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

Abstract

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

CLC Number:

TQ133.4

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.

Figures/Tables 12

Table 1

Gas analysis through dissolution experiment［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

Table 1

Table 2

Table 3

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Table 4

Fig.6

Fig.7

Fig.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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Research progress on dissolution behavior and mechanism of uranium dioxide in nitric acid

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