Article(id=1241064285368013515, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241064275599479114, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2025.05.022, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1745510400000, receivedDateStr=2025-04-25, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773822383491, onlineDateStr=2026-03-18, pubDate=1759248000000, pubDateStr=2025-10-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773822383491, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773822383491, creator=13701087609, updateTime=1773822383491, updator=13701087609, issue=Issue{id=1241064275599479114, tenantId=1146029695717560320, journalId=1235980550691926019, year='2025', volume='45', issue='5', pageStart='1', pageEnd='201', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773822381162, creator=13701087609, updateTime=1773822785847, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241065973038501946, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241064275599479114, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241065973038501947, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241064275599479114, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=124, endPage=130, ext={EN=ArticleExt(id=1241064285808415469, articleId=1241064285368013515, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Current Status of Gallium Resource and Research Progress in Refining Process, columnId=1236276106727321817, journalTitle=Mining and Metallurgical Engineering, columnName=METALLURGY, runingTitle=null, highlight=null, articleAbstract=

After an introduction of the current status of gallium resources and analysis of the occurrence state of gallium in sodium aluminate solution, zinc smelting slag, tailings from vanadium extraction and coal-based solid waste, progress in the research of gallium extraction processes is elaborated and the adaptability, advantages and disadvantages of each technique are also summarized. Finally, based on the discussion of problems faced by the gallium industry and the development direction in the future, it is suggested that iteration and upgrading of gallium extraction processes should be vigorously promoted based on China's scale advantage in alumina industry.

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介绍了镓的资源现状,分析了镓在铝酸钠溶液、锌冶炼渣、提钒尾渣和煤基固体废弃物中的赋存状态;阐述了提镓工艺的研究进展,并评述了各工艺的适应性和优缺点;最后对镓行业面临的问题及发展方向进行了讨论和展望,提出立足我国氧化铝产业规模优势,大力推动提镓工艺迭代升级的建议。

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房辉(1985—),男,河南新乡人,博士,高级工程师,主要从事氧化铝生产技术研究。E-mail:

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2.School of Metallurgy and Environment, Central South University, Changsha 410083, Hunan, China
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2.中南大学 冶金与环境学院,湖南 长沙 410083
3.山东南山铝业股份有限公司 有色金属产业研究院,山东 龙口 265713
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房辉(1985—),男,河南新乡人,博士,高级工程师,主要从事氧化铝生产技术研究。E-mail:

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房辉(1985—),男,河南新乡人,博士,高级工程师,主要从事氧化铝生产技术研究。E-mail:

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镓资源现状及提炼工艺研究进展
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房辉 1, 2, 3, 4 , 王壮 3, 5 , 徐良振 1
矿冶工程杂志 | 冶金 2025,45(5): 124-130
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矿冶工程杂志 | 冶金 2025, 45(5): 124-130
镓资源现状及提炼工艺研究进展
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房辉1, 2, 3, 4 , 王壮3, 5, 徐良振1
作者信息
  • 1.龙口东海氧化铝有限公司,山东 龙口 265713
  • 2.中南大学 冶金与环境学院,湖南 长沙 410083
  • 3.山东南山铝业股份有限公司 有色金属产业研究院,山东 龙口 265713
  • 4.烟台南山学院 材料科学与工程学院,山东 龙口 265700
  • 5.山东南山铝业股份有限公司 国家铝合金压力加工工程技术研究中心,山东 龙口 265713
  • 房辉(1985—),男,河南新乡人,博士,高级工程师,主要从事氧化铝生产技术研究。E-mail:

Current Status of Gallium Resource and Research Progress in Refining Process
Hui FANG1, 2, 3, 4 , Zhuang WANG3, 5, Liangzhen XU1
Affiliations
  • 1.Longkou Donghai Alumina Co., Ltd., Longkou 265713, Shandong, China
  • 2.School of Metallurgy and Environment, Central South University, Changsha 410083, Hunan, China
  • 3.Research Institute of Nonferrous Metal Industry, Shandong Nanshan Aluminum Co., Ltd., Longkou 265713, Shandong, China
  • 4.School of Materials Science and Engineering, Yantai Nanshan University, Longkou 265700, Shandong, China
  • 5.National Engineering and Technology Research Center for Aluminum Alloy Pressure Processing, Shandong Nanshan Aluminum Co., Ltd., Longkou 265713, Shandong, China
出版时间: 2025-10-01 doi: 10.3969/j.issn.0253-6099.2025.05.022
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介绍了镓的资源现状,分析了镓在铝酸钠溶液、锌冶炼渣、提钒尾渣和煤基固体废弃物中的赋存状态;阐述了提镓工艺的研究进展,并评述了各工艺的适应性和优缺点;最后对镓行业面临的问题及发展方向进行了讨论和展望,提出立足我国氧化铝产业规模优势,大力推动提镓工艺迭代升级的建议。

镓  /  铝酸钠溶液  /  锌冶炼渣  /  提钒尾渣  /  煤基固体废弃物  /  提镓

After an introduction of the current status of gallium resources and analysis of the occurrence state of gallium in sodium aluminate solution, zinc smelting slag, tailings from vanadium extraction and coal-based solid waste, progress in the research of gallium extraction processes is elaborated and the adaptability, advantages and disadvantages of each technique are also summarized. Finally, based on the discussion of problems faced by the gallium industry and the development direction in the future, it is suggested that iteration and upgrading of gallium extraction processes should be vigorously promoted based on China's scale advantage in alumina industry.

gallium  /  sodium aluminate solution  /  zinc smelting slag  /  tailings from vanadium extraction  /  coal-based solid waste  /  gallium extraction
房辉, 王壮, 徐良振. 镓资源现状及提炼工艺研究进展. 矿冶工程杂志, 2025 , 45 (5) : 124 -130 . DOI: 10.3969/j.issn.0253-6099.2025.05.022
Hui FANG, Zhuang WANG, Liangzhen XU. Current Status of Gallium Resource and Research Progress in Refining Process[J]. Mining and Metallurgical Engineering, 2025 , 45 (5) : 124 -130 . DOI: 10.3969/j.issn.0253-6099.2025.05.022
镓是一种典型的稀散金属元素,熔点为29.78 ℃,沸点2 403 ℃,最低过冷温度达-120 ℃,在“热缩冷胀”下的体积膨胀率为3.2%,固体和液体分别呈蓝灰色和银白色光泽。镓还属于两性金属,溶于酸和碱后分别产生Ga3+和Ga(OH)4-,而在常温下则会产生致密氧化膜,从而阻止内部进一步被氧化[1]。高纯镓及其化合物在电子通信、新能源、航空航天等高端技术领域的应用十分广泛,早已成为发展高新科技所依赖的重要支撑原材料之一[2]。镓具有优异的热传导和中子吸收性能,是原子能工业中不可或缺的关键金属材料。鉴于镓的军民两用属性及无可替代的地位,美、日、欧盟等国家和地区先后将其列入战略资源、关键原材料目录之中,中国则将其纳入战略储备金属之列,并已实施出口管制。在蓬勃发展的终端市场驱动下,下游产业对镓的需求量预计持续增加,未来镓行业有望迎来新的发展机遇[3]。在当今全球矿产资源供需格局深刻变革的背景下,面对广阔的市场应用前景,如何保障镓的稳定可持续供给愈发受到关注。本文总结了镓的资源现状,分析了其在各种富镓原料中的赋存状态,并阐述了提镓工艺的研究进展,最后探讨了镓行业发展趋势、面临的突出问题及解决对策,以期为金属镓的相关研究领域提供有益参考。
镓在地壳中的分布极为分散,因其成矿条件特殊,在自然界很少有独立矿物,通常伴生在铝土矿、铅锌矿、钒钛磁铁矿等金属矿以及煤矿中,并以类质同象形式进入主矿物的晶格中[2]。由于不同金属元素的赋存矿物性质存在差异,在这些金属矿物的富集过程中,同步进行着选矿作业,实现了各种伴生金属的初步分离,而镓一般富集在溶液或废渣中。因此,镓在铝、锌、钒等副产品中的品位较高,开发利用难度也较低,此类优质的富镓原料极具工业开采价值,这也是当前阶段镓资源的主要来源。除此之外,在特定的地质条件下,煤炭中伴生有“三稀”金属元素,特别是高铝煤炭,因其镓含量较高,烟气和粉煤灰中富集的镓相当可观[4]。我国是世界上最大的煤炭消耗国,具有开展燃煤渣提镓的资源优势。
镓的化学性质与铝相似,因而常伴生在含铝矿物中。镓在铝土矿中的丰度远高于在地壳中的丰度,目前世界上90%以上的镓来源于氧化铝生产过程。我国铝土矿资源丰富,并且镓的丰度较高,发展提镓产业具有显著优势。在氧化铝生产过程中,镓由铝土矿和煤带入,一部分在循环母液中富集,一部分则在各工序中损失掉。
在拜耳法工艺中,由于反应(1)的存在,镓在高温碱液的作用下,以NaGa(OH)4形式随铝进入溶液,并在循环母液中不断富集[5],质量浓度最高可达0.3 g/L。通过物料平衡计算发现,铝土矿中80%~85%的镓富集在循环母液中,加之氧化铝生产连续循环的作业方式,使得循环母液成为提镓的极佳原料[6]
在烧结法工艺中,矿石中的镓经过烧结反应,以Na2O·Ga2O3形式进入熟料,随后在溶出工序溶于碱液中,其化学反应如式(2)~(3)所示。在后续的碳酸化分解工序中,通过调整工艺参数,可实现铝镓分离,使镓留在碳分母液中,并经过循环后不断富集。
镓原子的电子构型与锌类似,晶体结构和化学性质也相似,故其常占据矿物晶格中锌的位置,闪锌矿普遍存在这种类质同象置换现象。火法炼锌过程中,镓主要富集在冶炼渣中[7]。在湿法炼锌时,镓同其他稀散金属共同进入浸出渣,赋存在铁酸盐和硅酸盐中,而在置换渣中以氧化物和复合氧化物形态存在[8]。在锌浸出渣中,铁酸锌是重要的富镓原料[9]。在锌回转窑渣中,71%~96%的镓以类质同象形式集中赋存在FeySx和α-Fe矿相中。在鼓风炉炼锌(ISP)工艺中,原料中90%的镓富集在炉渣中,呈类质同象进入方铁矿、锌尖晶石、锌黄长石及硫化铁等矿物中,具备开发利用潜力。
提钒尾渣又称钒渣,是钒钛磁铁矿经过冶炼提钒后产生的废渣,含有铁、钒、镓、铬、钛等有价金属。研究结果表明,钒钛磁铁矿中赋存有金属镓,镓品位为0.002 6%,大部分以类质同象形式存在[10]。我国钒钛磁铁矿潜在资源储量巨大,钢铁行业每年产生近100万t的钒渣,钒渣中的镓资源储量丰富,开发前景广阔。原矿经选矿处理后,50%的镓进入铁精矿。在高炉炼铁过程中,由于镓的亲铁属性,98%左右的镓进入铁水中,其余则分散在高炉渣和烟尘中[11]。某厂的生产实践表明,经过选矿、冶炼后,镓富集在提钒后的钒渣和炼钢烟尘中,但受技术条件限制,目前研究侧重于钒渣提镓工艺研发,烟尘提镓工艺和水平有待提升[12]。某钢铁厂在吹炼前增设了氧化脱钒工序,在回收钒的同时,得到富镓的氧化渣,分析检测结果发现,70%的镓以Ga2O3形态存在于钒铁晶石[Fe2+(V3+Fe3+)O4]中。镓在炼铁过程中的走向比较集中,最终在钒渣中富集。随着提取冶金技术的快速发展,钒渣提镓将成为今后重要的研究方向[13]
煤系共伴生矿产资源的高效提取是研究热点,煤基固体废弃物中镓的开发引起广泛关注。镓以无机物或有机物形式存在于燃煤中,其赋存状态及贫富程度也有差别。一般而言,燃煤中镓的含量(质量分数)为0.000 1%~0.004 5%。煤燃烧时大部分的镓挥发进入烟气,并以氧化物形式附着在烟尘颗粒表面。原煤含镓越高,挥发进入烟气的镓越多,经收尘后,烟尘中镓浓度(质量分数)可达0.38%~1.56%,为提镓创造了便利条件。燃煤中的小部分镓残留在粉煤灰中,其赋存状态有两种:一种是继续留在燃煤原矿里,另一种是燃烧后经过转化进入Al-Si玻璃体晶格中。受燃煤种类及燃烧工艺影响,镓在粉煤灰中的品位波动较大,通常为12~230 μg/g[14]。随着国民经济不断发展,我国能源消费需求将持续增长,煤炭的主体能源地位也将维持较长时期。同时,粉煤灰的产量也将保持增长趋势。我国粉煤灰体量巨大,蕴含的副产镓资源颇丰,针对粉煤灰开展提镓研究是实现资源化利用的有效途径[15]
铝酸钠溶液提镓工艺取决于氧化铝生产方法及母液含镓量,在工业上获得应用的有石灰乳法、离子交换树脂法和萃取法等。
石灰乳法的原理是:首先向铝酸钠溶液中通入二氧化碳至饱和状态,使镓和铝共沉淀生成丝钠铝(镓)石;再加入石灰乳脱铝,使镓溶解进入溶液,铝转变为沉淀,从而实现镓与铝的初步分离;然后向沉铝后的溶液再通入二氧化碳,使镓完全沉淀析出,再从沉淀中回收富集的镓。该方法在美国铝业公司和中铝山东有限公司进行过工业化生产,适用于从烧结法的低镓母液中提取镓,具有产品质量好、回收率高等优点;缺点是工艺流程较复杂、蒸水量大、返回液难以处理、废渣利用率低。
离子交换树脂法的原理是:将铝酸钠溶液通过树脂交换柱,首先使镓吸附到树脂上,然后再经洗涤、脱附工序得到镓溶液,随后再经净化、电解等工序得到金属镓,吸附后的溶液则返回氧化铝生产流程。该法是当前氧化铝行业工业化应用极为成熟的提镓工艺。日本住友株式商会Kataoka利用合成的偕胺肟浸渍酰胺树脂DHG586和Duolit Es-346回收铝酸钠溶液中的镓,镓吸附率达到96%[16]。丙烯酸离子交换剂对于强碱溶液中的镓有吸附作用,但对溶液温度有限制,温度控制在60 ℃时更有利于回收镓[17]。文献[18]研究发现,CL-P204树脂对镓的吸附率较高,可以达到94.5%,并且饱和吸附容量为42.4 mg/g。该方法工艺流程简单,生产成本较低,镓收得率及纯度较高,整个流程中无污染,对氧化铝生产也无不良影响,但需要设置前端除杂工序,以减少杂质对吸附率的影响。
萃取法的原理是:选用含适当配位体的有机物为萃取剂,将铝酸钠溶液中的镓萃取到有机相中,富镓有机相经多次洗涤后,再用反萃剂使有机相中的镓进入水相,富镓水相经处理后制成电解原液,电解后即可得到金属镓,有机相可再生返回使用,萃镓余液返回Al2O3生产系统。法国提出用Kelex-100作萃取剂从氧化铝循环母液中萃取镓,随后改进为8% Kelex-100+8%癸醇/煤油萃取体系,两级萃取率可达97%,并实现规模化生产[19]。我国上海有机化学研究所研发合成了3种不同取代基的Kelex-l00,其萃镓性能良好。研究表明,多种萃取剂如8-羟基喹啉、乙酰丙酮、高分子量季铵盐、7-代-8-羟基喹啉等均适合从铝酸钠溶液中萃取镓。萃取法简便易行,可以从镓含量低的铝酸钠溶液中直接提镓而不改变铝酸钠溶液的成分;缺点是萃取剂价格昂贵,其在碱液中的稳定性不强,萃取时间较长。
在湿法炼锌过程中,大约93.5%的镓富集在浸出渣中,一般需要经还原焙烧后酸浸,或直接酸浸处理,再对浸出液中的镓进行萃取。而在火法炼锌工艺中,镓主要富集在鼓风炉炉渣里,通常采用浸出法结合萃取法的两步提镓工艺。
文献[20]研究表明,在酸初始质量浓度153 g/L、浸出温度95 ℃、浸出时间3 h、液固比5.0~6.0条件下,镓浸出率可达88%;为进一步提高浸出率,以一段浸出渣为原料开展二段热酸浸出,经二段浸出后,镓的总浸出率达到91.5%。文献[21]探究了采用热酸浸出锌浸渣的工艺条件,在硫酸初始质量浓度188 g/L、浸出温度95 ℃、浸出时间3 h、液固比5∶1及搅拌速度300 r/min条件下,酸浸出液中镓浸出率高于86%。该法的优点是浸出率较高,但在除铁过程中会造成镓的损失。
文献[22]进行了碱浸-还原挥发工艺的试验研究,成功从镓锗置换渣中回收镓和锗,在NaOH浓度4 mol/L、反应温度90 ℃、液固比8 mL/g、搅拌速度400 r/min条件下,镓、锗浸出率分别为91.25%、78.95%。碱浸出工艺可以高效地从锌浸出渣中回收镓,并且镓的提取率较高,该法成本相对较低,但对操作条件要求较高。文献[23]通过常压浸出从锌置换渣中回收镓,在硫酸浓度1.5 mol/L、温度80 ℃、液固比7.5 mL/g、浸出时间3 h条件下,镓浸出率可达97.74%。
文献[24]研究了萃取剂HBL 121从锌置换渣的高浓度硫酸浸出液中萃取镓,通过优化萃取条件,镓萃取率可达到98.14%。文献[25]对锌渣置换后进行酸浸得到含镓、锗、铟的溶液,采用P204萃取铟,萃余液经P204+YW100萃取得到镓和锗。该工艺能够同时回收镓、锗、铟,流程短、效率高,金属回收率高,但YW100萃取剂易降解、稳定性差。文献[26]采用硫酸抑硅氧压浸出技术,使锌置换渣中的镓,浸出率达到94.04%,浸出液采用全萃法分离提取,镓萃取率达到98.57%,综合回收率92.70%。该工艺实现了镓、锌高效全值分离回收,并且溶液体系形成了闭路循环。萃取法效率高、选择性强、适用范围广、产品纯度高,目前其技术路线相对成熟、应用较为广泛。
文献[27]用P507萃取树脂对硫酸溶液中Ga、Zn和In的分离进行了研究,结果表明,Ga的饱和吸附量为31.0 mg/g。文献[28]制备了一种多孔新型树脂,将P507和TBP萃取剂通过真空浸渍和干燥合成附着在二氧化硅基材料上,在pH值3.3的低浓度硫酸溶液中,镓的吸附量为64.2 mg/g。树脂吸附法具有高选择性,能有效吸附镓而分离杂质,但生产成本较高,且吸附容量有限。
文献[29]以P204、TBP和TRPO为萃取剂,煤油为稀释剂,K4Fe(CN)6为内水相剂,加入表面活性剂,高速搅拌制成乳状液,制备好的乳液与含镓溶液进行搅拌,萃取溶液中的镓离子。文献[30]以TBP为萃取剂,选用油酸钠和十六烷基三甲基溴化铵为表面活性剂、正庚烷为稀释剂、盐酸为内水相制备液膜,在TBP浓度6%条件下,镓萃取率大于98%。文献[31]研究表明,将萃取剂0,0-二羟基磷氧肟酸、稀释剂磺化煤油、表面活性剂山梨醇单油酸酯和山梨醇酐单硬脂酸酯在2 mol/L的硫酸体系中混合,采用超声波形成乳状液膜体系,在萃取剂浓度(质量分数)5.0%和镓溶液/乳液体积比5.0时,萃取率可以达到90.3%,镓离子富集比可以达到27倍。该技术现处于初期研究阶段,存在杂质离子选择度不高、负载离子浓度低、体系稳定性差等缺点,尚未达到工业化应用水平,但其具有一体化的萃取和反萃过程,展现出独特的发展潜力。
提钒尾渣是一种富镓资源,具有多金属共存的特点。受钒渣元素成分多样性影响,制约提镓效率、成本的因素众多,通常根据成分确定技术路线,采取优势互补的组合方法,以此来改善生产效率低下的问题。
钒钛磁铁矿经雾化法提钒后,残渣中的镓含量(质量分数)约0.014%,可作为提镓原料。文献[32]采用氯化还原法,使钒渣中的镓挥发并富集到烟尘中,镓挥发率可达到46%,但由于后续的碱溶、电沉积等工序会造成镓损失,最终镓回收率约35%。文献[33]采用氯化还原法提镓,对Ga2O3含量(质量分数)0.022 3%的钒渣配入25%的CaCl2,在1 000 ℃下氯化焙烧2 h,镓的氯化挥发率达到58.5%。该方法将镓以气态形式从钒渣中提取,可获得纯度较高的镓,但其局限性在于废气废液污染问题明显,工业应用面临诸多困难。
文献[34]采用碱熔活化-碱浸法来提取钒渣中的镓,将提钒渣与25% Na2CO3、6% NaOH、40% CaO均匀混合,在1 000 ℃下焙烧2 h制备活化渣,再使用100 g/L的NaOH溶液进行碱浸,在液固比5∶1、温度80 ℃并不断搅拌的条件下,镓浸出率可达90%。该方法不仅可获得较高的镓浸出率,而且可有效减少和避免污染物的产生,具有较强的研究和推广应用价值。研究表明,在钒渣中加入CaO和Na2CO3,在950~1 000 ℃条件下进行碱熔活化,熟料经过冷却后再细磨,然后将细磨料进行水浸,得到含有镓、铬、钒的混合浸出液,镓浸出率可以达到85%[35]。该方法经一次焙烧就能得到镓,但焙烧温度过高,钒渣呈熔融状态,粘窑影响生产,且焙烧产物不易破碎,未能实现工业应用。
还原熔炼法是将钒渣配碳后在熔融状态下进行还原,得到铁镓合金,再通过电解等工序回收镓。文献[36-37]开展了钒渣在加碳条件下的熔融还原试验,在碳不饱和条件下,镓还原率达到了78.32%,时间对还原率影响较大,随着时间延长,镓挥发损失较大;而在碳饱和、添加CaO的条件下,镓还原率提高到了94.7%。但该工艺流程长、成本高,未能在工业上应用。文献[38]以攀钢生产的钒渣为原料,采用碳粉还原-铁电解-阳极泥酸浸-萃取-镓电解的工艺回收镓,酸浸采用6 mol/L浓盐酸,液固比3∶1,在95 ℃条件下浸出2 h,选用TBP为萃取剂,电解后镓回收率为64.9%。该工艺将镓富集到阳极泥中,提高了镓的品位,但存在工艺流程长、能耗高、成本高、镓回收率较低等问题。
在煤炭的开采利用过程中,镓的迁移规律受原煤性质及燃烧条件影响较大,并且镓在煤矸石、粉煤灰及气化灰渣等中的赋存状态不同。由于煤基固体废弃物成分复杂,而且镓含量较低,单一提取方法不能实现镓的高效分离,往往采取多种方法相结合的提镓工艺。
文献[39]研究了中性萃取剂P507、Cyanex 272对粉煤灰硫酸浸出液中各金属离子的萃取行为,其中使用萃取剂P507可有效萃取溶液中的Fe3+和Ti4+,然后控制pH值为2.4~2.6,Cyanex 272可与Ga3+形成配合物,镓萃取率达到81.7%。文献[40]研究了萃取剂Cyanex 921对粉煤灰盐酸浸出液中镓的萃取效果,在优化条件下镓回收率能够达到93%。但此法需要设置磁选除铁工序,否则铁会进入浸出液中,从而不利于镓的萃取分离。
文献[41]研究了在粉煤灰盐酸浸出体系中采用聚氨酯泡沫塑料对镓进行吸附,在较优条件下镓吸附率高于98%,静态吸附容量为46.7 mg/g,而且溶液经过除铁后其他离子对镓的吸附影响极小。文献[42]对粉煤灰原料进行预脱硅、熟料溶出等处理后,对溶出液进行碳分、沉淀酸溶,用聚氨酯泡沫塑料进行吸附、洗脱,其吸附率大于90%,溶液中镓离子浓度为0.87 μg/mL,镓沉淀率和回收率分别为86.12%和77.56%。文献[43]将粉煤灰焙烧活化预处理,破坏铝硅的玻璃体晶格后再用盐酸浸出,镓浸出率可达80%以上,然后用聚氨酯泡沫塑料吸附浸出液中的镓,吸附率为85.12%。聚氨酯泡沫塑料不仅可以反复再生使用,还可以负载萃取剂或螯合剂,提高其吸附选择性,但目前此法主要集中在实验室研究阶段。
文献[44]研究了不同种类的无机酸对粉煤灰中镓浸出的效果,盐酸比硫酸、硝酸浸出的效果更好。文献[45]在HCl溶液浓度1.8 mol/L、液固比5 mL/g、室温浸出24 h,从煤烟尘中得到浓度95 μg/g的含镓溶液,浸出液经处理后,镓吸附率大于95%。
文献[46]将高铝粉煤灰与Na2CO3、CaCO3和CaO均匀混合活化焙烧,得到的焙烧产物经一定浓度碱性溶液浸出,使镓形成镓酸根离子,然后用盐酸浸出变成镓离子,浸出液中镓含量达到41.438 g/t。文献[47]直接用NaOH浸出粉煤灰,经过预浓缩、两次碳化渗滤液沉淀分离镓,镓提取率达到60%~86%。碱浸法使用原料价廉、容易获得,且设备和材料来自粉煤灰系统内,碳酸氢钠可重复使用,生产成本较低。
从全球镓生产现状来看,90%镓来源于氧化铝生产过程,10%来源于锌冶炼过程。受限于提取技术、生产成本、开发条件等,尚未实现从提钒尾渣和煤基固体废弃物中工业化开发镓资源。镓的提取方法主要采用湿法工艺,部分采用火法与湿法联合工艺。
近年来,在有色金属行业快速发展背景下,国内镓产业蓬勃发展,但亦面临诸多亟待解决的问题,以下三个方面值得重点关注。
1)镓资源保障模式较为单一,缺乏有效补充途径。目前,我国镓产能主要集中在晋、豫、桂等地,依赖国产铝土矿资源生产过程,来源渠道较为单一,其他途径提镓的总产量十分有限。镓是氧化铝生产过程中的副产品,其产量与氧化铝行业景气度密切相关。当前海内外氧化铝产能过剩,我国氧化铝行业呈现弹性生产特征,尤其是国产矿主产区,受矿石供给制约,产能利用率波动较大,导致镓的产量和价格起伏变化。为避免国产矿短缺扰动镓市场,亟须加大各类富镓资源的开发力度,构建多元化的原料供应链,多途径保障镓产业链安全。
2)科技创新能力薄弱,关键技术积累不足。当前,我国氧化铝布局正加速由内陆向沿海转移,对海外矿的依存度持续攀升。矿石资源结构的改变给镓的生产带来新的挑战。虽然国产矿提镓技术已经相当成熟,但由于矿石的多样性和复杂性,现有技术面对进口矿则显现出局限性。我国对进口矿提镓研究起步较晚,关键技术储备相对不足,配套技术还不完善,存在提取效率低、生产成本高的突出问题,至今尚未开发出矿石适应性强、成熟可靠的工艺路线,导致产业化进展缓慢。未来,随着国产矿日渐枯竭及进口矿产能不断扩大,开发高效低成本的新一代提镓技术是提升供应链韧性的重要保障。
3)高度依附自然资源,城市矿产利用率低。镓在自然界无单独存在的矿床,常伴生在金属和煤炭等自然资源中,目前原生镓的提取以铝矿和锌矿资源为主。由于镓在原矿中的含量极低,并且是作为铝和锌冶炼的副产品,生产过程中损失较大,产量相对较低,因此,镓的生产高度依附自然资源。与此同时,我国对再生镓不够重视,城市矿产利用率低。随着数字产业化的发展,电子产品固体废弃物在逐年增加,积累的镓资源相当可观,与自然矿产资源相比已属富矿,极具开发利用价值。充分挖掘城市矿产资源,实现镓的循环利用,不仅可解决自然资源过度开发问题,还能推动镓产业链的低碳、绿色可持续发展。
  • 中国工程科技发展战略山东研究院项目(202301SDZD03)
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2025年第45卷第5期
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doi: 10.3969/j.issn.0253-6099.2025.05.022
  • 接收时间:2025-04-25
  • 首发时间:2026-03-18
  • 出版时间:2025-10-01
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  • 收稿日期:2025-04-25
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中国工程科技发展战略山东研究院项目(202301SDZD03)
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    1.龙口东海氧化铝有限公司,山东 龙口 265713
    2.中南大学 冶金与环境学院,湖南 长沙 410083
    3.山东南山铝业股份有限公司 有色金属产业研究院,山东 龙口 265713
    4.烟台南山学院 材料科学与工程学院,山东 龙口 265700
    5.山东南山铝业股份有限公司 国家铝合金压力加工工程技术研究中心,山东 龙口 265713
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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