锌的生物浸出技术现状及研究进展

李旭; 高文成; 温建康; 武彪; 刘学

doi:10.13374/j.issn2095-9389.2019.09.24.001

锌的生物浸出技术现状及研究进展

doi: 10.13374/j.issn2095-9389.2019.09.24.001

有研工程技术研究院有限公司生物冶金国家工程实验室，北京 101407

基金项目: 云南省科技厅重点研发计划资助项目（2018IB027）

详细信息

通讯作者:
E-mail：kang3412@126.com

中图分类号: TF18
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出版历程
- 收稿日期: 2019-09-24
- 刊出日期: 2020-06-01

Technology status and research progress of zinc bioleaching

National Engineering Laboratory of Biohydrometallury, GRIMAT Engineering Institute Co., Ltd, Beijing 101407, China

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Corresponding author: E-mail: kang3412@126.com

摘要

摘要: 锌是现代工业所必需的有色金属，属于很重要的战略资源，其在世界所有金属产量中排名第四，仅次于铁、铝和铜。随着低品位难处理锌资源的种类和产量的不断增加，以及湿法冶金技术的不断发展，锌的生物浸出技术得到了研究人员的广泛关注，并展示出了良好的潜在应用前景。本文首先较为详细的介绍了含锌资源的矿物特征，并对其生物可浸性进行了分析。其次，对目前锌的生物浸出体系，所用浸矿菌种，浸出过程所涉及的电化学、热力学、动力学以及浸出机理进行了归纳总结；接着，对锌的生物浸出技术现状和工艺新进展进行了阐述。最后，展望了锌的生物浸出工艺的发展趋势及后续的研究热点。研究表明高效浸锌菌种的选育驯化、与之相匹配的工艺及装备研发，是锌的生物浸出当今研究热点及未来发展方向。
- 锌 /
- 生物浸出 /
- 浸矿菌种 /
- 反应机理 /
- 回收
Abstract: Zinc is a nonferrous metal necessary for modern industry and an important strategic resource. It ranks fourth among all metals in terms of world production after iron, aluminum, and copper. Zinc sulfide ore is the most important zinc-producing mineral in the world, followed by associated zinc oxide ore and zinc-containing secondary resources. China is rich in zinc resources. Most of China’s lead–zinc and copper–zinc deposits are mainly lead–zinc integrated deposits, lead–zinc sulfide deposits, and other associated components. These types of mineral resources lead to wastage of resources in the development and utilization processes and affect the subsequent smelting process, which places considerable pressure on the production efficiency and ecological environment. The current mining and metallurgical industry vigorously promotes industrial development and has shifted in the favor of recycling, low-carbon, and green technologies. The biological leaching technology, as a green and low-carbon wet metallurgy technology, meets the current environmental protection policy requirements. This technology uses microorganisms and their metabolites to soak valuable metals in ores and has many advantages such as simple process, environmental protection, and capability to process low-grade ores. With the development of hydrometallurgical technology, the biological leaching technology of zinc from various types of low-grade zinc resources has attracted researchers’ attention and shown considerable application potential. First, this study introduced the mineral characteristics of zinc resources and analyzed their bioleachability. Then, the bioleaching process of zinc was summarized, and the leaching bacteria, electrochemistry, thermodynamics, kinetics, and leaching mechanism were systemically introduced. Furthermore, the current situation and/or progress of zinc bioleaching technology were generalized. Finally, the development trend of zinc bioleaching process and future research hotspots were considered. This study shows that the breeding of highly efficient bioleaching bacteria and the corresponding technology and equipment inventions are the current research hotspots and can also be the development directions for zinc bioleaching in the future. This will help ensure rapid and effective development of the zinc bioleaching technology.
- zinc /
- bioleaching /
- bacteria /
- reaction mechanism /
- extraction

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图 1 闪锌矿（ZnS）的晶格结构

Figure 1. Lattice structure of sphalerite (ZnS)

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图 2 铜绿假单胞菌电镜图（a）和琼脂平板菌落特征（b）

Figure 2. Electron microscopy image of Pseudomonas aeruginosa (a) and agar plate colony characteristics (b)

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图 3 生物活性剂鼠李糖脂单糖（a）和多糖（b）分子结构

Figure 3. Molecular structure of the monosaccharides (a) and polysaccharides (b) of rhamnolipids as bioactive agents

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图 4 ISR工艺示意图

Figure 4. Diagram of the ISR process

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表 1 锌的生物浸出特点

Table 1. Bioleaching characteristics of zinc

Types	Zinc resources	Bacterial species	Extractant	Characteristic
Sulfide ore	Sphalerite, marmatite, wurtzite	Inorganic acidophilic bacteria	Fe³⁺,H₂SO₄	Short leaching cycle and high efficiency
	Zinc-containing polymetallic sulfide ore	Inorganic acidophilic bacteria	Fe³⁺,H₂SO₄	Selective priority leaching
	Smithsonite, zincite, sillizonite, heteropolar	Heterotrophic alkaline bacteria	Organic acid	Need external energy substrate
Non-sulfide ore	Electronic waste such as zinc-manganese batteries	Inorganic acidophilic bacteria, heterotrophic alkaline bacteria	Fe³⁺,H₂SO₄, Organic acid	Need external energy substrate and low efficiency
	Lead-zinc smelting slag	Inorganic acidophilic bacteria, heterotrophic alkaline bacteria	Fe³⁺,H₂SO₄, Organic acid	High acid consumption and high leaching rate
	Zinc-containing sludge and wastewater	Inorganic acidophilic bacteria, heterotrophic alkaline bacteria	Fe³⁺,H₂SO₄, Organic acid	Direct decomposition of organic matter and sulfide

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表 2 部分常用浸矿细菌特征

Table 2. Some frequently used bioleaching bacteria characteristics

Types	Bioleaching bacteria	Growth environment	Optimum growth pH value	Energy substance	Oxidation products
Inorganic acidophilic bacteria	Acidithiobacillus ferrooxidans	Acidic	2.5	Fe²⁺,${{\rm{S}}_2}{\rm{O}}_3^{2 - }$,S⁰,Sulfide ore	Fe³⁺,${\rm{SO}}_4^{2 - }$
	Leptospirillum ferrooxidans	Acidic	1.5‒3.0	Fe²⁺	Fe^3+-
	Acidimirobium ferrooxidans	Acidic	2.0	Fe²⁺	Fe³⁺
	Sulfobacillus thermosul fidooxidans	Acidic	2.0	Fe²⁺,${{\rm{S}}_2}{\rm{O}}_3^{2 - }$,S⁰,Sulfide ore	Fe³⁺,${\rm{SO}}_4^{2 - }$
	Acidithiobacillus thiooxidans	Acidic	1.5‒3	${{\rm{S}}_2}{\rm{O}}_3^{2 - }$,S⁰,Sulfide ore
	Thioalklimicrobium	Alkaline	9.5‒10.0	${{\rm{S}}_2}{\rm{O}}_3^{2 - }$, S⁰,Sulfide ore	${\rm{SO}}_4^{2 - }$
	Thiobacillus novellus	Alkaline	7.8‒9.0	${{\rm{S}}_2}{\rm{O}}_3^{2 - }$,S⁰,Sulfide ore	${\rm{SO}}_4^{2 - }$
	Thioalkalivibrio	Alkaline	10.0‒10.2	${{\rm{S}}_2}{\rm{O}}_3^{2 - }$,Sulfide ore	S⁰
	Thiobacillus versutus	Alkaline	8.0‒9.0	${{\rm{S}}_2}{\rm{O}}_3^{2 - }$,Sulfide ore	${\rm{SO}}_4^{2 - }$
	Alpha proteobacterium	Alkaline	8.5‒8.8	${{\rm{S}}_2}{\rm{O}}_3^{2 - }$,Sulfide ore	S⁰
	Pseudomonas stutzeri	Alkaline	7.5‒8.0	Sulfide ore	${\rm{SO}}_4^{2 - }$
Heterotrophic alkaline bacteria	Pseudomonas aeruginosa	Alkaline	—	C₆H₁₂O₆,Sulfide ore	C₂H₄O₂、${\rm{SO}}_4^{2 - }$
	Arthrobacter oxydans	Alkaline	—	Organic compound	C₂H₂O₄、C₃H₆O₃
	Microbacterium sp.	Alkaline	—	Organic compound	C₂H₂O₄、C₆H₁₂O₇
	Bacillus megaterium	Alkaline	4.0‒7.5	Organic compound	C₆H₈O₇
	Promicromonospora sp.	Alkaline	—	Organic compound	C₆H₁₂O₇

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表 3 硫化矿物溶解的部分动力学模型^[43]

Table 3. Partial kinetic model for the dissolution of sulfide minerals^[43]

Number	Model	Types
1	${K_{\rm{t}}} = 1 - {(1 - X)^{\frac{2}{3}}}$	Hybrid control model of shrin-king core model (diffusion control; chemical reaction control)
2	${K_{\rm{t}}} = {[1 - {(1 - X)^{1/3}}]^2}$	Product layer diffusion model
3	${K_{\rm{t}}} = - \ln (1 - X)$	Hybrid control model (surface reaction control, sulfur layer diffusion control)
4	${K_{\rm{t}}} = 1 - \dfrac{2}{3}X - {\left( {1 - X} \right)^{{\frac{1}{3}}}}$	Diffusion of porous product layer based on shrinking core model
5	${K_{\rm{t}}} = \dfrac{1}{3}\ln (1 - X) + [{(1 - X)^{ - \frac{1}{3}}} - 1]$	Interface transfer and product layer diffusion
6	${K_{\rm{t}}} = 1 - 3{\left( {1 - X} \right)^{\frac{2}{3}}} + 2\left( {1 - X} \right)$	Diffusion of H⁺ in the product layer of the shrinking core model
7	${K_{\rm{t}}} = 1 - {(1 - 0.45X)^{1/3}}$	Surface chemical reaction diffusion of shrinking core model

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