硝酸中二氧化铀溶解行为与机理研究进展

doi:10.19964/j.issn.1006-4990.2024-0030

摘要/Abstract

摘要：

乏燃料的首端溶解是Purex流程的关键步骤，该步骤产生的料液直接影响后续的铀钚回收及分离效果。二氧化铀是乏燃料的主要成分，要实现乏燃料的有效溶解，必须要对二氧化铀的溶解行为及机理进行系统研究。首先，以二氧化铀与硝酸的基本反应为基础，结合对反应中产生气体的分析，探讨了氧化溶解的机理和溶解过程中亚硝酸的自催化作用，并系统分析了亚硝酸浓度、硝酸浓度、温度和芯块形态对二氧化铀溶解过程的影响；然后，介绍了二氧化铀在硝酸中溶解模型的研究进展，并对模型的适用性进行了探讨；最后，讨论了当前二氧化铀在硝酸中的溶解研究存在的主要问题，并对未来的发展方向进行了展望。

关键词: 二氧化铀, 溶解机理, 溶解动力学, 硝酸溶液, 影响因素

Abstract:

The dissolution of spent fuel is the head-end step in the Purex process，as the resulting feed liquid directly impacts the subsequent recovery and separation of uranium and plutonium.Spent fuel primarily consists of uranium dioxide，thus it is imperative to systematically investigate the dissolution behavior and mechanism of this compound for effective dissolution.By examining the fundamental reaction between uranium dioxide and nitric acid，as well as analyzing the gas generated during this reaction，the mechanism of oxidation dissolution and autocatalysis of nitrous acid in the dissolution process were discussed.The effects of nitrous acid concentration，nitric acid concentration，temperature and pellet shape on the dissolution process of uranium dioxide were systematically analyzed.Then the research progress of uranium dioxide dissolution model in nitric acid was introduced，and the applicability of the model was discussed.Finally，the main problems existing in the current research on the dissolution of uranium dioxide in nitric acid were discussed，and the future development direction was prospected.

Key words: uranium dioxide, mechanism of dissolution, dissolution kinetics, nitric acid, contributing factor

中图分类号:

TQ133.4

房帆, 姚本林, 肖益群, 贾艳虹, 陈辉, 李斌, 何辉. 硝酸中二氧化铀溶解行为与机理研究进展[J]. 无机盐工业, 2024, 56(9): 34-43.

FANG Fan, YAO Benlin, XIAO Yiqun, JIA Yanhong, CHEN Hui, LI Bin, HE Hui. Research progress on dissolution behavior and mechanism of uranium dioxide in nitric acid[J]. Inorganic Chemicals Industry, 2024, 56(9): 34-43.

图/表 12

表1

溶解实验生成气体分析［22］

分析的物质	检测方法	结果
N₂	气相色谱分析	未检出
$N H 4 +$	取溶液测量	未检出
NO	化学发光法和红外光谱法	检出
NO₂	化学发光法	检出
N₂O	红外光谱法	检出

表1

表2

表3

图1

图2

图3

图4

图5

表4

图6

图7

图8

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芯块质量/g	c（HNO₃）/ （mol·L^-1）	温度/ ℃	收集到NO _x 气体的量
芯块质量/g	c（HNO₃）/ （mol·L^-1）	温度/ ℃	总物质的量/（10^-3mol）	x（NO）/ %	x（NO₂）/ %
1.019 5	3.4	100	2.673	86	14
1.005 0	4.5		2.599	84	16
0.990 4	6.7		2.718	75	25
1.005 7	8.1		3.642	45	55
0.940 6	12.5		4.956	18	82

芯块质量/g	c（HNO₃）/ （mol·L^-1）	溶解1mol UO₂产生NO _x 的气体量/mol
芯块质量/g	c（HNO₃）/ （mol·L^-1）	n（NO _x ）	n（NO）	n（NO₂）
1.019 5	3.4	0.71	0.64	0.07
1.005 0	4.5	0.70	0.62	0.08
0.990 4	6.7	0.74	0.61	0.13
1.005 7	8.1	0.98	0.54	0.43
0.940 6	12.5	1.42	0.36	1.06

UO₂形态	活化能/ （kJ·mol^-1）	级数	c（HNO₃）/ （mol·L^-1）
芯块^［29］	47.99	2.27	3~10
芯块^［45］		2.3	2~10
粉末^［27］	30.67	1.21	0.5~2
芯块^［28］	107.11^a	3.3	4~10
粉末^［34］	70.88	1.9	4~10
芯块^［42］		3.2	7.3
粉末^［36］	59.50	2.74	6~9.5
芯块^［48］	59.71	2.13	5
粉末^［37］	73.20	1.58	4~8
芯块^［53］	24.35	4.44	0.1~4

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