Article(id=1241321698050494596, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241321691524158287, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2025.02.020, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1728489600000, receivedDateStr=2024-10-10, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773883755457, onlineDateStr=2026-03-19, pubDate=1743436800000, pubDateStr=2025-04-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773883755457, onlineIssueDateStr=2026-03-19, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773883755457, creator=13701087609, updateTime=1773883755457, updator=13701087609, issue=Issue{id=1241321691524158287, tenantId=1146029695717560320, journalId=1235980550691926019, year='2025', volume='45', issue='2', pageStart='1', pageEnd='204', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773883753901, creator=13701087609, updateTime=1773884632018, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241325374676726363, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241321691524158287, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241325374676726364, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241321691524158287, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=113, endPage=117, ext={EN=ArticleExt(id=1241321698503479466, articleId=1241321698050494596, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Process Mineralogy Study and Separation Process of Atmosphere Roasting and Dilute Sulfuric Acid Leaching for Mixed Rare Earth Concentrate, columnId=1236276106727321817, journalTitle=Mining and Metallurgical Engineering, columnName=METALLURGY, runingTitle=null, highlight=null, articleAbstract=

Based on process mineralogy study, a processing technique consisting of atmosphere roasting and leaching with dilute sulfuric acid was proposed to separate a kind of mixed rare earth concentrate containing 48.23% REO. It is found that the phase composition of such concentrate is mainly composed of bastnaesite, monazite, apatite and fluorite, with rare earth elements primarily existing in bastnaesite and monazite. Under air/argon atmosphere roasting, phases of monazite, apatite and fluorite can remain stable, and phase transition is mainly attributed to bastnaesite reaction. In an air atmosphere, bastnaesite is transitioned in the following steps, CeFCO3→Ce7O12→Ce11O20→CeO2, while its transition steps in an argon atmosphere include CeFCO3→Ce7O12, Th0.5Ce0.5O1.84→CeOF. After roasting in an air atmosphere at 500 ℃ followed by leaching with dilute sulfuric acid, the leaching rates of F-REO and P-REO can reach 86.67% and 1.70%, respectively, while the process of roasting at 700 ℃ in an argon atmosphere can lead to the leaching rates of F-REO and P-REO at 75.97% and 13.33% respectively. And the leaching residues obtained from above-mentioned two different processes have F-REO and P-REO contents of 6.92%, 26.02% and 11.86%, 21.81% respectively, all dominated by monazite. It is concluded that this processing technique of atmosphere roasting followed by dilute sulfuric acid leaching can effectively achieve separation between bastnaesite and monazite.

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在工艺矿物学研究基础上,针对某混合型稀土精矿提出了气氛焙烧-稀硫酸浸出的分离工艺。结果表明:混合型稀土精矿REO品位48.23%,主要矿相结构由氟碳铈矿、独居石、磷灰石、萤石构成,稀土元素主要赋存于氟碳铈矿与独居石中;混合型稀土精矿在空气/氩气气氛下焙烧,独居石、磷灰石和萤石物相均未发生明显变化,物相转变的差异性主要由氟碳铈矿的反应造成。空气下氟碳铈矿转变过程为CeFCO3→Ce7O12→Ce11O20→CeO2,氩气下氟碳铈矿转变过程为CeFCO3→Ce7O12、Th0.5Ce0.5O1.84→CeOF。稀土精矿经500 ℃空气气氛焙烧后稀硫酸浸出,F-REO、P-REO浸出率分别为86.67%、1.70%,700 ℃氩气气氛焙烧后对应的F-REO、P-REO浸出率分别为75.97%、13.33%,2种浸出渣中F-REO、P-REO含量(质量分数)分别为6.92%、26.02%和11.86%、21.81%,浸出渣均以独居石物相为主,通过气氛焙烧-稀硫酸浸出工艺达到了有效分离氟碳铈矿与独居石的目的。

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邓永春(1982—),男,山西宁武人,博士,副教授,主要研究方向为稀土冶金理论与工艺。E-mail:
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王亮(1998—),男,内蒙古呼和浩特人,硕士,主要研究方向为稀土冶金理论与工艺。E-mail:

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Study on technology of super gravity step separation of rare earth elements in Bayan Obo rare earth ore[J]. The Chinese Journal of Process Engineering, 2022, 22(10): 1429-1437., articleTitle=Study on technology of super gravity step separation of rare earth elements in Bayan Obo rare earth ore, refAbstract=null)], funds=[Fund(id=1241327688548414416, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, awardId=2022YFC2905800, language=CN, fundingSource=国家重点研发计划青年科学家项目(2022YFC2905800), fundOrder=null, country=null), Fund(id=1241327688657466326, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, awardId=YLXKZX-NKD-002/008, language=CN, fundingSource=一流学科科研专项项目(YLXKZX-NKD-002/008), fundOrder=null, country=null), Fund(id=1241327688779101149, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, awardId=2022QN05017, language=CN, fundingSource=内蒙古自治区自然科学基金(2022QN05017), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241327677571920147, tenantId=1146029695717560320, 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journalId=1235980550691926019, articleId=1241321698050494596, language=CN, label=图1, caption=气氛焙烧-稀硫酸浸出工艺流程, figureFileSmall=s+zwYpKfoaOhnpDOsXV0IA==, figureFileBig=Wi82NyroeEGMLdwQdEILsA==, tableContent=null), ArticleFig(id=1241327684962284335, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=EN, label=Fig.2, caption=XRD patterns of calcined products of rare earth concentrate, figureFileSmall=/Ocrv9kVBO/d4dqu9jdb2Q==, figureFileBig=y7KudtoQ91hHyD+a/su2Vw==, tableContent=null), ArticleFig(id=1241327685088113463, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=CN, label=图2, caption=稀土精矿焙烧产物XRD图谱

(a)空气气氛;(b)氩气气氛

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(a)空气气氛;(b)氩气气氛

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Analysis results of chemical composition of mixed rare earth concentrate

, figureFileSmall=null, figureFileBig=null, tableContent=
F-REOP-REOFPCaOTFeThO2SiO2Al2O3
31.9416.297.114.9811.564.100.182.380.29
), ArticleFig(id=1241327687319483251, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=CN, label=表1, caption=

混合型稀土精矿化学成分分析结果(质量分数)

, figureFileSmall=null, figureFileBig=null, tableContent=
F-REOP-REOFPCaOTFeThO2SiO2Al2O3
31.9416.297.114.9811.564.100.182.380.29
), ArticleFig(id=1241327687449506682, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=EN, label=Table 2, caption=

Mineral composition of mixed rare earth concentrate

, figureFileSmall=null, figureFileBig=null, tableContent=
氟碳铈矿独居石氟碳钙铈矿磷灰石萤石黄铁矿白云石磁/赤铁矿
35.4123.555.5911.196.144.632.351.63
方解石辉石黄河矿重晶石闪石硅钛铈矿褐帘石其他
1.361.061.021.010.950.070.063.98
), ArticleFig(id=1241327687596307338, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=CN, label=表2, caption=

混合型稀土精矿矿物组成及含量(质量分数)

, figureFileSmall=null, figureFileBig=null, tableContent=
氟碳铈矿独居石氟碳钙铈矿磷灰石萤石黄铁矿白云石磁/赤铁矿
35.4123.555.5911.196.144.632.351.63
方解石辉石黄河矿重晶石闪石硅钛铈矿褐帘石其他
1.361.061.021.010.950.070.063.98
), ArticleFig(id=1241327687755690902, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=EN, label=Table 3, caption=

Mineral liberation degree and locking degree of bastnaesite and monazite

, figureFileSmall=null, figureFileBig=null, tableContent=
矿物种类单体解离度/%连生度/%
萤石碳酸盐矿物硅酸盐矿物铁矿物磷灰石重晶石其他矿物
氟碳铈矿87.502.501.170.831.923.330.332.42
独居石87.771.981.031.032.073.010.262.84
), ArticleFig(id=1241327687864742816, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=CN, label=表3, caption=

氟碳铈矿与独居石的单体解离度及连生度

, figureFileSmall=null, figureFileBig=null, tableContent=
矿物种类单体解离度/%连生度/%
萤石碳酸盐矿物硅酸盐矿物铁矿物磷灰石重晶石其他矿物
氟碳铈矿87.502.501.170.831.923.330.332.42
独居石87.771.981.031.032.073.010.262.84
), ArticleFig(id=1241327687986377640, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=EN, label=Table 4, caption=

Results of dilute sulfuric acid leaching

, figureFileSmall=null, figureFileBig=null, tableContent=
焙烧条件焙烧料中稀土质量分数/%浸出液中稀土质量浓度/(g·L-1总稀土浸出率/%
未焙烧48.231.164.81
空气,500 ℃51.8915.0457.97
空气,700 ℃53.2010.4539.29
空气,900 ℃53.2311.8941.66
氩气,500 ℃48.695.2821.67
氩气,700 ℃53.8614.7654.81
氩气,900 ℃54.934.5416.53
), ArticleFig(id=1241327688082846643, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=CN, label=表4, caption=

稀硫酸浸出结果

, figureFileSmall=null, figureFileBig=null, tableContent=
焙烧条件焙烧料中稀土质量分数/%浸出液中稀土质量浓度/(g·L-1总稀土浸出率/%
未焙烧48.231.164.81
空气,500 ℃51.8915.0457.97
空气,700 ℃53.2010.4539.29
空气,900 ℃53.2311.8941.66
氩气,500 ℃48.695.2821.67
氩气,700 ℃53.8614.7654.81
氩气,900 ℃54.934.5416.53
), ArticleFig(id=1241327688179315644, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=EN, label=Table 5, caption=

Content of F-REO and P-REO in leaching residue and their leaching rates

, figureFileSmall=null, figureFileBig=null, tableContent=
焙烧条件含量(质量分数)/%浸出率/%
F-REOP-REOF-REOP-REO
空气,500 ℃6.9226.0286.671.70
氩气,700 ℃11.8621.8175.9713.33
), ArticleFig(id=1241327688292561859, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241321698050494596, language=CN, label=表5, caption=

浸出渣稀土元素含量及浸出率

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焙烧条件含量(质量分数)/%浸出率/%
F-REOP-REOF-REOP-REO
空气,500 ℃6.9226.0286.671.70
氩气,700 ℃11.8621.8175.9713.33
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混合型稀土精矿工艺矿物学及气氛焙烧-稀硫酸浸出分离稀土矿物研究
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王亮 1, 2, 3 , 辛文彬 1, 2, 3 , 李文博 4 , 邓永春 1, 2, 3 , 张小龙 4 , 姜银举 1, 2, 3 , 李健飞 1, 2, 3
矿冶工程杂志 | 冶金 2025,45(2): 113-117
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矿冶工程杂志 | 冶金 2025, 45(2): 113-117
混合型稀土精矿工艺矿物学及气氛焙烧-稀硫酸浸出分离稀土矿物研究
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王亮1, 2, 3 , 辛文彬1, 2, 3, 李文博4, 邓永春1, 2, 3 , 张小龙4, 姜银举1, 2, 3, 李健飞1, 2, 3
作者信息
  • 1.内蒙古科技大学 稀土产业学院(稀土工程技术学院),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(内蒙古科技大学),内蒙古 包头 014010
  • 3.轻稀土清洁提取与应用内蒙古自治区工程研究中心,内蒙古 包头 014010
  • 4.东北大学 资源与土木工程学院,辽宁 沈阳 110819
  • 王亮(1998—),男,内蒙古呼和浩特人,硕士,主要研究方向为稀土冶金理论与工艺。E-mail:

通讯作者:

邓永春(1982—),男,山西宁武人,博士,副教授,主要研究方向为稀土冶金理论与工艺。E-mail:
Process Mineralogy Study and Separation Process of Atmosphere Roasting and Dilute Sulfuric Acid Leaching for Mixed Rare Earth Concentrate
Liang WANG1, 2, 3 , Wenbin XIN1, 2, 3, Wenbo LI4, Yongchun DENG1, 2, 3 , Xiaolong ZHANG4, Yinju JIANG1, 2, 3, Jianfei LI1, 2, 3
Affiliations
  • 1.School of Rare Earth Industry (School of Rare Earth Engineering), Inner Mongolia University of Science and Technology, Baotou 014010, Inner Mongolia, China
  • 2.Key Laboratory of Green Extraction and Efficient Utilization of Light Rare Earth Resources of Ministry of Education, Inner Mongolia University of Science and Technology, Baotou 014010, Inner Mongolia, China
  • 3.Inner Mongolia Engineering Research Center for Clean Extraction of Light Rare Earth and Application, Baotou 014010, Inner Mongolia, China
  • 4.School of Resources and Civil Engineering, Northeastern University, Shenyang 110819, Liaoning, China
出版时间: 2025-04-01 doi: 10.3969/j.issn.0253-6099.2025.02.020
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在工艺矿物学研究基础上,针对某混合型稀土精矿提出了气氛焙烧-稀硫酸浸出的分离工艺。结果表明:混合型稀土精矿REO品位48.23%,主要矿相结构由氟碳铈矿、独居石、磷灰石、萤石构成,稀土元素主要赋存于氟碳铈矿与独居石中;混合型稀土精矿在空气/氩气气氛下焙烧,独居石、磷灰石和萤石物相均未发生明显变化,物相转变的差异性主要由氟碳铈矿的反应造成。空气下氟碳铈矿转变过程为CeFCO3→Ce7O12→Ce11O20→CeO2,氩气下氟碳铈矿转变过程为CeFCO3→Ce7O12、Th0.5Ce0.5O1.84→CeOF。稀土精矿经500 ℃空气气氛焙烧后稀硫酸浸出,F-REO、P-REO浸出率分别为86.67%、1.70%,700 ℃氩气气氛焙烧后对应的F-REO、P-REO浸出率分别为75.97%、13.33%,2种浸出渣中F-REO、P-REO含量(质量分数)分别为6.92%、26.02%和11.86%、21.81%,浸出渣均以独居石物相为主,通过气氛焙烧-稀硫酸浸出工艺达到了有效分离氟碳铈矿与独居石的目的。

稀土  /  氟碳铈矿  /  独居石  /  混合型稀土精矿  /  工艺矿物学  /  气氛焙烧  /  矿相转变  /  硫酸浸出

Based on process mineralogy study, a processing technique consisting of atmosphere roasting and leaching with dilute sulfuric acid was proposed to separate a kind of mixed rare earth concentrate containing 48.23% REO. It is found that the phase composition of such concentrate is mainly composed of bastnaesite, monazite, apatite and fluorite, with rare earth elements primarily existing in bastnaesite and monazite. Under air/argon atmosphere roasting, phases of monazite, apatite and fluorite can remain stable, and phase transition is mainly attributed to bastnaesite reaction. In an air atmosphere, bastnaesite is transitioned in the following steps, CeFCO3→Ce7O12→Ce11O20→CeO2, while its transition steps in an argon atmosphere include CeFCO3→Ce7O12, Th0.5Ce0.5O1.84→CeOF. After roasting in an air atmosphere at 500 ℃ followed by leaching with dilute sulfuric acid, the leaching rates of F-REO and P-REO can reach 86.67% and 1.70%, respectively, while the process of roasting at 700 ℃ in an argon atmosphere can lead to the leaching rates of F-REO and P-REO at 75.97% and 13.33% respectively. And the leaching residues obtained from above-mentioned two different processes have F-REO and P-REO contents of 6.92%, 26.02% and 11.86%, 21.81% respectively, all dominated by monazite. It is concluded that this processing technique of atmosphere roasting followed by dilute sulfuric acid leaching can effectively achieve separation between bastnaesite and monazite.

rare earth  /  bastnaesite  /  monazite  /  mixed rare earth concentrate  /  process mineralogy  /  atmosphere roasting  /  phase transition  /  sulfuric acid leaching
王亮, 辛文彬, 李文博, 邓永春, 张小龙, 姜银举, 李健飞. 混合型稀土精矿工艺矿物学及气氛焙烧-稀硫酸浸出分离稀土矿物研究. 矿冶工程杂志, 2025 , 45 (2) : 113 -117 . DOI: 10.3969/j.issn.0253-6099.2025.02.020
Liang WANG, Wenbin XIN, Wenbo LI, Yongchun DENG, Xiaolong ZHANG, Yinju JIANG, Jianfei LI. Process Mineralogy Study and Separation Process of Atmosphere Roasting and Dilute Sulfuric Acid Leaching for Mixed Rare Earth Concentrate[J]. Mining and Metallurgical Engineering, 2025 , 45 (2) : 113 -117 . DOI: 10.3969/j.issn.0253-6099.2025.02.020
我国大力发展稀土资源综合利用等相关技术,针对独特的稀土资源特点,开发系列世界领先的稀土提纯技术和分离技术。稀土已广泛应用于冶金、石油、纺织、农业等各行业[1-2]。稀土矿的类型主要有单一氟碳铈矿、独居石型和混合型稀土矿,以及离子吸附型稀土矿和磷钇稀土矿[3]。其中经传统选矿分离后的混合型稀土精矿以共生的氟碳铈矿和独居石为主,稀土品位40%~65%[4-5]
目前国内混合稀土精矿分离提取稀土的主流工艺为浓硫酸焙烧法,但由于前端未分离氟碳铈矿与独居石,存在硫酸消耗量大、含氟含硫气体同时排出等诸多问题。目前主要在选矿端采用磁选、浮选和重选的联合工艺分离氟碳铈矿与独居石,但由于混合稀土精矿中的杂质矿物种类多,且萤石、磷灰石、方解石和重晶石等矿物的可浮性与稀土矿类似,钠辉石、钠闪石和赤铁矿的磁性与稀土矿类似,并且各类矿物嵌布情况复杂,存在包裹连生的嵌布情况,大多数氟碳铈矿与独居石被其他矿物包裹,直接通过选矿分离矿物的难度极大,导致工艺指标不理想、有价矿物回收利用率低[6-7]、生产流程长、生产成本高[8-10]
本文对某混合型稀土精矿的工艺矿物学特性进行详细研究,明确混合稀土精矿中主要的矿物类型、稀土元素赋存状态、嵌布特征及各类矿物之间伴生关系等,并对空气/氩气2种气氛下混合型稀土精矿焙烧产物物相组成以及硫酸浸出液和浸出渣进行研究,为实现氟碳铈矿和独居石的有效分离提供一种湿法工艺思路。
实验原料为某公司提供的混合型稀土精矿,经筛分除杂、混合均匀后置于烘干箱中90 ℃干燥4 h,之后密封备用。实验用浓硫酸为市售分析纯试剂。
混合型稀土精矿化学成分分析结果如表1所示。混合稀土精矿中总稀土(TREO)含量(质量分数,下同)为48.23%,其中可溶于酸稀土(F-REO)含量为31.94%,不可溶于酸稀土(P-REO)含量为16.29%,需要排除的杂质成分CaO、F、P、Fe和SiO2含量均较高。
表2为混合型稀土精矿矿相组成及含量。由表2可以看出,混合型稀土精矿中矿物种类较为复杂,主要稀土富集矿物为氟碳铈矿、独居石、氟碳钙铈矿等,其中氟碳铈矿与独居石的质量比约为3∶2。硅钛铈矿、褐帘石中也含有少量稀土元素。脉石矿物主要为磷灰石、萤石、黄铁矿、白云石、磁/赤铁矿,次为方解石、辉石、黄河矿、重晶石等。
氟碳铈矿与独居石的单体解离度及连生度如表3所示。结果表明,在混合型稀土精矿中,氟碳铈矿单体解离度为87.50%,主要与磷灰石、萤石和铁矿物连生,其次与碳酸盐矿物和硅酸盐矿物连生;独居石单体解离度为87.77%,主要与磷灰石、铁矿物和萤石连生,与萤石的连生程度明显低于氟碳铈矿,其次与碳酸盐矿物和硅酸盐矿物连生。
扫描电镜背散射分析结果表明,氟碳铈矿是混合型稀土精矿中稀土含量最高的稀土矿物,其中包含Ce、La、Nd、Pr等稀土元素。氟碳铈矿单体颗粒度较大且呈不规则的块状和条状,部分呈浸染状沿裂缝填充于磷灰石中、呈散心状或细粒状填充于萤石中;部分氟碳铈矿紧密嵌布在磁铁矿边缘,少量以粒状镶嵌在磁铁矿内部。与氟碳铈矿成分极为接近的氟碳钙铈矿,常常以粒状被其包裹,也常被磁铁矿、钠闪石等包裹其中。独居石中主要包含Ce、La、Nd、Pr等稀土元素。独居石颗粒相对氟碳铈矿更细且呈不规则状,多数独居石嵌布在萤石和石英矿边缘,少量呈颗粒状被萤石包裹;部分独居石与氟碳铈矿和氟碳钙铈矿构成连生体矿物,少量以粒状嵌布在钛铁矿中。被其他矿包裹起来的氟碳铈矿与独居石粒度均低于75 μm,导致常规的物理分离工艺难以实现两者的有效分离。
根据混合型稀土精矿工艺矿物学特点,本文提出“气氛焙烧-稀硫酸浸出”的火法-湿法联合分离工艺。空气/氩气气氛焙烧后,混合型稀土精矿中主要物相氟碳铈矿发生矿相转变,利用转变后其化学浸出性的差异实现氟碳铈矿与独居石的分离,分离后氟碳铈矿中的稀土元素进入溶液,随后可以进入萃取分离工艺,而浸出渣物相以独居石为主,后续可采用浓硫酸焙烧法分离提取稀土元素。气氛焙烧-稀硫酸浸出工艺流程如图1所示。
气氛焙烧实验在空气和氩气2种气氛下进行,具体实验过程如下:将烘干后的混合型稀土精矿置于管式气氛炉中,升温速率10 ℃/min,焙烧时间60 min,焙烧温度分别为500、700和900 ℃,焙烧完成后,样品随炉冷却至室温,期间持续通入相应气体。
取10 g经气氛焙烧60 min的混合型稀土精矿,加入2.8 mol/L稀硫酸溶液80 mL,充分混合,于水浴锅中恒温搅拌浸出60 min,浸出结束后,过滤、定容,测定浸出液中稀土含量。所得浸出渣于烘箱中90 ℃下烘干12 h,记录干重,并测定渣中稀土含量及物相组成。
采用电感耦合等离子体发射光谱法(ICP-OES)分析稀土矿物多元素化学成分及稀土元素配分;利用X射线衍射仪(XRD)分析混合型稀土精矿的矿物物相种类;采用Sigma-500型场发射扫描电子显微镜及AMICS自动矿物分析系统分析矿物种类及含量;通过Axio Scope A1 Pol偏反光显微镜分析矿物解离及连生情况;采用傅里叶红外光谱(FT-IR)分析焙烧产物基团的变化情况。
空气和氩气2种气氛下的焙烧产物XRD图谱见图2
无论空气气氛还是氩气气氛,不同焙烧温度下独居石、磷灰石和萤石物相均未发生明显变化,其物相分别呈现CePO4、Ca5(PO43、CaF2的结构类型;2种气氛下焙烧过程物相转变均体现为氟碳铈矿发生不同转变,其中空气气氛下混合稀土精矿升温至500、700、900 ℃时,氟碳铈矿物相转变过程为CeFCO3→Ce7O12→Ce11O20→CeO2,空气气氛下升高焙烧温度会使CeFCO3中的Ce向高价形态转变,原精矿中的Ce3+在500、700 ℃时分别转变为同时含有Ce3+、Ce4+的Ce7O12、Ce11O20物相,900 ℃时转变为以Ce4+为主的CeO2物相;氩气气氛下混合稀土精矿升温至500、700、900 ℃时,氟碳铈矿物相转变过程为CeFCO3→Ce7O12、Th0.5Ce0.5O1.84→CeOF,氩气气氛下,升高焙烧温度同样会使Ce向高价形态转变,原精矿中的Ce3+在500、700 ℃时转变为同时含有Ce3+、Ce4+的Ce7O12、Th0.5Ce0.5O1.84物相,900 ℃时转变为以Ce3+为主的CeOF物相,说明空气焙烧时CeFCO3中Ce的氧化程度高于氩气焙烧时。
图3为不同气氛和温度下焙烧产物FT-IR图谱。可以看出,混合型稀土精矿FT-IR图谱中有明显的CO32-红外吸收峰,波数1 416、867、727 cm-1以及波数段953~1 093 cm-1和572~600 cm-1处为PO43-红外吸收峰区域,说明混合型稀土精矿原矿主要由碳酸盐矿物与磷酸盐矿物组成。经过2种气氛焙烧后,700、900 ℃产物中CO32-吸收峰均消失,而PO43-吸收峰依旧存在,说明在2种气氛条件下,主要发生碳酸盐矿物的分解反应且反应较为彻底,结合图2结果,氟碳铈矿在2种气氛下焙烧后物相消失,亦能说明焙烧过程的物相转变是由氟碳铈矿的反应所致。
稀硫酸浸出结果如表4所示,浸出渣稀土元素含量及浸出率如表5所示,部分浸出渣XRD图谱如图4所示。结果表明:未焙烧的混合型稀土精矿直接稀硫酸浸出的总稀土浸出率仅4.81%;空气气氛下500 ℃焙烧后稀硫酸浸出,F-REO浸出率为86.67%,P-REO浸出率仅1.70%,总稀土浸出率为57.97%,浸出液中总稀土元素质量浓度为15.04 g/L,浸出渣中F-REO和P-REO含量(质量分数)分别为6.92%和26.02%;氩气气氛下700 ℃焙烧后稀硫酸浸出,F-REO浸出率为75.97%,P-REO浸出率为13.33%,总稀土浸出率为54.81%,浸出液中总稀土质量浓度为14.76 g/L,浸出渣中F-REO和P-REO含量(质量分数)分别为11.86%和21.81%。
结合图23可知:空气焙烧过程中,CeFCO3基本转变为Ce7O12物相时,浸出液中稀土元素含量较高,物相转变为Ce11O20和CeO2时,浸出液中稀土元素含量较低;氩气焙烧过程中,CeFCO3完全转变为Ce7O12物相时,浸出液稀土含量较高,500 ℃焙烧料稀土浸出率低可能是CeFCO3未完全转变所致,物相转变为CeOF时,稀硫酸难以浸出稀土元素。由此可以得出,氟碳铈矿转变为Ce7O12物相时其中的稀土元素更容易被稀硫酸溶液浸出。结合图4,2种工艺处理后的浸出渣中稀土物相均以CePO4为主,未发现其他稀土物相的特征峰,说明2种焙烧条件下混合稀土精矿中绝大多数氟碳铈矿经气氛焙烧-稀硫酸浸出后,其中的稀土元素进入浸出液,浸出渣以独居石物相结构为主,通过气氛焙烧-稀硫酸浸出方法有效实现了两者的分离。
基于氟碳铈矿与独居石的矿物特征,提出空气/氩气焙烧-稀硫酸浸出工艺处理混合型稀土精矿,得出以下结论。
1)混合型稀土精矿TREO品位48.23%,其中F-REO品位31.94%、P-REO品位16.29%。混合型稀土精矿中氟碳铈矿和独居石矿物含量(质量分数)分别为35.41%和23.55%,脉石矿物主要为磷灰石、萤石、黄铁矿、白云石、磁/赤铁矿。氟碳铈矿与独居石粒度较细且与其他矿物嵌布特征较为复杂,存在包裹连生的嵌布情况。
2)空气和氩气2种气氛下焙烧,独居石、磷灰石和萤石物相均未发生明显变化,焙烧过程中物相转变均体现为氟碳铈矿发生不同转变,其中空气气氛下氟碳铈矿物相转变过程为CeFCO3→Ce7O12→Ce11O20→CeO2,氩气气氛下氟碳铈矿物相转变过程为CeFCO3→Ce7O12、Th0.5Ce0.5O1.84→CeOF。
3)混合型稀土精矿经500 ℃空气气氛焙烧后稀硫酸浸出,F-REO、P-REO浸出率分别为86.67%、1.70%,经700 ℃氩气气氛焙烧后稀硫酸浸出,F-REO、P-REO浸出率分别为75.97%、13.33%,2种浸出渣中F-REO、P-REO含量(质量分数)分别为6.92%、26.02%和11.86%、21.81%,2种浸出渣均以独居石物相为主,通过气氛焙烧-稀硫酸浸出达到了有效分离氟碳铈矿与独居石的目的。
  • 国家重点研发计划青年科学家项目(2022YFC2905800)
  • 一流学科科研专项项目(YLXKZX-NKD-002/008)
  • 内蒙古自治区自然科学基金(2022QN05017)
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2025年第45卷第2期
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doi: 10.3969/j.issn.0253-6099.2025.02.020
  • 接收时间:2024-10-10
  • 首发时间:2026-03-19
  • 出版时间:2025-04-01
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  • 收稿日期:2024-10-10
基金
国家重点研发计划青年科学家项目(2022YFC2905800)
一流学科科研专项项目(YLXKZX-NKD-002/008)
内蒙古自治区自然科学基金(2022QN05017)
作者信息
    1.内蒙古科技大学 稀土产业学院(稀土工程技术学院),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(内蒙古科技大学),内蒙古 包头 014010
    3.轻稀土清洁提取与应用内蒙古自治区工程研究中心,内蒙古 包头 014010
    4.东北大学 资源与土木工程学院,辽宁 沈阳 110819

通讯作者:

邓永春(1982—),男,山西宁武人,博士,副教授,主要研究方向为稀土冶金理论与工艺。E-mail:
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2种不同金属材料的力学参数

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属数
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genus
种数
Number of
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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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