碳酸铵高效浸出黄铜矿的机理研究

doi:10.12034/j.issn.1009-606X.225308

过程工程学报 ›› 2026, Vol. 26 ›› Issue (9): 1021-1030.DOI: 10.12034/j.issn.1009-606X.225308

碳酸铵高效浸出黄铜矿的机理研究

孙和云¹^,²^,³^,⁴(), 阮仁满²^,³(), 邓久帅¹^,⁴(), 牛晓鹏²^,³

^1.中国矿业大学(北京)化学与环境工程学院，有色金属行业三稀资源综合利用工程技术研究中心，有色金属行业共伴生资源分离加工重点实验室，北京 100083
^2.中国科学院过程工程研究所战略性金属资源绿色循环利用国家工程技术研究中心，北京 100190
^3.中国科学院过程工程研究所绿色过程与工程重点实验室，北京 100190
^4.中国矿业大学(北京)内蒙古研究院，内蒙古鄂尔多斯 017001

收稿日期:2025-12-09 修回日期:2026-02-09 出版日期:2026-03-04 发布日期:2026-09-28
通讯作者: 阮仁满,邓久帅 sunhy@ipe.ac.cn;rrruan@126.com;jsdeng@cumtb.edu.cn
作者简介:孙和云，博士研究生，高级工程师，矿物加工和湿法冶金专业，E-mail: sunhy@ipe.ac.cn；
阮仁满，研究员，研究方向为矿物加工和湿法冶金，E-mail: rrruan@126.com
邓久帅，教授，研究方向为矿物加工工程，E-mail: jsdeng@cumtb.edu.cn
基金资助:
中国科学院战略性先导科技专项(XDA0430304)

Mechanism study on efficient leaching of chalcopyrite by ammonium carbonate

Heyun SUN¹^,²^,³^,⁴(), Renman RUAN²^,³(), Jiushuai DENG¹^,⁴(), Xiaopeng NIU²^,³

^1.Key Laboratory of Separation and Processing of Symbiotic-associated Mineral Resources in Non-ferrous Metal Industry, Engineering Technology Research Center for Comprehensive Utilization of Rare Earth-rare Metal-rare Scattered in Non-ferrous Metal Industry, School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China
^2.National Engineering Research Center for Green Recycling of Strategic Metal Resources, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^4.Inner Mongolia Research Institute, China University of Mining and Technology (Beijing), Ordos, Inner Mongolia 017001, China

Received:2025-12-09 Revised:2026-02-09 Online:2026-03-04 Published:2026-09-28
Contact: Renman RUAN, Jiushuai DENG sunhy@ipe.ac.cn;rrruan@126.com;jsdeng@cumtb.edu.cn

摘要/Abstract

摘要：

黄铜矿氨浸过程中产生的铁氧化物等中间产物是导致矿物表面钝化和制约浸出效率的关键因素，一直是该领域的研究热点。为阐明(NH₄)₂CO₃体系浸出黄铜矿的速率显著高于其他铵盐体系的原因，本工作利用密闭的磁力搅拌装置，系统探究低氧条件下(NH₄)₂CO₃浸出黄铜矿的动力学行为及反应机理。结果表明，(NH₄)₂CO₃可高效浸出黄铜矿，密闭低氧条件下铜浸出率达89.67%。通过采用扫描电子显微镜-能量色散X射线谱仪(SEM-EDS)、X射线衍射(XRD)、拉曼光谱及热重-差示扫描量热法及TG-DSC等多种表征技术，发现(NH₄)₂CO₃浸出黄铜矿过程的中间产物为(NH₄)₂Fe₂(OH)₄(CO₃)₂·H₂O，该中间产物大多分散于浸出液中，部分以疏松多孔的形态沉积在黄铜矿表面，对黄铜矿浸出动力学影响较小。热力学计算与溶液化学实验证实，黄铜矿表面氧化溶解的Fe²⁺可与溶液中的 $C O 3 2 -$ 生成稳定可溶性络合物，并在 $N H 4 +$ 和OH^-的作用下，生成针状的(NH₄)₂Fe₂(OH)₄(CO₃)₂·H₂O中间产物；有氧条件下，该中间产物可进一步转化为相同晶型的赤铁矿等铁氧化物。本研究明确了黄铜矿氨浸过程中新的铁中间产物及其生成与转化路径，揭示了(NH₄)₂CO₃高效浸出黄铜矿的新机制，完善了黄铜矿氨浸机理，为该体系的工业化应用提供了重要理论支撑。

关键词: 黄铜矿, 碳酸铵, 碱式碳酸铁铵, 浸出

Abstract:

Intermediate iron oxides and other products formed during the ammonia leaching of chalcopyrite are considered primary causes of passivation and restricting leaching efficiency, making them a persistent research focus in this field. To elucidate why the leaching rate of chalcopyrite in the (NH₄)₂CO₃ system is significantly higher than in other ammonium salt systems, this work systematically investigates the kinetic behavior and reaction mechanism of chalcopyrite leaching by (NH₄)₂CO₃ under low-oxygen conditions using a sealed magnetic stirring apparatus. The results demonstrate that (NH₄)₂CO₃ can efficiently leach chalcopyrite, the copper extraction efficiency reaches 89.67%. Through various characterization techniques including scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), X-ray diffraction (XRD), Raman spectroscopy, and thermogravimetry-differential scanning calorimetry (TG-DSC), the intermediate product formed during the (NH₄)₂CO₃ leaching process is identified as (NH₄)₂Fe₂(OH)₄(CO₃)₂·H₂O. This intermediate product partially disperses in the leaching solution and partially deposits on the chalcopyrite surface in a loose, porous morphology, exerting minimal influence on leaching kinetics. Thermodynamic calculations and solution chemistry experiments confirmed that Fe²⁺ oxidized and dissolved from the chalcopyrite surface can form stable soluble complexes with $C O 3 2 -$ in solution, and subsequently generate needle-shaped (NH₄)₂Fe₂(OH)₄(CO₃)₂·H₂O intermediate products under the action of $N H 4 +$ and OH^-. Under aerobic conditions, this intermediate further transforms into iron oxides such as hematite with the same crystal structure. This study identifies a new iron intermediate product and its formation and transformation pathways during the ammonia leaching of chalcopyrite, reveals a novel mechanism for the efficient leaching of chalcopyrite by (NH₄)₂CO₃, refines the understanding of chalcopyrite ammonia leaching mechanisms, and provides important theoretical support for the industrial application of this system.

Key words: chalcopyrite, ammonium carbonate, basic ferric ammonium carbonate, leaching

中图分类号:

TF811

孙和云, 阮仁满, 邓久帅, 牛晓鹏. 碳酸铵高效浸出黄铜矿的机理研究[J]. 过程工程学报, 2026, 26(9): 1021-1030.

Heyun SUN, Renman RUAN, Jiushuai DENG, Xiaopeng NIU. Mechanism study on efficient leaching of chalcopyrite by ammonium carbonate[J]. The Chinese Journal of Process Engineering, 2026, 26(9): 1021-1030.

图/表 12

图1 氨浸黄铜矿过程的(a) 初始浸出液、(b) 中间浸出液、(c) 矿浆、(d) 原矿和(e) 浸渣

Fig.1 (a) The initial leachate, (b) intermediate leachate, (c)slurry, (d) initial chalcopyrite, and (e) leaching residue of the ammonia leaching process of chalcopyrite

图2 黄铜矿中铜浸出率随氨浸时间的变化

Fig.2 Variation of copper extraction efficiency of chalcopyrite with ammonia leaching time

图3 氨浸黄铜矿过程中(a) pH、(b) ORP、(c) 温度和(d) 氨浓度的变化[1 mol/L (NH4)2CO3，500 r/min，粒度-1000+105 µm，室温]

Fig.3 Variations of (a) pH, (b) ORP, (c) temperature, and (d) ammonia concentration in the ammonia leaching process of chalcopyrite [1 mol/L (NH4)2CO3, 500 r/min, size fraction of -1000+105 µm, and room temperature]

图4 (a) 黄铜矿对照组、(b) 浸出9天实验组和(c) 浸出48天终点浸渣的表面形貌及元素分布

Fig.4 Surface morphologies and element distributions of (a) control group of chalcopyrite, (b) leaching test group at 9 days, and (c) leaching endpoint at 48 days of leaching residue

表1 浸渣的EDS结果

Table 1 EDS results of the leaching residue

Sample	Spot	Content/at%				Cu/Fe	S/Fe
Sample	Spot	Cu	Fe	S	O	Cu/Fe	S/Fe
Initial chalcopyrite	1	23.43	24.27	46.68	5.62	0.97	1.92
Residue (9 day)	2	3.86	24.21	6.97	64.96	0.16	0.29
Residue (48 day)	3	1.54	29.48	0.00	68.97	0.05	0.00

图5 48天浸渣截面的SEM-EDS

Fig.5 Cross-sectional SEM-EDS micrograph of the leaching residue after 48 days

表2 48天浸渣截面的EDS结果

Table 2 Cross-sectional EDS results of the leaching residue after 48 days

Sample	Spot	Content/at%				Cu/Fe	S/Fe
Sample	Spot	Cu	Fe	S	O	Cu/Fe	S/Fe
Residue (48 day)	1	25.14	26.32	43.05	5.49	0.96	1.64
	2	16.32	26.64	33.11	23.92	0.61	1.24
	3	6.76	36.06	14.99	42.19	0.19	0.42
	4	3.35	45.25	7.64	43.75	0.07	0.17
	5	1.42	48.82	0.10	48.65	0.03	0.00

表3 48天浸渣的BET比表面积和孔隙率

Table 3 BET specific surface area and porosity of the leaching residue after 48 days

Sample	BET specific surface area/(m²/g)	Porosity/%
Initial chalcopyrite	0.053	0.19
Residue (48 day)	9.290	42.20

图6 纯黄铜矿和氨浸48天后黄铜矿浸渣的(a) XRD谱及(b) 拉曼光谱

Fig.6 (a) XRD patterns and (b) Raman spectra of pure chalcopyrite and chalcopyrite leaching residue by ammonia leaching after 48 days

图7 (NH4)2Fe2(OH)4(CO3)2·H2O的TG-DSC结果

Fig.7 TG-DSC result of (NH4)2Fe2(OH)4(CO3)2·H2O

图8 Cu-Fe-CO32-体系Eh-pH图 ([Cu2+]TOT=50.00 mmol/L, [CO32-]TOT=50.00 mmol/L, [Fe3+]TOT=50.00 mmol/L, [M]TOT表示对应元素/碳酸根的溶解浓度)

Fig.8 Eh-pH diagram of the Cu-Fe-CO32- system ([Cu2+]TOT=50.00 mmol/L, [CO32-]TOT=50.00 mmol/L, [Fe3+]TOT=50.00 mmol/L, [M]TOT represents the dissolved concentration of the corresponding element/carbonate)

图9 密封、低氧条件下(NH4)2CO3浸出黄铜矿的机理

Fig.9 Mechanism of chalcopyrite leaching by ammonium carbonate under sealed low-oxygen conditions

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碳酸铵高效浸出黄铜矿的机理研究

Mechanism study on efficient leaching of chalcopyrite by ammonium carbonate

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