稀土高温酸法工艺放射性废渣资源性研究
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摘要
对白云鄂博混合稀土精矿(REO~50%)浓硫酸高温分解工艺放射性废渣的产生过程、组成形貌、粒径分布和资源特性等进行了系统研究和鉴定分类,并对废渣蕴含的资源量及资源化开发进行了初步研究。通过研究得出,废渣富含稀土、钍、铌、磷、铁等多种有价元素,且所含的稀土较少,部分是以矿物形式存在,大部分是以包裹夹带形式存在,其中镨、钕、钆含量偏高,因此该废渣的资源储量和经济价值巨大。按照相关国家标准,废渣中α、β总比放为7.11×10~4Bq/kg左右,属于第Ⅰ级(低放废物);浸出毒性和腐蚀性符合国标要求,属于第Ⅰ类一般工业废物。在热的酸溶液中,可将废渣中各有价元素提取,为综合利用提供条件。
The radioactive waste slag were extracted from Bayun Obo mixed rare earth concentrate(REO ~ 50%) by traditional sulfuric acid decomposition process.The generation process,chemical composition,surface morphology and particle size distribution were investigated and identified systemically.Furthermore,some preliminary study has been done to quantify the resource of the waste slag and its related exploitation in future.It has found that the waste slag is rich in abundant valuable elements such as rare earth,thorium,niobium,phosphorus,iron etc,in which small amount of rare earths are in the form of mineral and most of the rare earths are bundled by other elements.And the contents of elements like praseodymium,neodymium,gadolinium are larger than other elements,so the waste slag has great resource reservation and economic value.According to national standards,if the totally specific radioactivity of α-ray and β-ray of waste slag is around 7.11 × 104 Bq/kg,the slag belongs to class-Ⅰ(low-radioactive wastes); Besides,its leaching toxicity and causticity are both accord with national standard,ascribing to class-Ⅰgeneral industrial waste.In addition,these valuable elements can be extracted from the heated acid solution,this will be beneficial for comprehensive utilization of waste slag.
The radioactive waste slag were extracted from Bayun Obo mixed rare earth concentrate(REO ~ 50%) by traditional sulfuric acid decomposition process.The generation process,chemical composition,surface morphology and particle size distribution were investigated and identified systemically.Furthermore,some preliminary study has been done to quantify the resource of the waste slag and its related exploitation in future.It has found that the waste slag is rich in abundant valuable elements such as rare earth,thorium,niobium,phosphorus,iron etc,in which small amount of rare earths are in the form of mineral and most of the rare earths are bundled by other elements.And the contents of elements like praseodymium,neodymium,gadolinium are larger than other elements,so the waste slag has great resource reservation and economic value.According to national standards,if the totally specific radioactivity of α-ray and β-ray of waste slag is around 7.11 × 104 Bq/kg,the slag belongs to class-Ⅰ(low-radioactive wastes); Besides,its leaching toxicity and causticity are both accord with national standard,ascribing to class-Ⅰgeneral industrial waste.In addition,these valuable elements can be extracted from the heated acid solution,this will be beneficial for comprehensive utilization of waste slag.
引文
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[2]赵长有.白云鄂博的钍与铀(一)[J].稀土信息,2006,(7):12-15.Zhao C Y.Thorium and uranium in Baiyunobo[J].Rare Earth Information,2006,(7):12-15.
[3]刘建亮,罗明标,平爱东,等.稀土精矿中钍的提取工艺研究进展[J].稀有金属,2012,36(4):651-658.Liu J L,Luo M B,Ping A D,et al.Progress in extraction technology of thorium from rare earth concentrate[J].Chinese Journal of Rare Metals,2012,36(4):651-658.
[4]黄小卫,龙志奇,李红卫,等.中国稀土湿法冶金技术的发展[J].稀土,2005,26(1):1-4.Huang X W,Long Z Q,Li H W,et al.Development of rare earth hydrometallurgy technology in China[J].Chinese Rare Earths,2005,26(1):1-4.
[5]陈立东.三代酸法稀土分离工艺改进和发展过程[J].包钢科技,2003,29(2):80-82.Chen L D.Improvement and development of the third acid generation RE separation[J].Science&Technology of Baotou Steel(Group)Corporation,2003,29(2):80-82.
[6]徐光宪,师昌绪,王淀佐,等.关于保护白云鄂博矿钍和稀土资源,避免黄河和包头受放射性污染的紧急呼吁[J].中国科学院院刊,2005,20(6):448-450.Xu G X,Shi C X,Wang D Z,et al.An urgent appeal for the protection of thorium and rare earth resources in Baiyunebo,to avoid the radioactive contamination of Baotou and the Yellow River[J].Bulletin of Chinese Academy of Sciences,2005,20(6):448-450.
[7]徐光宪.白云鄂博矿钍资源开发利用迫在眉睫[J].稀土信息,2005,(5):3-5.Xu G X.The development and utilization of thorium resources in Baiyun Obo mine is imminent[J].Rare Earth Information,2005,(5):3-5.
[8]李春龙,徐广尧.关于包头钍资源战略储备的剖析[J].稀土,2014,35(4):115-118.Li C L,Xu G Y.Analysis on the strategic reserves of thorium resources in Baotou[J].Chinese Rare Earths,2014,35(4):115-118.
[9]李春龙,李小刚,徐广尧.白云鄂博共伴生矿资源综合利用技术开发与产业化[J].稀土,2015,36(5):151-158.Li C L,Li X G,Xu G Y.Technology development and industrialization of resources comprehensive utilization of intergrowth and associated ore in Baiyun Obo[J].Chinese Rare Earths,2015,36(5):151-158.
[10]李德谦,左勇,白彦,等.一种从硫磷混酸体系中萃取分离钍和提取氯化稀土的工艺[P].中国:CN02123913,2003-02-05.Li D Q,Zuo Y,Bai Y,et al.A technology of extraction and separation of thorium and extraction of chloride rare earth from mixed acid system of sulfur and phosphorus[P].China:CN02123913,2003-02-05.
[11]苏文清,贺海钧,宋洪芳,等.包头白云鄂博矿钍资源的回收及用于核电燃料的研究现状[J].稀有金属,2005,29(6):914-918.Su W Q,He H J,Song H F,et al.Research status of recovery of thorium resource of Baotou Baiyun Obo Ore and application of thorium in nuclear power fuels[J].Chinese Journal of Rare Metals,2005,29(6):914-918.
[12]崔小震,陈月华,任萍,等.独居石酸溶渣资源综合回收绿色循环工艺[J].稀土,2015,36(3):61-66.Cui X Z,Chen Y H,Ren P,et al.Recycling of residual slag from monazite processing[J].Chinese Rare Earths,2015,36(3):61-66.
[13]黄小卫,张国成,龙志奇,等.从稀土矿中综合回收稀土和钍工艺方法[P].中国,CN200510085230,2006-01-08.Huang X W,Zhang G C,Long Z Q,et al.Process for comprehensive recovery of rare earth and thorium from rare earth ore[P].China:CN200510085230,2006-01-08.
[14]王敏,方方,帅震清,等.四川氟碳铈矿选冶工艺过程放射性污染现状[J].稀土,2011,32(3):94-97.Wang M,Fang F,Shuai Z Q,et al.The status of radioactive pollution during the mineral processing and smelting from sichuan bastnaesite[J].Chinese Rare Earths,2011,32(3):94-97.
[15]张书成,刘平,仉宝聚.钍资源及其利用[J].世界核地质科学,2005,22(2):98-103.Zhang S C,Liu P,Zhang B J.Thorium resources and their availability[J].World Nuclear Geoscience,2005,22(2):98-103.
[16]白丽娜,张利成,王灵秀.包头稀土生产带来的放射性环境污染及防治措施[J].稀土,2001,22(1):76-78.Bai L N,Zhang L C,Wang L X.Radioactive environmental pollution caused by rare earth production in Baotou and its prevention and cure measures[J].Chinese Rare Earths,2001,22(1):76-78.