CN113053554A - 一种通过水热-烧结联用固化放射性元素的方法 - Google Patents
一种通过水热-烧结联用固化放射性元素的方法 Download PDFInfo
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Abstract
本发明公开了一种通过水热‑烧结联用固化放射性元素的方法。该方法包括以下步骤:S1.将活化高岭土、CsCl和碱混合均匀,其中,混合物中碱、CsCl、Al2O3和SiO2的摩尔比为0.01‑10:0.01‑10:1‑3:2‑6;S2.以水固比为0.1~1.2的比例向S1所得混合物中加水,搅拌成型后凝固,得固化体;S3.于150~300℃对S2得到的固化体进行水热养护,养护20~30h后,于1200~1500℃烧结即可。本发明在水热合成基础上,可利用NaOH与CsCl的离子交换机制以促进Cs+在水热合成条件下形成的相关前驱物,并通过烧结方式进一步形成铯榴石结构,同时增强其结构的致密性,从而产生良好的固化性能。
Description
技术领域
本发明属于核废料固化技术领域,具体涉及一种通过水热-烧结联用固化放射性元素的方法。
背景技术
为了实现可持续发展,人类迫切地需要新的替代能源。目前,达到工业应用并可以大规模替代化石燃料的能源主要是核能。核电发展很好地遵守了可持续发展的某些原则,但仍有一些重要方面需要考虑。分别是铀的供应,核废物处置,核燃料安全循环以及核电厂运行安全等问题。其中,137Cs属于中、高毒性,半衰期较长,为30.5a,且放射性占混合裂变产物总放射性的比重大,一般需经几百年甚至更长的时间才能衰变至无害水平,因此科学安全地对核废物进行处理是一个重要课题。CsCl是放射性核废料中的一种常见形式,需要对其进行有效固化处理,以减少其对生物圈产生潜在的威胁,。
科学安全处置放射性137Cs的主流思想是,采用地聚物、玻璃或陶瓷对放射性核素进行固化以形成致密的显微结构或晶体结构从而有效阻止其对环境的迁移。随后,采用深地质(500-1000米)埋藏方式,对固化体进行存放直至核素衰变至对生物圈无害,但这将经历上百年乃至数万年的时间,因而对固化材料的长期稳定性提出要求。CsCl是放射性核废料中的一种常见的放射性137Cs的化合物存在形式,其可溶性和迁移极强,而且分解温度较高。通过水热方式对其固化时,可通过水热合成所形成的多孔沸石结构的吸附作用或形成似长石结构(如铯榴石)对其进行固化。然而,水热合成固化体的强度偏低,且固化体结构致密性较差,尤其对Cl-的固化能力较差,因此对CsCl的固化能力有限。
发明内容
针对现有技术中的上述不足,本发明提供一种通过水热-烧结联用固化放射性元素的方法,通过水热方式处理可初步形成以铯榴石为主的含铯稳定结构,并对铯进行有效固化。在此基础上,通过进一步的烧结处理,不仅可以继续增强铯榴石的稳定性,而且可以进一步促使结构的致密化,并有效减少铯的高温挥发。
为实现上述目的,本发明解决其技术问题所采用的技术方案是:
一种通过水热-烧结联用固化放射性元素的方法,其特征在于,包括以下步骤:
S1.将活化高岭土、CsCl和碱混合均匀,其中,混合物中碱、CsCl、Al2O3和SiO2的摩尔比为0.01-10:0.01-10:1-3:2-6;
S2.以水固比为0.1~1.2的比例向S1所得混合物中加水,搅拌至形成均匀的浆体,然后使其凝固,得固化体;
S3.于150~300℃对S2得到的固化体进行水热养护,养护20~30h后,于1200~1500℃烧结即可。
地聚物结构多以凝胶或半结晶结构为主,从材料热力学稳定性而言,仅仅以地聚物固封的形式长期处置放射性核素还不足以保证其能被稳定地固化和长期存放。为增强固化体结构的长期稳定性,可以通过水热或烧结的方式促进地聚物凝胶结构朝着更稳定的晶态结构过渡。通过水热养护可使地聚物形成规则多孔的沸石或似长石结构,并依靠其结构的吸附作用,可稳定阻止Cs元素的迁移,但水热养护地聚物致密性较低,而CsCl的可溶性极强,且分解温度极高,其固化效果并不理想。
通过在水热养护的基础上,进一步采用烧结的方式,不仅可以提高固化体的致密性,而且可以利用NaOH与CsCl的离子交换机制以促进Cs+在水热合成条件下形成以铯榴石为主的相关前驱物,并通过烧结方式进一步增强铯榴石结构,同时增强其结构的致密性,从而产生良好的固化性能。
而本发明的“水热-烧结”方式地聚固化CsCl的方法,还在水热养护阶段促使地聚结构初步形成沸石、方钠石和铯榴石等前驱结构,并在NaOH作用下促进CsCl与其产生离子交换以增强铯榴石结构的形成,而后通过烧结方式促成铯榴石结构形成的同时获得致密显微结构,通过铯榴石结构的存在而稳定固化Cs。该种“水热-烧结”方式地聚固化CsCl的工艺及方法可用于放射性废料和各种废弃放射性铯源的处理,也可以用于日常相关废弃元素的固化处理。
进一步地,活化高岭土的制备方法为:
将高岭土置于700~800℃环境中煅烧2~3h即可。
热活化是通过煅烧方法对高岭土加工进行热处理,把大部分或全部羟基脱掉。此时,新的稳定相(莫来石、方英石等)尚未形成,而Si和Al的溶出量非常大,因此具有很大的活性;煅烧还可以使高岭土的晶体结构发生改变(主要是由层间氢键的断裂及脱除结构水引起的),由原来有序的层状晶体结构的高岭石变成无序结构的偏高岭石,使得原晶体内层面的部分基团外露,并且由于结构水的脱去,表面活性点的种类和数量都增加了,使得反应活性增加,从而可作为高活性原料帮助合成相应的硅铝酸盐晶体或其他方法合成硅酸盐化合物。
进一步地,碱包括但不局限于氢氧化钠或氢氧化钾。
进一步地,水固比为0.6。
水固比过低可能会导致搅拌过程中无法形成浆体,过高则会使得浆体过稀,造成后续成型过程中固化体内部孔洞较多等现象,使固化体整体结构松散,强度降低。因此,本申请在步骤S2中选用水固比为0.1~1.2的比例进行处理,尤其是以0.6的水固比为最佳。
进一步地,水热养护温度为200℃,养护时间为24h。
进一步地,烧结温度为1200℃,烧结时间为2~3h。
在1200~1500℃温度范围内烧结可保证地聚物转变为陶瓷。若烧结温度过高,可能会出现过烧等现象,若温度过低,则会造成固化体结构松散、未成瓷等现象,使固化性能降低甚至失去固化性能。而1200℃则是本申请方案中最佳的成瓷温度或致密化烧结点。
本发明的有益效果:
1、本发明中,以碱、CsCl、Al2O3和SiO2的摩尔比为0.01-10:0.01-10:1-3:2-6作为地聚物设计组成,采用水热养护,而后进行常压烧结,主要晶体结构为铯榴石,铯的浸出能力按照美国标准C1285-14测试,Cs+浸出分数低至0.03wt%。
2、本发明采用一种“水热-烧结”方式,通过形成铯榴石结构,并对Cs进行有效固化。
3、本发明无需掺入表面活性剂或晶种,无需复杂的化学工艺除Cl-,工艺方法及设备简单,操作方便,容易实现规模化生产。
4、本发明的基于地聚物“水热-烧结”方式固化处理CsCl的方法,还可以极大地去除Cl-并吸收废料中的铯,且由于成熟的工艺技术而有益于废料固化过程中的各种操作和控制。
5、本发明的基于地聚物“水热-烧结”方式固化处理CsCl的工艺及方法可用于放射性废料和各种含铯盐废弃放射性铯源的处理,也可以用于日常相关废弃元素的固化处理。
附图说明
图1为本发明烧结前后样品结构表征图;
图2为本发明烧结前后样品结构表征图;
图3为本发明烧结前后样品结构表征图;
图4为本发明水热后未烧结固化体50000倍放大的显微结构图;
图5为本发明烧结后样品50000倍放大的显微结构图。
具体实施方式
下面对本发明的具体实施方式进行描述,以便于本技术领域的技术人员理解本发明,但应该清楚,本发明不限于具体实施方式的范围,对本技术领域的普通技术人员来讲,只要各种变化在所附的权利要求限定和确定的本发明的精神和范围内,这些变化是显而易见的,一切利用本发明构思的发明创造均在保护之列。
实施例1
一种通过水热-烧结联用固化放射性元素的方法,包括以下步骤:
(1)取固体原料活化高岭土、氯化铯和氢氧化钠,按照化学元素的摩尔比为2.4NaOH·3.2CsCl·2SiO2·Al2O3的组成,进行配比称量后,按0.6水固比加入去离子后搅拌;
(2)搅拌均匀后,倒出浆体置于模具中,在70-90℃的温度烘干24小时凝固;
(3)烘干后,将磨具中的固化体置于反应釜中,在200℃的温度水热24小时;
(4)水热后,进行烧结,烧结温度设定在1200℃,烧结时间2小时,得到样品,标为实施方案1。
实施例2
一种通过水热-烧结联用固化放射性元素的方法,包括以下步骤:
(1)取固体原料活化高岭土、氯化铯和氢氧化钠,按照化学元素的摩尔比为1.6NaOH·4.8CsCl·2.3SiO2·Al2O3的组成,进行配比称量后,按0.6水固比加入去离子后搅拌;
(2)搅拌均匀后,倒出浆体置于模具中,在70-90℃的温度烘干24小时凝固;
(3)烘干后,将磨具中的固化体置于反应釜中,在200℃的温度水热24小时;
(4)水热后,进行烧结,烧结温度设定在1200℃,烧结时间2小时,得到样品,标为实施方案2。
实施例3
一种通过水热-烧结联用固化放射性元素的方法,包括以下步骤:
(1)取固体原料活化高岭土、氯化铯和氢氧化钠,按照化学元素的摩尔比为0.8NaOH·6.4CsCl·2.6SiO2·Al2O3的组成,进行配比称量后,按0.6水固比加入去离子后搅拌;
(2)搅拌均匀后,倒出浆体置于模具中,在70-90℃的温度烘干24小时凝固;
(3)烘干后,将磨具中的固化体置于反应釜中,在200℃的温度水热24小时;
(4)水热后,进行烧结,烧结温度设定在1200℃,烧结时间2小时,得到样品,标为实施方案3。
实验例1
分别对实施例1-3所得烧结前后的样品实施方案1、实施方案2、实施方案3进行结构表征,结果分别如图1-3所示。
由图1-3可知,烧结前,样品内相结构较为复杂,且实施方案2和3内还有氯化铯剩余,烧结后,样品实施方案1、2、3皆可形成单一的铯榴石结构,该结构与X衍射数据库中的铯榴石结构(PDF:88-0055)相吻合,即实施例1-3的产品均为铯榴石。
实验例2
对实施例2所得固化体和样品实施方案2进行显微结构分析,结果如图4、图5所示。
图4为水热合成样品的微观形貌、图5是水热合成样品经烧结后所得到的微观形貌,比较二图,说明“水热-烧结”方式可以促使结构更致密,从而实施例2得到了结构致密的铯榴石。
实验例3
分别测试实施例1-3所得样品实施方案1、实施方案2、实施方案3的铯离子浸出性能。
参照美国标准C1285-14进行测试,基本方法是:准确称量大于1克以上样品,按照去离子水固比10:1放入密封良好的304不锈钢瓶中,同条件下,每个样品至少进行3个平行样品进行同条件测试。装好的实验装置称量后,放入烘箱在90℃恒温条件下实验7天±3.4小时。测试时间结束,取出实验装置室温冷却后称重,前后重量损失在标准要求误差范围内后,取出溶液进行离心分离,取上清液测试浸出离子浓度,结果如下表1:
表1铯离子浸出平均分数表
Claims (7)
1.一种通过水热-烧结联用固化放射性元素的方法,其特征在于,包括以下步骤:
S1.将活化高岭土、放射性材料和碱混合均匀,其中,混合物中碱、放射性材料、Al2O3和SiO2的摩尔比为0.01-10:0.01-10:1-3:2-6;
S2.以水固比为0.1~1.2的比例向S1所得混合物中加水,搅拌成型后凝固,得固化体;
S3.于150~300℃对S2得到的固化体进行水热养护,养护20~30h后,于1200~1500℃烧结即可。
2.根据权利要求1所述的通过水热-烧结联用固化放射性元素的方法,其特征在于,所述活化高岭土的制备方法为:
将高岭土置于700~800℃环境中煅烧2~3h即可。
3.根据权利要求1所述的通过水热-烧结联用固化放射性元素的方法,其特征在于,所述碱为氢氧化钠或氢氧化钾。
4.根据权利要求1所述的通过水热-烧结联用固化放射性元素的方法,其特征在于,所述水固比为0.6。
5.根据权利要求1所述的通过水热-烧结联用固化放射性元素的方法,其特征在于,所述水热养护温度为200℃,养护时间为24h。
6.根据权利要求1所述的通过水热-烧结联用固化放射性元素的方法,其特征在于,所述烧结温度为1200℃,烧结时间为2~3h。
7.根据权利要求1所述的通过水热-烧结联用固化放射性元素的方法,其特征在于,所述放射性材料为CsCl。
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