Article(id=1148110005775102050, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1148109990923072455, articleNumber=1009-2617(2025)02-0133-10, orderNo=null, doi=10.13355/j.cnki.sfyj.2025.02.001, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1731081600000, receivedDateStr=2024-11-09, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1751660356229, onlineDateStr=2025-07-05, pubDate=1745769600000, pubDateStr=2025-04-28, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1751660356229, onlineIssueDateStr=2025-07-05, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1751660356229, creator=13701087609, updateTime=1751660356229, updator=13701087609, issue=Issue{id=1148109990923072455, tenantId=1146029695717560320, journalId=1146120122248306696, year='2025', volume='44', issue='2', pageStart='133', pageEnd='279', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1751660352687, creator=13701087609, updateTime=1758246043500, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1175732380301148501, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1148109990923072455, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1175732380301148502, tenantId=1146029695717560320, journalId=1146120122248306696, issueId=1148109990923072455, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=133, endPage=142, ext={EN=ArticleExt(id=1148110006014177405, articleId=1148110005775102050, tenantId=1146029695717560320, journalId=1146120122248306696, language=EN, title=Research Status and Development Direction of Recycling NdFeB Wastes by Hydrometallurgy, columnId=1152626642049446094, journalTitle=Hydrometallurgy of China, columnName=Reviews, runingTitle=null, highlight=null, articleAbstract=

In the production and processing of NdFeB,more than 30% of rare earth metals will be transferred to the waste, resulting in NdFeB waste can not be effectively used. With the rapid development of new energy automobile industry,the green recycling of NdfeB waste has become a research hotspot in this field. The current research status of hydrometallurgy for recycling NdFeB waste at home and abroad, including acid leaching,precipitation, solvent extraction, alkali decomposition, ionic liquid recovery, hydrolysis and microbial decomposition, are reviewed. At the same time, the technical difficulties facing the current research are pointed out. Finally, the main research direction of NdFeB waste recycling in the future is put forward, which provides valuable reference for the secondary utilization of rare earth resources.

, correspAuthors=Xiaowei ZHANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Xiaodong WANG, Xiaowei ZHANG, Feng GUO, Jianfei LI, Chuxuan DENG, Shuang WANG), CN=ArticleExt(id=1148110016994865198, articleId=1148110005775102050, tenantId=1146029695717560320, journalId=1146120122248306696, language=CN, title=湿法工艺回收钕铁硼废料的研究现状及发展方向, columnId=1152626642166886607, journalTitle=湿法冶金, columnName=综合评述, runingTitle=null, highlight=null, articleAbstract=

钕铁硼在生产加工过程中,有超过30%的稀土金属转移到废料中,导致钕铁硼废料未能得到有效利用,而随着新能源汽车行业的快速发展,钕铁硼废料的绿色回收已成为该领域的研究热点。综述了目前国内外回收钕铁硼废料的湿法工艺研究现状,包括酸浸法、沉淀法、溶剂萃取法、碱分解法、离子液体回收法、水解法及微生物分解法等多种方法的原理及优缺点,同时指出了当前研究面临的技术难点,最后提出了未来钕铁硼废料回收利用的主要研究方向,为稀土资源二次利用提供有价值的参考。

, correspAuthors=张晓伟, authorNote=null, correspAuthorsNote=
张晓伟(1983—),男,博士,副教授,主要研究方向为稀土湿法冶金及二次资源循环利用。E-mail:
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王晓东(2000—),男,硕士研究生,主要研究方向为稀土矿物绿色提取与高质化应用。

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王晓东(2000—),男,硕士研究生,主要研究方向为稀土矿物绿色提取与高质化应用。

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王晓东(2000—),男,硕士研究生,主要研究方向为稀土矿物绿色提取与高质化应用。

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湿法工艺回收钕铁硼废料的研究现状及发展方向
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王晓东 1, 2 , 张晓伟 1, 2 , 郭峰 1, 2 , 李健飞 1, 2 , 邓楚璇 1, 2 , 王双 1, 2
湿法冶金 | 综合评述 2025,44(2): 133-142
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湿法冶金 | 综合评述 2025, 44(2): 133-142
湿法工艺回收钕铁硼废料的研究现状及发展方向
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王晓东1, 2, 张晓伟1, 2 , 郭峰1, 2, 李健飞1, 2, 邓楚璇1, 2, 王双1, 2
作者信息
  • 1 内蒙古科技大学 稀土产业学院, 内蒙古 包头 014010
  • 2 轻稀土资源绿色提取与高效利用教育部重点实验室, 内蒙古 包头 014010
  • 王晓东(2000—),男,硕士研究生,主要研究方向为稀土矿物绿色提取与高质化应用。

通讯作者:

张晓伟(1983—),男,博士,副教授,主要研究方向为稀土湿法冶金及二次资源循环利用。E-mail:
Research Status and Development Direction of Recycling NdFeB Wastes by Hydrometallurgy
Xiaodong WANG1, 2, Xiaowei ZHANG1, 2 , Feng GUO1, 2, Jianfei LI1, 2, Chuxuan DENG1, 2, Shuang WANG1, 2
Affiliations
  • 1 College of Rare Earth Industry, Inner Mongolia University of Science and Technology, Baotou 014010, China
  • 2 Key Laboratory of Green Extraction and Efficient Utilization of Light Rare Earth Resources, Ministry of Education, Baotou 014010, China
出版时间: 2025-04-28 doi: 10.13355/j.cnki.sfyj.2025.02.001
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钕铁硼在生产加工过程中,有超过30%的稀土金属转移到废料中,导致钕铁硼废料未能得到有效利用,而随着新能源汽车行业的快速发展,钕铁硼废料的绿色回收已成为该领域的研究热点。综述了目前国内外回收钕铁硼废料的湿法工艺研究现状,包括酸浸法、沉淀法、溶剂萃取法、碱分解法、离子液体回收法、水解法及微生物分解法等多种方法的原理及优缺点,同时指出了当前研究面临的技术难点,最后提出了未来钕铁硼废料回收利用的主要研究方向,为稀土资源二次利用提供有价值的参考。

钕铁硼  /  废料  /  稀土  /  湿法  /  回收  /  研究现状  /  发展方向

In the production and processing of NdFeB,more than 30% of rare earth metals will be transferred to the waste, resulting in NdFeB waste can not be effectively used. With the rapid development of new energy automobile industry,the green recycling of NdfeB waste has become a research hotspot in this field. The current research status of hydrometallurgy for recycling NdFeB waste at home and abroad, including acid leaching,precipitation, solvent extraction, alkali decomposition, ionic liquid recovery, hydrolysis and microbial decomposition, are reviewed. At the same time, the technical difficulties facing the current research are pointed out. Finally, the main research direction of NdFeB waste recycling in the future is put forward, which provides valuable reference for the secondary utilization of rare earth resources.

NdFeB  /  waste  /  rare earth  /  hydrometallurgy  /  recovery  /  research status  /  development direction
王晓东, 张晓伟, 郭峰, 李健飞, 邓楚璇, 王双. 湿法工艺回收钕铁硼废料的研究现状及发展方向. 湿法冶金, 2025 , 44 (2) : 133 -142 . DOI: 10.13355/j.cnki.sfyj.2025.02.001
Xiaodong WANG, Xiaowei ZHANG, Feng GUO, Jianfei LI, Chuxuan DENG, Shuang WANG. Research Status and Development Direction of Recycling NdFeB Wastes by Hydrometallurgy[J]. Hydrometallurgy of China, 2025 , 44 (2) : 133 -142 . DOI: 10.13355/j.cnki.sfyj.2025.02.001
钕铁硼是目前仅次于在绝对零度以下的钬磁铁的永久磁铁,同时也是一种稀土永磁材料[1],因具有极高的磁能积和优异的磁性能,在材料科学与工程、电机与电力工程、信息存储与磁记录及新能源与环境保护等多个领域得到了广泛应用[2]。在钕铁硼的生产过程中,由于工艺和设备等条件限制,会产生占原材料约25%的废料,其中稀土元素质量分数约占33%[3],这些钕铁硼废料若得不到合理的回收处理,不仅会导致巨大的资源浪费,而且会对环境造成严重污染。因此对钕铁硼二次资源加以回收再利用,不仅符合稀土的可持续发展战略,也具有极大的经济价值和环境效益[4]
目前,国内外回收钕铁硼废料的湿法工艺已有多种,包括酸浸法、沉淀法、溶剂萃取法、碱分解法、离子液体回收法、水解法及微生物分解法等。本文综述了这些工艺的原理及优缺点,并指出了各工艺当前存在的技术难点,同时提出了未来钕铁硼废料回收利用的主要研究方向,以期为稀土资源二次回收利用提供参考。
钕铁硼材料的化学组成为Nd2Fe14B,钕铁硼磁体由25%~35%的稀土元素、60%~70%的铁及1%左右的硼组成[5],晶体结构如图1所示。
钕铁硼材料具有四面体结构[6],其晶体结构属于六角最密堆积结构,由钕原子形成四面体结构的中心,而铁原子则位于四面体结构的顶点上,硼原子填充在四面体结构之间的空隙中[7]。正是因为稀土元素在钕铁硼的晶体结构中以离子形式存在,使得其在溶液中具有较高的溶解性。这种特性为湿法工艺提供了有利条件,使得稀土元素能更有效地从钕铁硼废料中提取出来[8]
湿法回收工艺主要是通过水溶液溶解初级和次级资源中的稀土元素,随后利用沉淀、萃取或离子交换等手段实现这些元素的分离和纯化,因其具有回收率高和选择性好等优点,在处理复杂废物方面具有明显优势[9]。目前常见的从钕铁硼废料中湿法回收稀土元素的工艺主要包括酸浸法、沉淀法、溶剂萃取法、碱分解法、离子液体回收法、水解法及生物分解法等。
无机酸浸出法是从钕铁硼废料中回收稀土元素的常用方法。当钕铁硼磁体在稀酸中溶解时,溶液中的Nd、Fe和B离子会与H+相互作用而浸出,后续再通过分离和纯化工序得到回收。
Tian Y.L.等[10]研究了以盐酸为浸出剂、六亚甲基四胺(HMTA)或酒石酸为螯合剂,从钕铁硼废料中选择性浸出稀土,并通过焙烧得到稀土氧化物,工艺流程如图2所示。结果表明:在盐酸浓度6 mol/L、酒石酸质量浓度50 g/L、温度313 K优化条件下,稀土浸出率达99.27%,铁浸出率为67.99%;在草酸与酸浸液固液质量体积比(g/mL)为1.5/1、pH=1.5条件下沉淀稀土,之后在900 ℃高温下焙烧2 h,可得到纯度为95.83%的Nd2O3产品,稀土回收率为90.18%。
Yan Z.M.等[11]研究了采用硝酸从钕铁硼废料中选择性浸出稀土,工艺流程如图3所示。结果表明:在硝酸浓度0.5 mol/L、液固体积质量比(mL/g)为20/1、浸出温度180 ℃、浸出时间1.5 h优化条件下,稀土浸出率超过95%,而铁溶解度低于0.3%;添加Na2S对过渡金属杂质的去除效果较好,但会导致约10%的稀土损失;直接用草酸沉淀可得到纯度超过97.5%的稀土氧化物。该工艺通过高压选择性浸出和沉淀能获得高纯度稀土氧化物,回收率超过95%,产生的电解废料仍可进一步循环回收,从而实现稀土回收最大化。
Zhang L.P.等[12]研究了采用硫酸从钕铁硼浸出渣中回收稀土,工艺流程如图4所示。
钕铁硼浸出渣经研磨后用硫酸浸出,之后通过添加铜粉还原,得到的浸出液通过选择性沉淀后,铜再次循环利用;然后向浸出液中加入氨水,将铁杂质氧化合成晶种和颜料,再通过向富含氨基硫酸盐溶液中加入Ca(OH)2,通过蒸发得到稀土溶液和氨水,以实现氨水的循环利用;得到的稀土溶液中再加入磷酸锆,通过吸附分离,得到氧化稀土和氧化钴。结果表明:在酸浸阶段,控制酸浸温度363 K、硫酸浓度1.4 mol/L、固液质量体积比(g/L)为80/1、铜粉作为还原剂(n(Cu)∶n(Fe3+)=1∶2),并在吸附分离阶段调节pH=1.87、同时以稀释的HNO3为洗脱剂,钴、钕、镨、铈回收率分别为90.6%、89.1%、77.2%、88.7%;用铁粉可成功回收铜粉,回收率为99.93%,纯度为93.42%。该工艺能在低酸消耗下获得稀土元素的最佳回收效果,具有一定的可持续性。
He L.X.等[13]研究了用磷酸为浸出剂分离回收钕铁硼废料中的稀土和铁,工艺流程如图5所示。
钕铁硼废料用磷酸浸出得到稀土磷酸盐沉淀和富铁溶液,再向稀土磷酸盐沉淀加入盐酸反应得到稀土溶液,稀土溶液中的铁再通过加入草酸加以回收。结果表明:在浸出温度80 ℃、液固体积质量比(mL/g)30/1、浸出时间90 min条件下,98.91%的稀土以REPO4·nH2O沉淀形式留在浸出渣中,98.7%的铁以Fe2+形式存在于溶液中;所得稀土磷酸盐沉淀再用2 mol盐酸,在60 ℃下酸浸2 h,得到氯化稀土溶液,氯化稀土溶液加入草酸并在800 ℃下焙烧可得到纯度为99.49%多稀土氧化物。
无机酸浸出法作为回收钕铁硼废料中稀土元素的常用技术之一,能有效溶解钕铁硼废料中的稀土元素,回收率较高,操作流程相对简单,易于工业化应用;但该法的化学试剂消耗较大,且后续还需对废水进行处理,生产成本较高。
相较于无机酸浸出法,采用有机酸浸出法处理钕铁硼废料的优势在于化学试剂消耗小且更加环保[14]
Belfqueh等[15]研究了用有机酸(乙酸、甲酸、枸橼酸和酒石酸)从钕铁硼磁体中回收稀土,工艺流程如图6所示。在固液质量体积比(g/mL)为1/(20~200)、酸浓度1.6~10 mol/L、温度60 ℃、酸浸时间24 h最佳条件下,分别采用酒石酸、甲酸、乙酸、枸橼酸浸出钕铁硼磁体,最高稀土浸出率分别为35%、73%、90%、95%;由于乙酸在不同的固液质量体积比和酸度条件下浸出率均大于90%,浸出性能优异,具有较强的适应性,因此建议选用乙酸从钕铁硼磁粉中浸出稀土元素。
Reisdorfer等[16]研究了采用苹果酸和枸橼酸从废弃钕铁硼永磁体中回收钕。结果表明:未焙烧的NdFeB粉末在温度90 ℃、有机酸浓度1.0 mol/L、固液质量体积比1/20条件下,用苹果酸浸出360 min,钕回收率可达99%,而枸橼酸浸出60 min,钕回收率为72.8%;相同条件下,分别用苹果酸和枸橼酸浸出焙烧后的NdFeB粉末,钕回收率均比未焙烧的低,分别为22%和32.1%,但研究发现二者对钕的选择性均显著提高,苹果酸为86%,枸橼酸为98%。随后,该团队又采用超临界CO2作为助溶手段进一步进行了研究[17]。结果表明:利用超临界CO2从含有苹果酸的未焙烧磁体粉末中回收钕时,浸出时间缩短至30 min,钕回收率可达99.9%;对于经焙烧处理的钕铁硼粉末,用苹果酸和枸橼酸浸出120 min后,钕回收率分别为99.5%和30.6%。
沉淀法是将钕铁硼废料溶解在酸溶液中,再通过添加沉淀剂,使稀土元素形成沉淀物的方法。该法能有效提高稀土资源利用率,减少资源浪费,主要分为复盐沉淀法、共沉淀法、草酸直接沉淀法等。
复盐沉淀法是通过添加沉淀剂使钕铁硼废料中的稀土金属与沉淀剂反应,形成不溶性沉淀,从溶液中分离并回收稀土金属,常用的复盐有Na2SO4、(NH4)2SO4、NaCl、Na3PO4等。该法通常是通过一系列工序,包括氧化焙烧、酸液浸出、复盐沉淀、碱转、萃取分离、沉淀、焙烧从钕铁硼材料中提取有价元素,并制得高纯度氧化钕的方法[18]。Nguyen等[19]研究了采用硫酸溶解—硫酸钠沉淀法从钕铁硼废料中沉淀回收稀土,工艺流程如图7所示。
该工艺在温度80 ℃、Na2SO4与RE3+物质的量比为2.5∶1条件下,稀土可完全沉淀;沉淀物中Nd、Pr、Ce、Na质量分数分别为22.99%、7.27%、7.07%和4.80%,稀土纯度高于99.9%;经铁粉还原得到的Na2SO4可循环使用,大大降低成本。该工艺具有操作流程简洁、生产成本较低等优势,特别是对于富含Nd的稀土废料,效果尤为突出;但在实际生产中,不能有效回收硫酸亚铁,直接排放会对环境造成不利影响。
与选择性沉淀法相比,共沉淀法可同时回收钕铁硼磁铁浸出液中的金属离子,获得含有稀土、铁和钴的复合粉末[20]。田忆兰等[21]研究了采用共沉淀法从钕铁硼废料中沉淀稀土,工艺流程如图8所示。结果表明:在浸出温度65 ℃、溶液pH=3条件下,稀土元素回收率为94.92%,Fe回收率达99.49%。该法具有工艺流程短、操作可控、节能环保等特点;但所得产物为铁与稀土的混合氧化物,因仅有少量纯的稀土氧化物,后续仍需进一步通过还原反应来制取再生钕铁硼磁体。
草酸直接沉淀法是将草酸直接加入钕铁硼废料的酸性溶液中制得稀土草酸盐。钕铁硼废料经溶解后,溶液中Fe和稀土离子与草酸形成的盐类物质的溶解度存在明显差异,根据其溶解度差异可使Fe和稀土实现分离。尹小文等[22]研究了采用草酸直接沉淀法回收钕铁硼废料中的稀土,工艺流程如图9所示。
该工艺在温度80 ℃、溶液pH=1.5~2.0、草酸与酸浸液固液质量体积比(g/mL)为1.5/1条件下,稀土回收率可达95.4%,而后在800 ℃下焙烧可得到纯度为99.27%的稀土氧化物。该法对稀土与铁的分离效果明显,工艺流程简单,稀土回收率高,且无需昂贵的萃取剂;但需精准控制沉淀过程pH、温度及草酸用量,目前实现工业化还有一定难度。
溶剂萃取法是通过使用有机溶剂选择性地溶解钕铁硼废料中的稀土金属离子,利用相分配原理分离并回收金属,常用的萃取剂有四辛基二甘酰胺、辛基膦酸、三辛基胺、二乙基己基磷酸等。将钕铁硼废料进行酸溶后,添加对稀土元素具有较高亲和力的萃取剂,使二者形成配合物后,再分离有机相与水相,最后通过反萃取剂(如稀酸或碱)将稀土元素从有机相中重新转移到水相中,以实现回收和进一步纯化。
Choubey等[23]研究了用Cyanex272萃取剂从钕铁硼废料中萃取回收稀土。首先用硫酸浸出钕铁硼废料,向所得含稀土浸出液中加入Cyanex272萃取剂萃取稀土,负载稀土有机相经反萃、焙烧得到稀土氧化物,萃余液经NH4OH沉淀后得到Fe2O3,工艺流程如图10所示。结果表明:在酸浸条件(酸浸温度75 ℃、硫酸浓度2 mol/L、浆体密度100 g/L)下,控制溶液pH=3时,钕浸出率达95.5%,镨、镝浸出率均达99.9%;96.5%的铁可以离子形式沉淀,从而实现了钕、铁有效分离。
Belfqueh等[24]研究了用四辛基二甘酰胺(TODGA)从钕铁硼乙酸浸出液中萃取稀土,工艺流程如图11所示。结果表明:向钕铁硼乙酸浸出液中加入TODGA萃取剂,在相比(Vo/Va)为1/1、温度20 ℃条件下萃取60 min,Nd、Pr和Dy回收率分别为92%、88%和99%。采用TODGA作为萃取剂萃取钕铁硼废料中的稀土,可多次循环使用,且萃取效率和选择性较高,回收率稳定;但该法试剂成本较高,虽然用有机酸酸浸代替无机酸可减小对环境的影响,但萃取和反萃取过程中仍会产生大量废水,需进一步处理。
碱分解法是利用碱性物质与钕铁硼磁体反应,有效分离钕和其他稀土元素的方法,在此过程中,钕可转化为可溶性的钕化合物,而铁等杂质则形成难溶物,从而实现二者的高效分离和提纯。
Yoon等[25]研究了采用氢氧化钠分解工艺从钕铁硼废料回收稀土,NaOH与钕铁硼废料经研磨洗涤后分离得到Nd(OH)3和碱液,Nd(OH)3经氧化焙烧、醋酸浸出和萃取分离得到Nd2O3,而碱液则直接进行回收,工艺流程如图12所示。结果表明:在焙烧温度400 ℃、碱焙烧时间2 h优化条件下,加入1 mol/L乙酸并浸出180 min,钕、镝、铁浸出率分别为94.2%、93.1%、1.0%。
Önal等[26]在相对较低温度(150~200 ℃)下对钕铁硼粉末进行短时间(30~450 min)的加碱焙烧,焙烧过程中稀土转化为相应的氢氧化物,而铁金属形成NaFeO2。将焙烧粉末采用20%Versatic Acid 10(一种商业化的混合羧酸)作为溶剂,在固液质量体积比(g/mL)为20/1、反应时间1 h条件下从焙烧产物中浸出稀土,之后用草酸沉淀,再经过反萃取、焙烧,可得到纯度为98.4%的稀土氧化物。
碱分解法回收稀土的优势在于稀土元素回收率高、化学试剂消耗较少,且更为环保;该法对严重氧化的废料回收效果差,在浸出和分离过程中会产生含碱废水,处理不当会造成环境污染。
离子液体回收法是一种新工艺,其原理是利用有机萃取剂对金属阳离子具有不同的吸附能力的特性实现金属的分离。相较于传统萃取技术,离子液体萃取系统稳定性更强,分离效果和选择性更佳[27-29]
Sasaya等[30]采用硝酸溶解钕铁硼磁体废渣回收稀土,之后进行脱铁制得稀土硝酸盐;再将稀土硝酸盐溶于二硝酰胺铵溶液中,进行电沉积并获得稀土金属。该方法可得到纯度为99%的稀土氧化物,且具有工艺简单、试剂消耗小等优点;但浸出时间较长,达48 h,目前还很难进行大规模的应用推广[31]
Sun H.等[32]采用含氟离子的酸洗废水从超细钕铁硼废料中回收稀土,工艺流程如图13所示。将不锈钢酸洗废水(主要有氢阳离子、铁阳离子、硝酸根阴离子和氟离子)加入到超细钕铁硼废料中,二者会反应生成Nd(OH)2F,之后再经焙烧处理,得到最终产物NdOF。在氢离子浓度3.16 mol/L、氟离子浓度1.5 mol/L条件下,Nd(OH)2F回收率可达97%。该法不仅能达到从超细NdFeB废料中回收稀土元素的目的,还能降低含氟废水中氟离子浓度,具有双重效益;但该法仅适用于超细钕铁硼废料,对于其他类型或粒径的钕铁硼废料回收效果有限,此外,工艺对酸洗液中氟离子浓度要求也较高,使其应用受到一定限制。
水解法主要是充分利用稀土碳化物易水解的特性,实现对稀土的有效回收。首先将钕铁硼废矿进行焙烧碳化处理,之后通过水解得到稀土氢氧化物,最后采用磁选方式分离稀土氢氧化物和铁。
卞玉洋[33]采用真空感应炉对钕铁硼废渣进行熔融,再与石墨坩埚发生反应,形成钕铁硼碳化物,之后将钕铁硼碳化物加入到去离子水溶液中进行水解得到稀土和铁基合金粉末;再采用磁选分离法分离稀土和铁,最终获得了纯度达99.7%的稀土氢氧化物。该法稀土产品纯度高,工艺流程简单,较易实现工业化。
Liu B.W.等[34]研究了采用一种新的碳化/氢化水解工艺从废弃钕铁硼磁体中回收稀土元素,工艺流程如图14所示。结果表明,在1 400 ℃条件下,将钕铁硼粉末的碳化/氢化处理90 min,再通过水解和磁选分离处理,可得到纯度为99.43%的稀土氢氧化物,稀土回收率可达88.4%。
水解法对废料的预处理要求较高,分离提纯过程也较为复杂:但该法具有稀土回收率高、环境污染小、工艺流程较简单及适应性强等优点,具有一定的推广应用潜力。
生物浸出法是利用微生物将不溶性金属化合物以水溶解的方式进行生物转化,其原理是通过生物氧化和配合,使金属离子在水中转移,微生物在此过程中起着至关重要的作用[35]
Auerbach等[36]研究了采用酸性嗜铁细菌浸出废弃磁性材料回收稀土,工艺流程如图15所示,先采用DEHPA及CyphosIL101等萃取剂将稀土元素从浸出液中萃取到有机相中;再通过反萃取将稀土元素从有机相中转移到水相,得到高纯度的稀土金属离子溶液。结果表明:在浸出温度40 ℃、pH=3.0适宜条件下,细菌能保持活性并促进金属溶解;在各类菌种中,酸性氧化铁硫杆菌和氧化亚铁螺旋体对稀土的浸出率最高,Pr浸出率可达100%。
生物浸出法与传统的酸浸法相比,对环境污染更小,没有酸性废水产生,能耗也相对较低,无需高温高压,主要利用微生物的代谢活动实现金属浸出,是一种环境友好型的工艺;但该法须严格控制工艺条件,如pH、温度和微生物种类等,操作较为复杂。
钕铁硼废料回收技术包括酸浸法、沉淀法、溶剂萃取法、碱分解法、离子液体回收法、水解法和微生物分解法等。酸浸法高效,但有腐蚀性,易造成污染;沉淀法成本低,但效率较低;溶剂萃取法能高效分离,但成本较高;碱分解法在钕和铁回收中有效,但污染大;离子液体回收法高效,但成本较高;水解法适用于简单合金,但回收率低;微生物分解法环保且选择性强,但仍处于研究阶段。为更好地对钕铁硼废料进行回收利用,建议今后可从以下几个方面进行优化:
1)强化绿色环保与低污染技术。酸浸法、碱分解法等传统方法在环境污染方面存在一定风险,建议通过优化工艺或开发新型绿色溶剂(如离子液体、绿色化学试剂)来减少环境影响,推动废料回收过程的绿色转型十分必要。
2)提升回收工艺的高效性和经济性。溶剂萃取法、离子液体回收法等虽具有较高回收效率,但成本较高,今后应聚焦于降低技术操作成本和能耗,如通过优化溶剂的选择和回收工艺、提升设备能效,以及实现工艺的自动化和智能化等措施,使钕铁硼回收更具经济性。
3)进一步探索新型回收技术。微生物分解法、超临界流体萃取法等新兴技术仍处于研究阶段,需进一步探索和优化,尤其是微生物分解法,虽具有较强的选择性和环境友好性,但技术成熟度不足,未来可以通过基因工程改造微生物、提高其对稀土元素的吸附与解吸能力,提升其实际应用效果。
4)推动循环经济模式与资源综合利用。钕铁硼废料回收不仅要注重金属的提取,还要考虑回收过程中其他副产物,如铁、铝等金属和硼化合物的综合回收和利用,推动钕铁硼回收技术与循环经济的深度融合。
5)促进技术集成与规模化应用。单一的回收方法可能无法满足大规模废料回收需求,因此,将多种回收技术集成应用,如将酸浸与溶剂萃取、微生物处理与离子液体法相结合等,可能成为提升回收效率和经济性的关键路径。
  • 国家自然科学基金资助项目(51964040)
  • 国家自然科学基金资助项目(51564042)
  • 内蒙古自治区基本科研业务(2023QNJS191)
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2025年第44卷第2期
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doi: 10.13355/j.cnki.sfyj.2025.02.001
  • 接收时间:2024-11-09
  • 首发时间:2025-07-05
  • 出版时间:2025-04-28
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  • 收稿日期:2024-11-09
基金
国家自然科学基金资助项目(51964040)
国家自然科学基金资助项目(51564042)
内蒙古自治区基本科研业务(2023QNJS191)
作者信息
    1 内蒙古科技大学 稀土产业学院, 内蒙古 包头 014010
    2 轻稀土资源绿色提取与高效利用教育部重点实验室, 内蒙古 包头 014010

通讯作者:

张晓伟(1983—),男,博士,副教授,主要研究方向为稀土湿法冶金及二次资源循环利用。E-mail:
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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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