深海热液喷口多金属硫化物原位保真采样−解离机理与绿色提取技术研究

Research on in situ fidelity sampling, dissociation mechanisms, and green extraction technologies for deep-sea hydrothermal vent polymetallic sulfides

摘要

深海热液喷口多金属硫化物矿床富含铜、锌、金、银等高价值金属及稀散元素，然而，深海极端环境和矿物复杂共生特性使其开发利用面临“采样—解离—提取”全链条技术挑战. 系统综述该领域的研究进展与技术瓶颈：采样技术方面，分析了从机械采样到智能化集成系统的演进历程，识别出保真度低导致样品矿物氧化失真问题，提出构建多参数智能感知与自适应保真采样系统的解决方案；解离机理方面，阐述了黄铁矿、黄铜矿、闪锌矿等主要矿物在压力–温度耦合条件下的氧化溶解动力学，揭示多矿物体系的原电池效应、协同作用和竞争机制，指出需建立跨尺度解离理论框架和动力学数据库；绿色提取技术方面，总结了生物冶金、电化学提取、超临界流体提取、微波辅助提取等技术的优势与局限，提出发展多技术协同集成工艺. 提出未来四大突破方向：开发智能化原位保真采样装备获取原始保真样本开展科学研究，深化压力–温度耦合解离机理研究，构建集成化绿色提取工艺体系，建立采样—解离—提取全流程数字孪生与智能协同调控平台. 研究成果为深海矿产资源开发提供理论指导和技术支撑，对保障国家资源安全、推动海洋强国建设具有重要意义.

Abstract

Deep-sea hydrothermal vent polymetallic sulfide deposits exhibit significant enrichment in strategic metallic elements, including copper, zinc, gold, and silver, and critical rare-earth elements, such as cobalt, selenium, tellurium, and indium, which represents the most economically valuable mineral resources of the 21st century. These deposits, formed through complex hydrothermal processes involving mid-ocean ridge systems and back-arc spreading centers, demonstrate metal concentrations frequently exceeding conventional terrestrial ore deposits by several orders of magnitude, rendering them essential for future mineral resource security. Nevertheless, the harsh deep-sea environment characterized by water depths of 1500–5000 meters, extreme hydrostatic pressures up to 50 MPa, aggressive marine corrosion, and complex sulfide mineral assemblages presents formidable technical challenges throughout the complete “sampling—dissociation—extraction” processing chain for sustainable resource development. This study examines the current technological advances and identifies critical bottlenecks in this strategically significant research domain. Regarding sampling technologies, the evolution from conventional mechanical approaches to intelligent integrated systems is analyzed, encompassing multi-platform operations employing human-occupied vehicles (HOVs), remotely operated vehicles (ROVs), and autonomous underwater vehicles (AUVs). Critical sample preservation issues are identified as fundamental concerns, whereby recovered specimens experience severe temperature variations exceeding 300℃ and pressure differentials of 20–50 MPa during ascent from seafloor to surface, inevitably causing mineral phase transitions, oxidation reactions, and microstructural alterations that compromise analytical precision. The proposed innovations include the development of multiparameter monitoring systems with real-time sensing capabilities for temperature, pressure, pH, and electrochemical potential (Eh) coupled with adaptive sample preservation systems utilizing conservation protocols, including pressure compensation chambers, thermal regulation units, and inert gas protection systems, to maintain mineralogical stability and specimen integrity. Concerning dissolution mechanisms, the oxidative leaching kinetics of primary sulfide phases—including pyrite (FeS₂), chalcopyrite (CuFeS₂), and sphalerite (ZnS)—under coupled pressure-temperature conditions are investigated, encompassing elementary processes such as surface metal-sulfur bond dissociation, electrochemical electron transfer reactions, and aqueous ionic transport phenomena. The galvanic coupling effects characterized by electrochemical potential differences ranging from 0.1–0.5 V, synergistic dissolution enhancement, and competitive inhibition mechanisms within polymetallic sulfide assemblages are elucidated through electrochemical characterization methods. The necessity for establishing multiscale theoretical frameworks spanning five hierarchical levels from atomic-scale quantum mechanics to macroscopic continuum behavior, complemented by kinetic databases integrating density functional theory (DFT) calculations, molecular dynamics (MD) simulations, and in situ spectroscopic characterization techniques, is emphasized for a fundamental mechanistic understanding. Regarding environmentally sustainable extraction methodologies, the advantages and limitations of various green processing technologies are assessed, including biohydrometallurgical processes (specific energy consumption: 100–300 kW·h·t⁻¹), electrochemical extraction techniques (current density: 50–200 A·m⁻²), supercritical fluid extraction methods (operating parameters: 150–200 °C, 15–25 MPa), and microwave-assisted leaching technologies. The strategic implementation of integrated multi-technology synergistic processes is advocated, incorporating processing schemes such as combined biochemical leaching, microwave-ultrasonic coupling, and electrochemical-ultrasonic enhancement, targeting improvements in metal recovery efficiency of 10–20 percentage points and energy consumption reduction of 20%–30%. Four strategic research directions for future breakthroughs are proposed: (1) development of intelligent in situ sample preservation systems, (2) fundamental investigation of coupled pressure–temperature dissolution kinetics, (3) construction of integrated sustainable extraction processes achieving specific energy consumption < 1000 kW·h·t⁻¹ with metal recovery rates > 90%, and (4) establishment of digital twin control platforms with intelligent process optimization. These findings provide an essential theoretical foundation and practical technological guidance for deep-sea mineral resource development and represent critical contributions to national resource security and maritime technological advancement.

关键词

深海热液喷口 / 多金属硫化物 / 原位保真采样 / 解离机理 / 绿色提取技术 / 智能化协同控制

Key words

deep-sea hydrothermal vents / polymetallic sulfides / in situ fidelity sampling / dissociation mechanisms / green extraction technology / intelligent collaborative control

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基金资助

国家自然科学基金面上资助项目(52374357)

教育部基础学科和交叉学科突破计划资助项目(JYB2025XDXM802)

深圳市科技计划资助项目(KJZD20231025152759002)

深圳市科技计划资助项目(JSGG20220831105002005)