Recent Developments in Preparation Process of High-Purity Gold and Gold Target Materials
Citations
NING Rui,LIU Zhizhong,MA Dengfeng,LI Wei,CHEN Song,YIN Yanxi. Recent developments in preparation process of high-purity gold and gold target materials[J]. Copper Engineering,2025(6):73-84.
图1 化学还原法制备高纯金流程示意图
图2 金萃取流程示意图
图3 金电解示意图
图4 不同电源电流波形图:(a)直流电;(b)交流电;(c)脉动电流;(d)周期换向电流
表1 GB/T 25933—2010高纯金杂质含量标准
表2 部分金属标准电极电势
铜业工程 第6期 73-84
doi:10.3969/j.issn.1009-3842.2025.06.008
材料制备与加工工程(Material Preparation and Process Engineering)
2.Key Laboratory of Nonferrous Metals Metallurgy and Recycling in Hubei Province,Huangshi435002,China
3.GRINM Resources and Environment Tech. Co.,Ltd.,Beijing101407,China
4.General Research Institute for Nonferrous Metals,Beijing100088,China
5.National Engineering Research Center for Environment-Friendly Metallurgy in Producing Premium Non-Ferrous Metals,GRINM Group Corporation Limited,Beijing100088,China
6.Beijing Engineering Research Center of Strategic Nonferrous Metals Green Manufacturing Technology,Beijing100088,China
Citations
NING Rui,LIU Zhizhong,MA Dengfeng,LI Wei,CHEN Song,YIN Yanxi. Recent developments in preparation process of high-purity gold and gold target materials[J]. Copper Engineering,2025(6):73-84.
Abstract
High-purity gold (Au) and gold targets are among the fundamental raw materials for integrated circuit and semiconductor chip manufacturing, primarily used in metallization systems of high-end chips and advanced packaging. In order to protect the supply chain security of China's high-end chips, Chinese enterprises are constantly devoted to the research and development and industrialization of high-purity gold and gold target preparation technology. This paper outlined the technical requirements and preparation challenges of high-purity gold and gold targets for semiconductor applications, providing an overview of global preparation technologies and research advancements, and analyzed the advantages and disadvantages of various methods. In the preparation of high-purity gold, the direct chemical reduction method features short processing flow and high efficiency but suffers from unstable product quality. The solvent extraction-reduction method ensures stable quality and high purity yet causes severe environmental pollution. The electrolysis method delivers high quality and purity with low cost but requires extended production cycles. The primary method for preparing gold targets was the melting-thermomechanical processing method, which achieved an average grain size of less than 100 μm in the resulting products. The preparation of high purity gold and gold target for semiconductor chips must be combined with the advantages of various purification processes and adopt a variety of combined processes in order to stably remove specific impurities and meet the high purity gold standard for semiconductors.
随着大规模集成电路和半导体芯片制造技术的飞速发展,集成电路单位面积上可容纳的晶体管数量成倍增加,芯片制程不断缩小[ ZHANG L. Silicon process and manufacturing technology evolution:An overview of advancements in chip making[J]. IEEE Consumer Electronics Magazine,2014,3(3):44-48. TANG J C,JIANG J F,GAO X Y,et al. Low-power 2D gate-all-around logics via epitaxial monolithic 3D integration[J]. Nature Materials,2025,24(4):519-526. 1-2]。在电路变得更窄的同时,电流密度将更大,半导体芯片中金属材料的纯度和稳定性成为影响芯片质量和使用寿命的重要因素[ 何金江,吕保国,贾倩,等. 集成电路用高纯金属溅射靶材发展研究[J]. 中国工程科学,2023,25(1):79-87. 李亚强,马晓川,张锦秋,等. 芯片制程中金属互连工艺及其相关理论研究进展[J]. 表面技术,2021,50(7):24-43,164. LUO J F,FANG Y Y,XU G J,et al. Development of ferromagnetic sputtering targets with high performance[J]. Mater. Science. Forum,2020,993:820-825. 3-5]。
高纯金(Au)具有电阻低、电迁移低、热稳定性高、抗氧化和耐腐蚀能力强等诸多优点,能与半导体形成欧姆接触,并能良好地附着于硅基体,因此被大量应用于半导体芯片领域的金属化系统[ CAO A,GONG Y,LIU D L,et al. Rapid fabrication of gold microsphere arrays with stable deep-pressing anisotropic conductivity for advanced packaging[J]. Nature Communications,2024,15:9182. ZHANG L Q,WU X L,MIAO W Q,et al. Process of Au-free source/drain ohmic contact to AlGaN/GaN HEMT[J]. Crystals,2022,12(6):826. MOHAMMAD S N. Contact mechanisms and design principles for nonalloyed ohmic contacts to n-GaN[J]. Journal of Applied Physics,2004,95(9):4856-4865. 6-8]。此外高纯金还用于集成电路和芯片的先进封装、键合以及焊接材料等[ WANG W C,LIU Z Y,QIU D L,et al. A method for fast Au-Sn bonding at low temperature using thermal gradient[J]. Micromachines,2023,14(12):2242. KARBOWNIK P,TRAJNEROWICZ A,SZERLING A,et al. Direct Au–Au bonding technology for high performance GaAs/AlGaAs quantum cascade lasers[J]. Optical & Quantum Electronics,2015,47(4):893-899. 王美玉,胡伟波,孙晓冬,等. 功率电子封装关键材料和结构设计的研究进展[J]. 电子与封装,2021,21(10):106-115. 9-11]。高纯金在集成电路和芯片制造领域的主要应用形式是高纯金溅射靶材。利用真空磁控溅射技术将高纯金镀覆于基体表面,再在镀覆的金膜上进行刻蚀,即可形成集成电路及芯片中的微细连接[ YAN C,ZHANG Q Y. Study on low-energy sputtering near the threshold energy by molecular dynamics simulations[J]. Aip Advances,2012,2(3):032107. BAGHERPOUR E,PARDIS N,REIHANIAN M,et al. An overview on severe plastic deformation:research status,techniques classification,microstructure evolution,and applications[J]. International Journal of Advanced Manufacturing Technology,2019,100:1647-1694. 王楠,宋贵宏,陈雨,等. Ni掺杂对β-Cu2Se薄膜微观结构和热电性能的影响[J]. 稀有金属,2024,48(3):365-377. 12-14]。
高纯金的制备过程实质是粗Au精炼提纯的过程,粗Au的精炼方法分为火法和湿法[ WU W H,YANG Y C,QIU H X,et al. Sustainable strategy for removing Ag impurities from crude gold via a vacuum distillation process to produce a 4N gold product[J]. Journal of Cleaner Production,2025,500:145248. MAHYAPOUR H,MOHAMMADNEJAD S. Optimization of the operating parameters in gold electro-refining[J]. Minerals Engineering,2022,186:107738. BALASUBRAMANIAN S K,YANG L,YUNG LY L,et al. Characterization,purification,and stability of gold nanoparticles[J]. Biomaterials,2010,31(34):9023-9030. GOMES C P,ALMEIDA M F,LOUREIRO J M. Gold recovery with ion exchange used resins[J]. Separation and Purification Technology,2001,24(1-2):35-57. 15-18]。火法过程工艺控制不稳定,产品纯度不高,主要用于高纯金制备的前处理过程,而湿法产品质量稳定,可制备出纯度大于5N(99.999%)的高纯金[ COTTY S R,KIM N,SU X. Electrochemically mediated recovery and purification of gold for sustainable mining and electronic waste recycling[J]. ACS Sustainable Chemistry & Engineering,2023,11(9):3975-3986. JUNG B H,PARK Y Y,AN J W,et al. Processing of high purity gold from scraps using diethylene glycol di-N-butyl ether (dibutyl carbitol)[J]. Hydrometallurgy,2009,95(3-4):262-266. 19-20]。Au的湿法精炼有直接还原法、溶剂萃取-还原法和电解法,3种方法各有其优缺点及技术难点[ LI J S,SAFARZADEH M S,MOATS M S,et al. Thiocyanate hydrometallurgy for the recovery of gold. Part V:process alternatives for solution concentration and purification[J]. Hydrometallurgy,2012,113:31-38. RAO M D,SINGH K K,MORRISON C A,et al. Recycling copper and gold from e-waste by a two-stage leaching and solvent extraction process[J]. Separation and Purification Technology,2021,263:118400. 刘庆杰,周洪杰,李文军. 控制电位法在氰化金泥提纯黄金中的应用[J]. 有色矿冶,2019,35(4):30-32. 21-23]。本文综述了国内外对高纯金及金靶材制备工艺的研究进展,分析了高纯金及金靶材制备过程的难点及各方法的优缺点,并对高纯金及金靶材的未来发展进行了展望。
Au的氧化精炼是将粗Au和氧化剂、造渣剂一起进行熔炼,在高温(1200~1350 ℃)下将粗Au中的杂质(Zn,Fe,Sn,As,Sb,Pb和Cu等)氧化造渣除去,最终得到较高纯度的Au[ CHEN A L,PENG Z W,HWANG J Y,et al. Recovery of silver and gold from copper anode slimes[J]. JOM,2015,67(2):493-502. 35]。
Au的湿法精炼主要在氯化溶液体系中进行,采用湿法冶金中的溶液净化和还原等方法对Au溶液进行深度净化除杂和还原,进而得到高纯金[ 梁柱俊,孙敬韬. 氯酸钠对铜阳极泥提取金的影响研究[J].铜业工程,2023(1):144-147. 36]。Au的湿法精炼主要有直接化学还原法、萃取-还原法和电解法。与火法过程相比,Au的湿法精炼过程更加可控,产品质量更加稳定,纯度也更高,可以制备出纯度99.999%的高纯金。 因此,高纯金的制备通常采用湿法[ MORRIS D,KHAN M A. Application of solvent extraction to the refining of precious metals—Ⅲ:purification of gold[J]. Talanta,1968,15(11):1301-1305. 37]。
通常Au在选择性还原后呈海绵状或砂状,经洗涤、熔炼后纯度可达99.999%。Zhang等[ ZHANG Z T,NIE H P. Extraction of gold from gold chloride solution by the depth reduction based on potential controlling in the process of treating copper anode slime[J]. JOM,2022,74:234-239. 41]研究了亚硫酸钠还原氯金酸溶液过程溶液电位、Au离子浓度及Au还原率之间的关系,结果表明还原过程分为两个阶段:第一阶段为快速还原阶段,当溶液电位降低至760 mV时溶液中Au离子浓度随还原过程的进行迅速下降;第二阶段为慢还原阶段,此阶段溶液中Au离子浓度较低,还原过程缓慢,最终当溶液电位降低至550 mV以下时,溶液中的Au离子浓度可降低至5 mg/L以下,Au的还原率可达99.7%,但同时部分杂质也会被还原,降低Au的纯度。郭晓亮等[ 郭晓亮,邓丰卓,吕超飞,等. 粗金粉中金的氯浸-控制电位还原精炼[J]. 贵金属,2022,43(1):54-60. 42]以氰化金泥中回收的粗金粉(纯度为91%~98%)为原料,采用氯酸钠-盐酸法溶金,金液经过加水稀释、冷却除杂后用焦亚硫酸钠还原,控制电位在690~700 mV,还原率约为85%,残留Au二次还原后得到黑金粉进入下一批次溶解,产品经洗涤、硝酸浸煮除杂后铸锭,最终能够稳定生产出国家标准金锭GB/T 4134—2014[ 国家市场监督管理总局.金锭: GB/T 4134—2021[S].2021. 43]中的IC-Au99.99级产品。庄宇凯等[ 庄宇凯,纪鹏. 二次氯化-二次还原法精炼高纯金工艺研究[J]. 黄金,2014,35(2):57-60. 44]以纯度大于99.9%的金锭为原料,采用水溶液氯化法溶金,焦亚硫酸钠为还原剂,溶液氧化还原电位控制为690~700 mV,经过两次溶解-还原过程,制备出满足国标GB/T 25933—2010的5N(99.999%)级高纯金。李光胜等[ 李光胜,王明双,马涌,等. 化学还原法制备高纯金试验研究[J]. 黄金科学技术,2015,23(2):103-106. 45]用王水法溶金,分别以质量分数约为91.8%,95.9%和99.8%的3种粗Au为原料,通过控制还原剂加入量使溶液氧化还原电位控制在690~720 mV,经过二次王水-二次还原后分别得到纯度为99.9995%,99.9997%和99.9998%的高纯金。赵家春等[ 赵家春,阳岸恒,吴跃东,等. 蒸发材料用高纯金的制备研究[J]. 贵金属,2021,42(2):27-31. 46]以纯度99.95%的金锭为原料,采用王水法溶金,使用NaOH调节溶液pH,将溶液中的贱金属杂质以氢氧化物的形式沉淀除去,并在还原之前严格控制过滤条件,避免溶液中的微细沉淀粒子穿滤造成污染,过滤后的溶液经稀释并用NaOH调节pH后还原,最终金粉洗涤后纯度可达99.999%,且用此金粉熔炼加工制成的蒸发材料纯度大于99.999%,可用作制造集成电路芯片的蒸发材料。
DBC对[AuCl4]−的结合力强是其萃取效果好的根本原因,但强的结合力会导致后续Au的反萃困难,需要用热草酸(80~85 ℃)或亚硫酸钠溶液反萃才能取得很好的反萃效果[ 马荣骏.萃取冶金[M]. 北京:冶金工业出版社,2009:699-700. 50, HORIUCHI T,OSHIMA T,BABA Y. Separation of Au (Ⅲ) from other precious and base metals using 1-methoxy-2-octoxybenzene in acidic chloride media[J].Hydrometallurgy,2018,178:176-180. 59]。Jung等[ JUNG B H,PARK Y Y,AN J W,et al. Processing of high purity gold from scraps using diethylene glycol di-N-butyl ether (dibutyl carbitol)[J]. Hydrometallurgy,2009,95(3-4):262-266. 20]对DBC反萃工艺进行了改进,将负载有机相直接与浓氨水接触,生成固体中间产物雷金(Au2O3·3NH3),雷金后续用水合肼还原为金粉,制备出99.9998%的高纯金。
除DBC萃取剂外,一些新的萃取剂也在不断地被用于Au的萃取。Oshima等[ OSHIMA T,MIYAKE K. Au (Ⅲ) extraction using ketone compounds with physical properties superior to current commercial extractants[J]. AlChE Journal,2021,67(7):e17214. 60]介绍了一种市售的新型醚化溶剂环戊基甲醚(CPME),可用于萃取酸性介质中的Au3+,CPME对Au3+的负载量高达60 g/L,且在较高酸度条件下对Au的萃取率可达98%,虽略低于DBC的萃取率,但反萃率更高。Horiuch等[ HORIUCHI T,OSHIMA T,BABA Y. Separation of Au (Ⅲ) from other precious and base metals using 1-methoxy-2-octoxybenzene in acidic chloride media[J].Hydrometallurgy,2018,178:176-180. 59]研制了一种芳香醚类化合物o-MOB,其对Au3+的萃取率高于DBC,且有较好的选择性。还有研究表明,脂肪酮类化合物如2-壬酮等对Au也有良好的萃取性能,这些酮类化合物与商用萃取剂相比,具有更好的物理性能,如更低的水溶解度、黏度以及更高的闪点等[ OSHIMA T,MIYAKE K. Au (Ⅲ) extraction using ketone compounds with physical properties superior to current commercial extractants[J]. AlChE Journal,2021,67(7):e17214. 60]。
金粉的产生不利于高效生产,将导致Au的直收率降低,因此需要抑制金粉产生。Schalch等[ SCHALCH E,NICOL M J. A study of certain problems associated with the electrolytic refining of gold[J]. Gold Bulletin,1978,11(4):117-123. 65]认为电解过程中阳极生成的Au+有两个去处,一部分在阳极表面被氧化为Au3+,而另一部分会逸散到溶液中,歧化生成金粉或在阴极析出。他研究了不同条件下阳极Au的溶解,并测定溶液中的Au+浓度,实验结果表明:提高电流密度、降低电解液温度、降低搅拌转速、降低氯离子浓度等手段可以降低溶液中Au+的浓度。此项研究为Au电解过程参数控制提供了参考,并用于兰德精炼厂99.99%纯度Au的连续生产,减少了电解槽中金粉的数量。此外,部分精炼厂会在电解液中添加硝酸[ MOSTERT P J,RADCLIFFE P H. Recent advances in gold refining technology at Rand Refinery[J]. Developments in Mineral Processing,2005,15:653-670. 66]。硝酸的作用主要包括两个方面:一是将Au+氧化为Au3+,从而减少Au+歧化反应产生的金泥;二是溶解电解槽中已产生的金粉并加速阳极粗Au溶解,其原理和王水溶金相同[ MOOIMAN M B,Simpson L. Refining of gold-and silver-bearing dore[M]// Gold Ore Processing:Elsevier,2016:595-615. 67]。
正常电解条件下,阳极只发生溶解反应,但当电解液中盐酸浓度和温度较低时,Au阳极会有钝化倾向,开始析出氯气甚至氧气,使电化学溶解过程中断,电解液中Au3+得不到补充,影响阴极产品质量[ 余建民.贵金属分离与精炼工艺学[M]. 北京:化学工业出版社,2006:150-151. 39]。此外,粗Au中所含的Ag也会造成阳极钝化,Ag在电解过程中会生成不溶AgCl包裹阳极,阻碍Au的溶解。为解决Ag造成的阳极钝化,孙戬等[ 孙戬.金银冶金[M]. 北京:冶金工业出版社,1986:376-379. 68]提出在电解时同时通入交流电和直流电形成脉动电流,电流大小呈周期性变化,波峰时阳极的瞬时电流密度大,析出气体破坏AgCl包裹层,消除阳极钝化,波谷时电流为负,抑制AgCl生成。此法在中国株洲冶炼厂[ 王定良,毛仕杰. 沃耳维尔法电解金的生产实践[J]. 湖南冶金,1989(2):24-26. 69]、白银公司冶炼厂[ 盛枝,张墨霞. 黄金电解电源[J]. 白银科技,1995(2):50-53. 70]以及江铜贵溪冶炼厂[ 赵忱. 金电解电源装置的优化设计与应用[J]. 矿冶,2002,11(3):77-79. 赵忱. 交直流叠加在金电解中的应用[J]. 设备管理与维修,2003(3):19. 71-72]进行了工业实践,均取得良好效果。除交直流叠加电源外,新的电解电源也不断被开发并用于Au的电解,如非对称交流电源[ 付国民. 非对称交流电源在金电解生产中的应用[J]. 黄金,2000(5):37-39. 73]、周期换向电源[ 郑勇. 周期(2π)换向金电解电源[J]. 黄金,1999(12):29-33. 郑勇,常占河,李德俊. 周期自动换向金电解新工艺[J]. 黄金,1996(4):35-38. 74-75]等。不同电源电流波形图如图4所示。Granato等[ GRANATO M,SOBRAL L G S. Electrorefining of high silver content gold bullion using pulsating currents[J]. Minerals Engineering,1990,3(5):501-508. 76]分别用非对称交流电源(AAC)和周期换向电源(PRC)进行Au电解实验研究,研究结果表明:两种电源均能克服阳极钝化,对Ag含量为17.1%的粗Au进行电解精炼,产品纯度达99.99%,两种电源均对消除阳极Au+的歧化有积极作用,可以抑制金粉的产生;采用非对称交流电源电解所获产品形貌比周期换向电源更加致密、均匀,但都优于直流电源所获产品。
图4 不同电源电流波形图:(a)直流电;(b)交流电;(c)脉动电流;(d)周期换向电流
Fig. 4 Images of current waveform with different power supplies:(a) Direct current;(b) Alternating current;(c) Pulsating current;(d) Periodic commutation current
Au电解过程参数会直接影响阴极产品质量,这些参数包括Au电解液中Au离子浓度和盐酸浓度、电流密度、电解温度、极间距等。电解液中Au离子浓度会影响电流效率和生产效率,Au离子浓度高,阴极板上新晶核形成快,生产效率高,但Au离子浓度过高会造成严重的浓差极化,导致阴极板上下产品形貌不均,影响产品质量。盐酸能够增强溶液导电性,抑制阳极钝化,但酸度过高会降低阴极析氢所需过电位,降低电流效率。阴极电流密度会影响阴极Au的沉积,电流密度低时,晶粒生长速度大于新晶核形成速度,得到的产品晶粒粗大,表面平整;提高电流密度,新晶核形成速度随之加快,产品晶粒细小,同时表面粗糙;电流密度如果过高,Au的沉积速度大于扩散速度,在Au离子密度更高的地方更易晶粒形核与生长,因而产生枝晶,影响阴极形貌且有短路风险[ 柳旭,张国清,陈怡兰,等. 国内电解精炼法制备高纯金综述[J]. 贵金属,2017,38(4):87-94. 77]。电解过程溶液保持一定温度可以加强溶液传质速率,提高电导率,缓解浓差极化,但温度过高会加快电解液蒸发速率。极间距主要影响槽电压,二者是正相关关系,极间距过大则会导致槽电压高,增加电解过程能耗[ 夏志薇,马坚刚,夏兴旺,等. 影响金电解电流效率的因素及对策[J]. 铜业工程,2021(6):51-53, 80. 78]。Schalch等[ SCHALCH E,NICOL M J. A study of certain problems associated with the electrolytic refining of gold[J]. Gold Bulletin,1978,11(4):117-123. 65]在Au离子质量浓度为70 g/L、盐酸质量浓度为120 g/L的条件下探究了不同温度、阴阳极电流密度对阴极形貌的影响,结果表明:在电解温度为20~25 ℃,阴极和阳极电流密度为400 A/m2的条件下,阴极产品3/4部分呈现光滑、平整的形貌;电解液温度为50 ℃、阴极和阳极电流密度为850 A/m2时所得产品表面更加粗糙,且边缘有大量葡萄状结晶;保持阴极电流密度不变,阳极电流密度提高至1600 A/m2后,所得产品边缘无葡萄状结晶,阴极表面更加规整,原因可能是更高的阳极电流密度使得阳极粗Au溶解速度加快,电解液中的Au离子得到及时补充,这也表示阳极电流密度高对产品形貌控制是有利的。
真空磁控溅射法是物理气相沉积法(PVD)制备薄膜材料的关键技术之一,其制备出的薄膜材料具有致密度高、附着性好等优点,被广泛应用于电子、半导体、航空航天和太阳能电池等行业[ LE FEBVRIER A,LANDÄLV L,LIERSCH T,et al. An upgraded ultra-high vacuum magnetron-sputtering system for high-versatility and software-controlled deposition[J]. Vacuum,2021,187:110137. 87]。高纯金属溅射靶材是真空磁控溅射法制备高性能薄膜材料的关键材料,溅射靶材的主要制备方法包括粉末冶金法和熔炼-热机械处理法[ GARG R,GONUGUNTLA S,SK S,et al. Sputtering thin films:materials,applications,challenges and future directions[J]. Advances in Colloid and Interface Science,2024,330:103203. 88]。
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