Article(id=1147999693730214020, tenantId=1146029695717560320, journalId=1146123346816638986, issueId=1147999688122430098, articleNumber=1000-8063(2025)02-0142-09, orderNo=null, doi=10.13426/j.cnki.yky.2024.09.04, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1725552000000, receivedDateStr=2024-09-06, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1751634055788, onlineDateStr=2025-07-04, pubDate=1747670400000, pubDateStr=2025-05-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1751634055788, onlineIssueDateStr=2025-07-04, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1751634055788, creator=13701087609, updateTime=1751634055788, updator=13701087609, issue=Issue{id=1147999688122430098, tenantId=1146029695717560320, journalId=1146123346816638986, year='2025', volume='44', issue='2', pageStart='1', pageEnd='160', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1751634054451, creator=13701087609, updateTime=1759123795578, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1179413939365491632, tenantId=1146029695717560320, journalId=1146123346816638986, issueId=1147999688122430098, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1179413939365491633, tenantId=1146029695717560320, journalId=1146123346816638986, issueId=1147999688122430098, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=142, endPage=150, ext={EN=ArticleExt(id=1147999693897986204, articleId=1147999693730214020, tenantId=1146029695717560320, journalId=1146123346816638986, language=EN, title=Technological Innovation and Practice Analysis in the Development of Complex Associated Uranium Molybdenum Resources from the Perspective of New Quality Productivity, columnId=1175805042197152439, journalTitle=Uranium Mining and Metallurgy, columnName=SAFETY AND ENVIRONMENT PROTECTION, runingTitle=null, highlight=null, articleAbstract=

Guyuan 460 associated uranium molybdenum resources belong to amorphous colloidal sulfur molybdenum ore, which has the characteristics of complex mineral properties, difficult beneficiation and metallurgy, and long process flow. After more than 20 years of experimental research and production practice, a process development technology system of "oxygen pressure acid leaching modified filtration extraction separation process water cycle" has been formed. This article summarizes the technological innovation process of Guyuan 460 uranium molybdenum mine, which comprehensively innovates and practices from multiple aspects such as efficient leaching of uranium molybdenum ore, solid-liquid separation of slurry, separation and purification of uranium molybdenum, product preparation, process water recycling, key equipment and material engineering applications. Finally, an oxygen pressure leaching demonstration mine with an annual processing capacity of 200 000 tons of uranium molybdenum ore was built, greatly improving the scientific and technological level of complex associated uranium molybdenum resource development in China. It is a typical embodiment of new quality productivity in the mineral field.

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沽源460伴生铀钼资源属于非晶质胶硫钼矿,具有矿性复杂、选冶难度大、工艺流程长等特点,经过二十余年的试验研究和生产实践,形成了“氧压酸浸—改性过滤—萃取分离—工艺水循环”工艺开发技术体系。综述了沽源460铀钼矿的技术创新历程,分别从铀钼矿高效浸出、矿浆固液分离、铀钼分离纯化、产品制备、工艺水循环利用、关键设备和材料工程应用等方面进行了技术创新与实践,建成了年处理20万吨铀钼原矿的氧压浸出示范矿山,大幅提升了中国复杂伴生铀钼资源开发的科技水平。该矿山是矿产领域新质生产力的典型体现。

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隋杰(1973—),男,内蒙古赤峰人,学士,高级工程师,主要从事铀钼矿生产技术管理工作。

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隋杰(1973—),男,内蒙古赤峰人,学士,高级工程师,主要从事铀钼矿生产技术管理工作。

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隋杰(1973—),男,内蒙古赤峰人,学士,高级工程师,主要从事铀钼矿生产技术管理工作。

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Uranium Mining and Metallurgy, 2023, 42(1):15-22+54 (in Chinese)., articleTitle=A safe and efficient method of tailings recovery for dry tailings pond, refAbstract=null), Reference(id=1179483301212467911, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, doi=null, pmid=null, pmcid=null, year=2022, volume=51, issue=20, pageStart=154, pageEnd=156, url=null, language=null, rfNumber=[22], rfOrder=41, authorNames=任志刚, 程瑞泉, 刘永涛, journalName=山东化工, refType=null, unstructuredReference=任志刚, 程瑞泉, 刘永涛, 等. 某铀钼矿尾渣特性及浸出工艺研究[J]. 山东化工, 2022, 51(20):154-156+159., articleTitle=某铀钼矿尾渣特性及浸出工艺研究, refAbstract=null), Reference(id=1179483301275382472, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, doi=null, pmid=null, pmcid=null, year=2022, volume=51, issue=20, pageStart=154, pageEnd=156, url=null, language=null, rfNumber=[22], rfOrder=42, authorNames=REN Zhigang, CHENG Ruiquan, LIU Yongtao, journalName=Shandong Chemical Industry, refType=null, unstructuredReference=REN Zhigang, CHENG Ruiquan, LIU Yongtao, et al. Study on characteristics and leaching process of tailings from a uranium molybdenum ore[J]. Shandong Chemical Industry, 2022, 51(20):154-156+159 (in Chinese)., articleTitle=Study on characteristics and leaching process of tailings from a uranium molybdenum ore, refAbstract=null)], funds=[Fund(id=1179483297982853788, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, awardId=中核科发〔2021〕292号, language=CN, fundingSource=中核集团集中研发项目(中核科发〔2021〕292号), fundOrder=null, country=null), Fund(id=1179483298037379741, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, awardId=null, language=CN, fundingSource=中核集团集中研发项目(铀钼矿尾渣中钼的再回收技术研究), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1179483292769333817, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, xref=1, ext=[AuthorCompanyExt(id=1179483292777722426, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, companyId=1179483292769333817, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 Guyuan Uranium Co., Ltd., CNNC, Zhangjiakou 076561, China), AuthorCompanyExt(id=1179483292836442683, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, companyId=1179483292769333817, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1 中核沽源铀业有限责任公司, 河北 张家口 076561)]), AuthorCompany(id=1179483292911940156, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, xref=2, ext=[AuthorCompanyExt(id=1179483292920328765, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, companyId=1179483292911940156, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2 China Uranium Industry Co., Ltd., Beijing 100013, China), AuthorCompanyExt(id=1179483292924523070, 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city=null, postcode=null, companyName=null, departmentName=null, remark=3 核工业北京化工冶金研究院, 北京 101149)])], figs=[ArticleFig(id=1179483296674230922, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=EN, label=Fig. 1, caption=U-Mo-S-H2O equilibrium phase diagram, figureFileSmall=726uHIQiqqZyxGPK03ji2g==, figureFileBig=TscKWKHj+1PmHAC0+sSr1g==, tableContent=null), ArticleFig(id=1179483296737145483, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=CN, label=图1, caption=U-Mo-S-H2O平衡相图, figureFileSmall=726uHIQiqqZyxGPK03ji2g==, figureFileBig=TscKWKHj+1PmHAC0+sSr1g==, tableContent=null), ArticleFig(id=1179483296900723340, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=EN, label=Fig. 2, caption=Treatment process for acid precipitation mother liquor, figureFileSmall=nHLCLJiJLj+xR2W6JU7kyQ==, figureFileBig=sHXuf4zHy+DJkcg9/X//wA==, tableContent=null), ArticleFig(id=1179483296972026509, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=CN, label=图2, caption=酸沉母液处理工艺流程, figureFileSmall=nHLCLJiJLj+xR2W6JU7kyQ==, figureFileBig=sHXuf4zHy+DJkcg9/X//wA==, tableContent=null), ArticleFig(id=1179483297022358158, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=EN, label=Fig. 3, caption=Flocculation and sedimentation curves at different slurry concentrations, figureFileSmall=mlD0+hc6J8np/QQaWgB7+w==, figureFileBig=fvyZmLGEfrQzrLOLYtmPZQ==, tableContent=null), ArticleFig(id=1179483297068495503, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=CN, label=图3, caption=不同矿浆浓度下的絮凝沉降曲线, figureFileSmall=mlD0+hc6J8np/QQaWgB7+w==, figureFileBig=fvyZmLGEfrQzrLOLYtmPZQ==, tableContent=null), ArticleFig(id=1179483297114632848, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=EN, label=Fig. 4, caption=Phase transition diagram of calcium sulfate precipitation, figureFileSmall=tcnrQHf/rqRLh+9Jy6cMuQ==, figureFileBig=1p3grhYQ7zDmcAD+xDVzrw==, tableContent=null), ArticleFig(id=1179483297202713233, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=CN, label=图4, caption=硫酸钙沉淀相变图, figureFileSmall=tcnrQHf/rqRLh+9Jy6cMuQ==, figureFileBig=1p3grhYQ7zDmcAD+xDVzrw==, tableContent=null), ArticleFig(id=1179483297257239186, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=EN, label=Fig. 5, caption=Results of multi-stage countercurrent extraction of molybdenum and uranium, figureFileSmall=mTc29h1G8ugAVxF0etlJKA==, figureFileBig=qNRcToOGLlXliWlP3IMsOQ==, tableContent=null), ArticleFig(id=1179483297345319571, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=CN, label=图5, caption=钼、铀多级逆流萃取结果, figureFileSmall=mTc29h1G8ugAVxF0etlJKA==, figureFileBig=qNRcToOGLlXliWlP3IMsOQ==, tableContent=null), ArticleFig(id=1179483297404039828, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=EN, label=Table 1, caption=

Molybdenum mineral phase analysis results

, figureFileSmall=null, figureFileBig=null, tableContent=
矿床层位 Mo相态含量/%
简单氧化物类 复杂氧化态类钼矿物 胶硫钼矿
表层氧化带 70.51 9.19 20.30
中层过渡带 47.90 8.38 43.72
深部原生带 36.16 6.98 56.86
), ArticleFig(id=1179483297450177173, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=CN, label=表1, caption=

钼矿物物相分析结果

, figureFileSmall=null, figureFileBig=null, tableContent=
矿床层位 Mo相态含量/%
简单氧化物类 复杂氧化态类钼矿物 胶硫钼矿
表层氧化带 70.51 9.19 20.30
中层过渡带 47.90 8.38 43.72
深部原生带 36.16 6.98 56.86
), ArticleFig(id=1179483297500508822, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=EN, label=Table 2, caption=

Analysis results of uranium and molybdenum products

, figureFileSmall=null, figureFileBig=null, tableContent=
钼产品/(Bq/kg) 铀产品/%
项目 含量 国标要求 项目 含量 国标要求
238U 13.3 <1 000 U 69.34 ≥50
226Ra 4.48 <1 000 ${SO}_{4}^{2-}$ 1.495 ≤5
232Th 1.95 <1 000 SiO2 0.041 ≤2
40K 19.9 <10 000 ${PO}_{4}^{3-}$ 0.032 ≤5
总放射性 <0.04 <10 F- 0.022 ≤0.2
Cl- 0.054 ≤0.3
), ArticleFig(id=1179483297555034775, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=CN, label=表2, caption=

铀、钼产品分析结果

, figureFileSmall=null, figureFileBig=null, tableContent=
钼产品/(Bq/kg) 铀产品/%
项目 含量 国标要求 项目 含量 国标要求
238U 13.3 <1 000 U 69.34 ≥50
226Ra 4.48 <1 000 ${SO}_{4}^{2-}$ 1.495 ≤5
232Th 1.95 <1 000 SiO2 0.041 ≤2
40K 19.9 <10 000 ${PO}_{4}^{3-}$ 0.032 ≤5
总放射性 <0.04 <10 F- 0.022 ≤0.2
Cl- 0.054 ≤0.3
), ArticleFig(id=1179483297605366424, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=EN, label=Table 3, caption=

Composition of residual water treated solutiong/L

, figureFileSmall=null, figureFileBig=null, tableContent=
U Mo SiO2 As Ca Mg
<1 <0.01 0.156~0.208 0.010~0.023 0.500~0.600 0.189~0.256
Al Mn P ${SO}_{4}^{2-}$ ∑Fe 浊度
0.97~0.87 0.86~1.38 <0.005 2.86~3.55 0.056~0.086 <50
), ArticleFig(id=1179483297655698073, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=CN, label=表3, caption=

萃余水处理后溶液组成

, figureFileSmall=null, figureFileBig=null, tableContent=
U Mo SiO2 As Ca Mg
<1 <0.01 0.156~0.208 0.010~0.023 0.500~0.600 0.189~0.256
Al Mn P ${SO}_{4}^{2-}$ ∑Fe 浊度
0.97~0.87 0.86~1.38 <0.005 2.86~3.55 0.056~0.086 <50
), ArticleFig(id=1179483297743778458, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=EN, label=Table 4, caption=

Experimental results of tailings leaching under different process conditions

, figureFileSmall=null, figureFileBig=null, tableContent=
条件 滤液 滤渣
氧压
酸浸
ρ(H2SO4)/
(g/L)
电位/mV ρ(U)/(g/L) ρ(Mo)/(g/L) w(U)/% w(Mo)/% U渣计浸出率/% Mo渣计浸出率/%
29.84 -372 0.058 2.07 0.008 0.123 66.17 80.86
氧压
碱浸
(NaOH)
ρ(NaOH)/
(g/L)
ρ(Na2CO3)/
(g/L)
ρ(U)/(g/L) ρ(Mo)/(g/L) w(U)/% w(Mo)/% U渣计浸出率/% Mo渣计浸出率/%
0.838 4.85 - 2.59 - 0.092 - 85.48
氧压
碱浸
(Na2CO3)
ρ(Na2CO3)/
(g/L)
ρ(NaHCO3)/
(g/L)
ρ(U)/(g/L) ρ(Mo)/(g/L) w(U)/% w(Mo)/% U渣计浸出率/% Mo渣计浸出率/%
4.64 13.12 0.074 2.56 0.008 0.119 65.38 81.06
), ArticleFig(id=1179483297831858843, tenantId=1146029695717560320, journalId=1146123346816638986, articleId=1147999693730214020, language=CN, label=表4, caption=

不同工艺条件尾渣浸出结果

, figureFileSmall=null, figureFileBig=null, tableContent=
条件 滤液 滤渣
氧压
酸浸
ρ(H2SO4)/
(g/L)
电位/mV ρ(U)/(g/L) ρ(Mo)/(g/L) w(U)/% w(Mo)/% U渣计浸出率/% Mo渣计浸出率/%
29.84 -372 0.058 2.07 0.008 0.123 66.17 80.86
氧压
碱浸
(NaOH)
ρ(NaOH)/
(g/L)
ρ(Na2CO3)/
(g/L)
ρ(U)/(g/L) ρ(Mo)/(g/L) w(U)/% w(Mo)/% U渣计浸出率/% Mo渣计浸出率/%
0.838 4.85 - 2.59 - 0.092 - 85.48
氧压
碱浸
(Na2CO3)
ρ(Na2CO3)/
(g/L)
ρ(NaHCO3)/
(g/L)
ρ(U)/(g/L) ρ(Mo)/(g/L) w(U)/% w(Mo)/% U渣计浸出率/% Mo渣计浸出率/%
4.64 13.12 0.074 2.56 0.008 0.119 65.38 81.06
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新质生产力视角下复杂伴生铀钼资源开发技术创新与实践分析
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隋杰 1 , 苏学斌 2 , 刘永涛 1 , 李映兵 1 , 高东星 1 , 程瑞泉 1 , 霍玉宝 1 , 刘辉 3 , 周志全 3 , 刘会武 3 , 师留印 3 , 康绍辉 3
铀矿冶 | 安全·环保 2025,44(2): 142-150
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铀矿冶 | 安全·环保 2025, 44(2): 142-150
新质生产力视角下复杂伴生铀钼资源开发技术创新与实践分析
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隋杰1, 苏学斌2, 刘永涛1, 李映兵1, 高东星1, 程瑞泉1, 霍玉宝1, 刘辉3, 周志全3, 刘会武3, 师留印3, 康绍辉3
作者信息
  • 1 中核沽源铀业有限责任公司, 河北 张家口 076561
  • 2 中国铀业股份有限公司, 北京 100013
  • 3 核工业北京化工冶金研究院, 北京 101149
  • 隋杰(1973—),男,内蒙古赤峰人,学士,高级工程师,主要从事铀钼矿生产技术管理工作。

Technological Innovation and Practice Analysis in the Development of Complex Associated Uranium Molybdenum Resources from the Perspective of New Quality Productivity
Jie SUI1, Xuebin SU2, Yongtao LIU1, Yingbing LI1, Dongxing GAO1, Ruiquan CHENG1, Yubao HUO1, Hui LIU3, Zhiquan ZHOU3, Huiwu LIU3, Liuyin SHI3, Shaohui KANG3
Affiliations
  • 1 Guyuan Uranium Co., Ltd., CNNC, Zhangjiakou 076561, China
  • 2 China Uranium Industry Co., Ltd., Beijing 100013, China
  • 3 Beijing Research Institute of Chemical Engineering and Metallurgy, CNNC, Beijing 101149, China
出版时间: 2025-05-20 doi: 10.13426/j.cnki.yky.2024.09.04
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沽源460伴生铀钼资源属于非晶质胶硫钼矿,具有矿性复杂、选冶难度大、工艺流程长等特点,经过二十余年的试验研究和生产实践,形成了“氧压酸浸—改性过滤—萃取分离—工艺水循环”工艺开发技术体系。综述了沽源460铀钼矿的技术创新历程,分别从铀钼矿高效浸出、矿浆固液分离、铀钼分离纯化、产品制备、工艺水循环利用、关键设备和材料工程应用等方面进行了技术创新与实践,建成了年处理20万吨铀钼原矿的氧压浸出示范矿山,大幅提升了中国复杂伴生铀钼资源开发的科技水平。该矿山是矿产领域新质生产力的典型体现。

新质生产力  /  铀钼矿  /  加压氧化  /  技术创新  /  示范矿山

Guyuan 460 associated uranium molybdenum resources belong to amorphous colloidal sulfur molybdenum ore, which has the characteristics of complex mineral properties, difficult beneficiation and metallurgy, and long process flow. After more than 20 years of experimental research and production practice, a process development technology system of "oxygen pressure acid leaching modified filtration extraction separation process water cycle" has been formed. This article summarizes the technological innovation process of Guyuan 460 uranium molybdenum mine, which comprehensively innovates and practices from multiple aspects such as efficient leaching of uranium molybdenum ore, solid-liquid separation of slurry, separation and purification of uranium molybdenum, product preparation, process water recycling, key equipment and material engineering applications. Finally, an oxygen pressure leaching demonstration mine with an annual processing capacity of 200 000 tons of uranium molybdenum ore was built, greatly improving the scientific and technological level of complex associated uranium molybdenum resource development in China. It is a typical embodiment of new quality productivity in the mineral field.

new quality productivity  /  uranium molybdenum ore  /  pressurized oxidation  /  technological innovation  /  demonstration mine
隋杰, 苏学斌, 刘永涛, 李映兵, 高东星, 程瑞泉, 霍玉宝, 刘辉, 周志全, 刘会武, 师留印, 康绍辉. 新质生产力视角下复杂伴生铀钼资源开发技术创新与实践分析. 铀矿冶, 2025 , 44 (2) : 142 -150 . DOI: 10.13426/j.cnki.yky.2024.09.04
Jie SUI, Xuebin SU, Yongtao LIU, Yingbing LI, Dongxing GAO, Ruiquan CHENG, Yubao HUO, Hui LIU, Zhiquan ZHOU, Huiwu LIU, Liuyin SHI, Shaohui KANG. Technological Innovation and Practice Analysis in the Development of Complex Associated Uranium Molybdenum Resources from the Perspective of New Quality Productivity[J]. Uranium Mining and Metallurgy, 2025 , 44 (2) : 142 -150 . DOI: 10.13426/j.cnki.yky.2024.09.04
新质生产力是以创新为主导的先进生产力质态,具有技术革命性突破、生产要素创新性配置和产业深度转型升级等催生动力,能助力形成凸显高科技、高效能、高质量等核心特质的生产力[1]。在复杂矿产资源开发领域,应主动适应劳动者、劳动资料和劳动对象的革新,通过生产力的跃迁赢得发展主动权,以核心技术创新为驱动,把握世界科技前沿,加快科技自主攻关,重视基础科学研究和基础技术研发,打造新形势下复杂矿产资源开发方面的中国特色,不断培育和发展新质生产力。
世界范围内的铀钼伴生资源较为普遍,中国的铀钼矿资源主要集中在新疆、内蒙古、河北、江西、湖南等地的火山岩中,其中河北沽源460包裹型非晶质胶硫钼矿是典型的铀钼伴生矿,选冶难度大[2];国外的铀钼矿存在于美国、法国、尼日尔、墨西哥等国的沉积砂岩中。中国对于铀钼矿的研究大体经历了3个阶段:1)提铀树脂解毒,从解毒液附带回收钼[3];2)加压碱浸阶段[4],由于硫化矿氧化,碱耗较高,且铀钼分离需要调酸,该工艺较复杂;3)强化堆浸技术阶段[5],该工艺因黏土矿物易泥化而导致渗透性差。国外对铀钼矿的研究和开发较多,但效果均不太理想,如美国格兰次厂钼回收率<10%;尼日尔阿库塔厂铀回收率只有50%~80%,钼浸出率更低;法国洛代夫厂钼产品含钼只有15%;墨西哥利亚阿尔达马厂钼回收率虽然达到74.8%,但铀回收只有68.7%[6]。整体来看,过去国内外均没有做到真正意义上铀钼高效综合回收。
从规模上看,河北沽源460铀钼矿是大型矿床[7],工业开发利用价值高。从地质方面看,矿床整体埋藏较浅,适宜露天开采,有利于降低采矿成本;但钼矿体大于铀矿体,呈鸡蛋状包裹,两者紧密伴生,开采条件复杂。从矿石矿性分析,矿床整体变化较大,从矿床表层到内部大体分为表层氧化带、过渡带、原生带,矿石浸出试剂消耗高,工艺复杂;且矿石中硅、铝含量高,矿石浸出时杂质溶出多,矿浆中胶体物质较多,矿浆黏性大,固液分离难度大;矿石浸出所得浸出液中既含铀又含钼,铀钼性质相近,易被共萃取,铀钼分离纯化难度也很大。从矿床位置来看,矿床处于滦河源头,旅游资源丰富,环境敏感,对工艺水回用和废物排放的要求高。
该铀钼矿中的Mo矿物包括钼华、铁钼华、钼钨钙矿、钼铅矿、胶硫钼矿、水钼铀矿、钙钼铀矿、紫钼铀矿等[8],其中:钼华、铁钼华、紫钼铀矿为简单氧化物类,较易浸出;钼钨钙矿、钼铅矿、钙钼铀矿、水钼铀矿为复杂氧化态类钼矿物,具有一定的浸出难度,需要一些特殊的处理手段,但其所占比例较低,对最终浸出率影响不大;胶硫钼矿(辉钼矿)为原生钼矿物,其硫质与钼矿物在形成过程中反复附着包裹,形成胶质形式,不易被破解,严重阻碍了浸出试剂与目标矿物的有效接触,原生钼矿消耗的氧化剂较大。因此,胶硫钼矿是影响钼总体浸出率的关键,是开发研究的难点。钼矿物物相分析结果见表1。可以看出,沽源460铀钼矿矿性复杂,钼的矿物类型多,且还原态矿物占比呈现快速增加的态势。
新质生产力是符合新发展理念的先进生产力质态,以创新为主导,具有高科技、高效能、高质量特征,是体现创新、协调、绿色、开放、共享等新发展理念的先进生产力。
针对沽源460复杂包裹型铀钼矿石,从开采、选矿、浸出、固液分离、金属回收、产品制备等方面开展了大量研究[9-13]。最初投产时采用原矿直接常压搅拌浸出工艺流程,随着矿山开采深度的逐渐增加,胶硫钼矿的占比越来越高,钼的浸出率逐年降低,部分难浸矿石的钼浸出率甚至不足20%;且矿石中硫含量升高,导致氧化剂(双氧水)的消耗增加,生产成本居高不下。为此,通过不断技术创新,沽源460矿完成了“600 t/d复杂钼矿氧压浸出技术改造项目”,将钼浸出率从30%提高至80%,形成了铀钼矿石高效氧压浸出技术体系。该技术创新工作取得了一系列重大突破。
研究发现,元素硫在被氧化为正六价硫时存在300 kJ/mol的能垒,这使得元素硫的稳定区比预期的大。根据这一能垒,绘制了Mo-S-H2O系ε-pH图,并将铀的ε-pH图进行了叠加(图1)。
图1可见,MoS2的稳定区随着元素硫稳定区域的增加而增大,进而导致MoS2比预期的分解难度大。由于MoS2的稳定区与元素硫的稳定区(图中虚线所围区域)不再是包含与被包含的关系,而是部分重叠,这就使得MoS2氧化的直接产物为元素硫,而不是硫酸根和硫酸氢根。MoS2氧化生成的元素硫一般附着在MoS2的表面,形成一种阻滞膜,对MoS2形成保护作用,这一现象随原生矿物比例的增加而加剧,软锰矿和三价铁等氧化剂很难将其破解,只有氧化电位更高的氧化剂才能将其破解。
沽源460铀钼矿浸出的难点在于胶硫钼矿的浸出,主要原因:1)硫质与钼矿物附着包裹,不易破解;2)原生钼矿量大,需要消耗大量氧化剂。由于常规浸出方法的浸出率低,通过提高浸出温度、降低化学反应活化能、增加氧气在液体中的溶解度及持续供给,可保障还原态矿物的有效氧化,发生的反应为2MoS2+9O2+2H2O→2MoO2(SO4${)}_{2}^{2-}$+4H+,最终形成铀钼原矿酸法加压氧浸工艺,实现复杂铀钼矿的高效浸出。酸法加压氧浸工艺的铀浸出率达90%,钼浸出率从30%提升至80%,浸出时间为1.5 h,浸出效率高。
1)建成了集磨矿制浆、氧压浸出、闪蒸换热、板框过滤、萃取回收等为一体的氧压中试扩大试验平台,该平台氧压釜体积为10 m3。该平台解决了高浓度、粗粒级、高氟氯、高酸度的物料对设备的耐磨、耐腐性能问题,整个系统的材质标准高,具备更强的防堵塞、耐腐蚀、抗纯氧等优点,保证在高温高酸条件下反应釜的绝对安全。目前,该氧压中试扩大试验平台已打造成为中核共伴生放射性矿产资源综合利用工程技术中心的重要研发平台,将在共伴生放射性矿产资源中试研究方面发挥重要作用。
2)建成了一条年处理20万吨铀钼原矿的氧压酸浸生产线。针对高氟、高氯、高固矿浆极易腐蚀磨损设备的技术难题,将耐酸砖、双相钢应用于氧压釜釜体结构与混合装置,成功研制了预浸—氧压—闪蒸—辅助等全套浸出设备,各种易损件使用寿命超过国内同行;同时研发了铀钼矿氧压浸出工艺的热量循环系统,实现热量在整个氧化浸出系统中的循环利用,热量消耗降低40%,最终形成了整套氧压浸出装备。
氧压项目投产初期,随着回用水在氧压生产系统中的不断循环,钼的浸出率逐步从85%降低到70%。针对这一生产技术问题,从机理上查明了酸沉母液中的高浓度${\mathrm{NH}}_{4}^{+}$是影响钼浸出率的主要原因,涉及的反应如下:
铁氧化反应
$4 \mathrm{FeSO}_{4}+\mathrm{O}_{2}+2 \mathrm{H}_{2} \mathrm{SO}_{4}=2 \mathrm{Fe}_{2}\left(\mathrm{SO}_{4}\right)_{3}+2 \mathrm{H}_{2} \mathrm{O} ;$
钼浸出反应
$\begin{array}{l}2 \mathrm{MoS}_{2}+9 \mathrm{O}_{2}+2 \mathrm{H}_{2} \mathrm{O}= \\2 \mathrm{MoO}_{2} \cdot \mathrm{SO}_{4}+2 \mathrm{H}_{2} \mathrm{SO}_{4} ;\end{array}$
三价铁与铵离子沉淀形成铁矾的反应

(NH4)2SO4+3Fe2(SO4)3+12H2O=2NH4Fe3(SO4)2(OH)6+6H2SO4;

钼与铁矾共沉淀反应

NH4Fe3(SO4)2(OH)6+Mo${\mathrm{O}}_{4}^{2-}$+H2O=NH4Fe3(SO4)(MoO4)(OH)6(H2O)+${\mathrm{SO}}_{4}^{2-}$

基于酸碱质子理论中强弱碱稳定性差异,提出了“TFA萃取回收酸沉母液中的钼、萃余水中和汽提生产氨水”工艺(图2),该工艺的铵去除率达99.7%,既避免了${\mathrm{NH}}_{4}^{+}$引入生产系统水中,又实现了酸沉母液中钼金属和副产品氨水的回收,有效确保了氧压生产工艺钼的浸出率维持在80%以上。
针对球磨后中性矿浆硅铝含量高、易形成胶质物、难以沉降的特点,基于磺酸基对铝硅酸盐的减水机理,利用化学改性法成功研发出对铝硅酸盐具有特殊减水性的磺酸功能基新型絮凝剂,该絮凝剂使矿浆沉降速度由1 mm/min提高到10 mm/min(图3)。沉降后的矿浆采用深锥高效浓密机,增加浓缩区高度,提高了浓缩效率,获得了底流矿浆质量百分比浓度>50%的矿浆,同时使溢流液含固量<0.01%,清液可返回磨矿循环使用。该项技术使浓密机生产能力较设计能力提高20%,絮凝剂用量降低49.3%。
酸法加压氧浸技术大幅提高了浸出率,但也导致浸出矿浆呈现:1)高酸度溶蚀造成了细粒级矿粉泥化,细泥含量高;2)高酸高温增加了脉石矿物溶解,矿浆中铝、硅、硫酸根等杂质含量高,黏度增加,难以获取萃取清液和含水率20%左右的干渣。
基于溶度积理论,揭示了CaSO4相变优势场(图4),通过向矿浆中加入适量的废弃电石渣进而生成粗大晶体CaSO4助滤剂,使过滤速度由0.032 m3/(h·m2)提高到0.19 m3/(h·m2),整体过滤时间缩短60%以上。通过辅加絮凝剂,使细微颗粒进一步附着在硫酸钙晶体表面,以形成多孔隙滤饼,加快了过滤速度;再选用压滤方式,提高过滤效率的同时,进一步压实滤饼,降低滤饼含水率,以实现过滤渣的干渣排放。
针对铀钼萃取性能相近,且萃原液杂质和余酸含量高、难以高效分离等技术难题,基于胺类萃取剂与U(Ⅵ)、Mo(Ⅵ)、Mo(Ⅴ)的配合机理,以三脂肪胺为单一萃取体系,开发了钼萃取—酸洗—水洗—反萃取与铀萃取—反萃取的铀钼分离工艺,钼反萃取液中铀含量<0.01%。钼、铀多级逆流萃取结果见图5
针对钼反萃取过程出现大量三相物的问题,一方面提出从源头上采用浓密沉降、调整溶液电位、除硅剂降硅、助滤剂深度过滤等技术手段以控制料液悬浮物的含量,降低溶液固含量,降低硅含量,从而降低三相物产生量;另一方面针对产生的三相物渣,开发了从非晶质三相物渣中回收铀钼技术,相关原理如下:钼反萃取过程中夹带的钼酸铵是三相物渣中钼的主要存在形式,被还原Mo5+的聚合物次之。三相物渣加水制浆得到的溶液pH>7,夹带的钼酸铵可完全溶解;在pH>7的条件下进而与被还原的Mo5+发生歧化反应,在没有氧化剂的情况下以Mo6+的形式进入溶液。铀的存在形式为重铀酸铵,可与硫酸发生溶解反应。相关反应为
$\begin{array}{c} 3 \mathrm{Mo}^{5+} \xrightarrow{\mathrm{OH}^{-}} \mathrm{Mo}^{3+}+2 \mathrm{Mo}^{6+} ; \\ \left(\mathrm{NH}_{4}\right)_{2} \mathrm{U}_{2} \mathrm{O}_{7}+3 \mathrm{H}_{2} \mathrm{SO}_{4}=2 \mathrm{UO}_{2} \mathrm{SO}_{4}+ \\ \left(\mathrm{NH}_{4}\right)_{2} \mathrm{SO}_{4}+3 \mathrm{H}_{2} \mathrm{O} 。 \end{array}$
通过“先水洗钼、后酸溶铀”分步处理工艺,三相物中铀、钼回收率分别高达98.93%、96.08%。
针对钼反萃取液纯化难题,研制了镁盐、铝盐和活性炭复合沉淀药剂,使磷、砷、硅等杂质生成复盐沉淀,制备的钼酸铵符合GB/T 3460标准的最高纯度要求,总放射性<0.04 Bq/g,远低于10 Bq/g国家标准[20];建立了碱性体系间歇式浆体循环沉淀方法,通过强化洗涤解决了铀产品中硫酸根、碳酸根含量高的问题以及低温条件下铀产品易盐胀问题,制得的铀产品达到EJ/T 803—93一级品要求。
沽源460铀钼矿山位于京津冀水源地,环保要求高,不允许废水排放。应用以下技术实现了各工艺废水的闭路循环:1)通过中性矿浆絮凝—浓缩技术的研发和深锥高效浓密机的应用,实现了磨矿用水的闭路循环;2)通过双氧水氧化、加压氧浸、硫酸浸出、洗涤、钼产品制备等技术研究和应用,避免引入氯离子、硝酸根离子、锰离子等难处理杂质,实现了洗涤液、沉淀母液流程内的闭路循环使用;3)针对萃余水中杂质含量高、存在含油悬浊物和溶解的有机相等问题,首先利用电石渣中和沉淀过滤除杂,除杂液再利用活性炭吸附深度除油,有效去除了萃余水中溶解的萃取剂,实现了萃余水返回磨矿的工艺水闭路循环,运行结果见表3
沽源铀尾渣库堆存有约120万吨原工艺处理的高品位含钼尾渣(钼品位0.70%、铀品位0.022%),同时还承担着现有氧压生产线低品位尾渣的堆存任务。为便于尾渣综合利用、提高矿产资源综合利用率、增加企业经济效益、降低尾渣库环境风险,综合沽源尾渣库堆存的现状及相关标准要求,开发了干式尾渣库尾渣安全高效利用技术,将回采区域划分为回采条带和回采线路,采用双回采线路波形啮合的回采推进方法,消除了回采机械之间的相互干扰,上下各层回采线路可同时进行回采,回采效率高。已于2023年底完成了整个回采工程实施,提高尾渣回采量近20万吨,增加回采尾渣金属总价值约4亿元。
与铀钼原矿氧压酸浸不同,针对经过常压酸浸的含钼尾渣进行再处理,存在不同处理路线的优选,尤其是与氧压酸浸相比,氧压碱浸的浸出温度和压力等工艺条件较为弱化,在碱性环境下矿浆中杂质离子浸出相对较少,对设备耐蚀、耐磨的要求较低。不同工艺条件尾渣浸出结果见表4。可以看出,不同氧压浸出条件下尾渣中钼含量均可降至0.15%,钼浸出率均可达80%;同时,氧压酸浸和碳酸钠氧浸条件下的铀金属浸出率均可达60%,而氢氧化钠体系中铀金属未被浸出。综合比较试剂成本,以及与沽源生产体系的配套问题,推荐采用氧压酸浸工艺路线处理铀钼矿尾渣,以年处理20万吨尾渣、钼酸铵产品18.5万元/t计算,年回收铀、钼金属价值共约31 514.02万元,净利润约3 129.12万元。
要形成新质生产力,关键在于发挥科技创新的增量器作用,加大源头性技术储备,为企业高质量发展构建新竞争力和持久动力。围绕沽源460复杂伴生铀钼资源开发,形成了以加压浸出工艺、加压关键设备、萃取分离、铀钼产品制备、工艺水零排放等为核心的技术研发和工业生产体系,具备开展氧压条件试验、台架试验、扩大试验、工业运行的技术能力和装备能力。结合现有铀钼原矿氧压生产线,以氧压技术为核心,围绕钼精矿、钼中矿、镍钼矿和钼的二次资源等其他钼矿资源开发,将进一步加快工业化开发研究,培育形成新产业。这不但可以推进钼工业持续稳定发展,还可以实现经济效益与环境保护的统一。
1)以氧压技术为核心的沽源460复杂铀钼矿工业化项目实现了中国铀钼矿开发历史性突破,在经济、社会、环保、资源等方面均取得了显著效益,确保了矿产资源开发与生态环境保护协调发展和可持续发展,促进了铀钼矿、低品位复杂钼矿湿法冶炼行业的技术进步,具有重要的示范、引领和带动作用,是矿产领域新质生产力的典型体现。
2)通过理论创新和技术方法集成,解决了复杂铀钼矿综合回收开发建设中的重大技术难题,形成了一套完整的、成熟的氧压工艺技术体系和工程化应用技术。下一步将在复杂共伴生放射性矿产资源、钼精矿、钼中矿、镍钼矿和钼的二次资源等其他钼矿资源开发方面不断培育新产业。
  • 中核集团集中研发项目(中核科发〔2021〕292号)
  • 中核集团集中研发项目(铀钼矿尾渣中钼的再回收技术研究)
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2025年第44卷第2期
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doi: 10.13426/j.cnki.yky.2024.09.04
  • 接收时间:2024-09-06
  • 首发时间:2025-07-04
  • 出版时间:2025-05-20
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  • 收稿日期:2024-09-06
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中核集团集中研发项目(中核科发〔2021〕292号)
中核集团集中研发项目(铀钼矿尾渣中钼的再回收技术研究)
作者信息
    1 中核沽源铀业有限责任公司, 河北 张家口 076561
    2 中国铀业股份有限公司, 北京 100013
    3 核工业北京化工冶金研究院, 北京 101149
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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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