.61
MnO	0.45
CdO	0.27
As₂O₃	0.24

表2 锌焙砂含锌物相分析

物相	各物相占锌焙砂的质量分数/%	各物相中锌占总锌的质量分数/%
ZnSO₄	0.34	0.19
ZnO	49.42	53.22
Zn₂SiO₄	21.86	17.18
ZnFe₂O₄	24.40	8.83
ZnS	0.43	0.39
其他锌	3.54	20.19

图1 锌焙砂的XRD图谱分析

表3 参数设置

参数	值
机械活化时间/min	5、10、15、20、30、60
球料比	1∶2、1∶1、2∶1、3∶1、5∶1
硫酸浓度/g·L^-1	50、60、70、80、90
液固比/mL·g^-1	5∶1、7∶1、10∶1、13∶1、15∶1
温度/℃	25、35、45、55、65

图2 机械活化时间对锌的浸出率、浸出液中金属浓度和pH的影响[球料比1∶2，温度25℃，硫酸浓度70g/L，液固比10∶1(mL/g)，浸出时间120min]

图3 不同机械活化时间产物的XRD图谱

图4 球料比对锌的浸出率、浸出液中金属浓度和pH的影响[机械活化10min，温度25℃，硫酸浓度70g/L，液固比10∶1(mL/g)，浸出时间120min]

图5 不同球料比机械活化产物的XRD图谱

图6 硫酸浓度对锌的浸出率、浸出液中金属浓度和pH的影响[机械活化10min，球料比1∶2，温度25℃，液固比10∶1(mL/g)，浸出时间120min]

图7 液固比对锌的浸出率、浸出液中金属浓度和pH的影响[机械活化10min，球料比1∶2，温度25℃，硫酸浓度70g/L，浸出时间120min]

图8 温度对锌的浸出率、浸出液中金属浓度和pH的影响[机械活化10min，球料比1∶2，硫酸浓度70g/L，液固比10∶1(mL/g)，浸出时间120min]

图9 机械活化不同时间的粒度分布曲线

表4 机械活化时间对锌焙砂d10、d50、d90的影响

机械活化时间/min	d10/μm	d50/μm	d90/μm	锌浸出率/%
0	16.609	140.078	384.732	82.59
5	12.445	74.643	181.673	83.94
10	10.51	60.105	143.677	87.61
15	7.688	43.075	107.423	83.96
30	5.777	31.328	81.197	83.51
45	3.781	20.651	61.409	82.95
60	3.201	73.033	44.136	83.7

图10 不同样品的XRD图谱(1)锌焙砂；(2)球磨后的锌焙砂；(3)锌焙砂与H2C2O4·2H2O的机械活化产物；(4)将(1)浸出后得到的样品；(5)将(3)浸出后得到的样品

图11 不同样品的红外图谱

图12 不同样品的SEM表观形貌图和EDS图谱

图13 不同样品的XPS图谱(1) 锌焙砂；(2) 锌焙砂与H2C2O4·2H2O机械活化产物；(3) 将(2)浸出后得到的样品

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