Circulating adsorption-desorption properties and kinetic analysis of uranium by strong basic anion resins

doi:10.16085/j.issn.1000-6613.2022-2072

Abstract

Abstract:

201×7 strong basic anion resin was used to investigate the effects of circulating adsorption times, solution concentration and solution flow rate on the penetration time and saturation capacity of uranium adsorbed by a fixed bed dynamic adsorption. Dynamic circulating adsorption-desorption-transformation test of resin adsorb uranium was carried out. Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Mineral Liberation Analyzer (MLA) were characterized and analyzed on the resins surface before and after adsorption. Content of impurity elements in saturated resin and lean resin was tested to discuss physicochemical mechanism of resins "poisoned" and effective detoxification method. The kinetic model of uranium adsorption by resin was deduced theoretically and the experimental data were fitted to verify the accuracy of the model. The results showed that penetration time and saturated adsorption capacity of resins was seriously impacted by times of circulating adsorption, concentration of adsorbed solution and flow rate of adsorbed solution. When the dynamic circulating adsorption-desorption-transformation times reached to 10, resins surface and pores attached sediment and internal functional group accumulated with PO₄^3-, Mo, SiO₂ and other impurities, resulting in resin "poisoned". Compare to first circulating time, the resins adsorption saturation capacity decreased by 13.7% and the desorption solution concentration peak decreased by 28.9%. Resin "poisoned" was mainly precipitate blocking resin channel, resulting in the physical failure of the functional group, and impurities elements occupied the functional group, leading to the chemical failure of the functional group. After resins detoxified by NaOH, the saturated adsorption capacity of resins increased by 9.9% and desorption rate of the resins reached to 99.8% compared with that before detoxification, and the resins had strong stability. The fixed bed adsorption kinetic model derived from the theory can describe the kinetic process of uranium adsorption by resin with high fitting accuracy.

Key words: uranium solution, circulating adsorption, circulating desorption, circulating transformation, resin poisoned, model of dynamics

摘要：

采用201×7强碱性阴离子树脂，通过固定床动态吸附试验，考察了循环吸附次数、吸附原液浓度、吸附原液流量等因素对树脂吸附铀穿透时间与饱和容量影响；开展树脂对铀的动态循环吸附-淋洗-转型试验，采用电感耦合等离子体质谱仪（ICP-MS）和工艺矿物学参数测试系统（MLA）对吸附前后树脂的表面进行表征和分析，测试饱和树脂与贫树脂杂质元素含量，探讨树脂“中毒”的物理化学机理以及有效的解毒方式；理论推导出树脂吸附铀动力学模型，并对试验数据进行拟合，验证模型的精确度。结果表明：循环吸附次数、吸附原液浓度、吸附原液流量等因素对树脂吸附穿透时间与饱和容量有较大影响。当动态循环吸附-淋洗-转型次数达到10次时，树脂表面和孔隙积累了沉淀物，功能基团上积累PO₄^3-、Mo、SiO₂等杂质元素，造成树脂“中毒”，树脂吸附饱和容量降低了13.7%，淋洗峰值降低了28.9%；树脂“中毒”主要是沉淀物堵塞树脂通道造成功能基团物理失效，以及亲基性杂质元素占据功能基团造成功能基团化学失效。NaOH“解毒”树脂后，树脂饱和容量较解毒前提高了9.9%，树脂的淋洗率达到99.8%，树脂具有较强的稳定性。理论推导出的固定床吸附动力学模型能很好地描述树脂吸附铀的动力学过程，拟合精度高。

关键词: 铀溶液, 循环吸附, 循环淋洗, 循环转型, 树脂中毒, 动力学模型

CLC Number:

TF84

LIU Yulong, HU Nan, CHEN Xiangbiao, CHEN Sencai, ZENG Bingyong, DING Dexin. Circulating adsorption-desorption properties and kinetic analysis of uranium by strong basic anion resins[J]. Chemical Industry and Engineering Progress, 2023, 42(10): 5574-5583.

刘玉龙, 胡南, 陈祥标, 陈森才, 曾冰勇, 丁德馨. 强碱性阴离子树脂对铀的循环吸附-淋洗性能及动力学分析[J]. 化工进展, 2023, 42(10): 5574-5583.

Figures/Tables 18

n	$V k v$	$V v τ$	R²
1	4.51	82.27	0.9800
3	6.37	93.24	0.9781
5	7.42	73.26	0.9903
7	8.85	78.12	0.9983
9	9.63	75.27	0.9738

n	$V k v$	$V v τ$	R²
1	4.51	82.27	0.9800
3	6.37	93.24	0.9781
5	7.42	73.26	0.9903
7	8.85	78.12	0.9983
9	9.63	75.27	0.9738

n	Q/mg·mL^-1
1	62.88
3	62.06
5	58.65
7	57.61
9	54.85

原液浓度/g·L^-1	$V k v$	$V v τ$	R²
0.51	4.85	102.12	0.9501
0.98	3.68	67.88	0.9903
1.44	2.95	45.94	0.9769
2.22	3.00	32.46	0.9196

原液浓度/g·L^-1	$V k v$	$V v τ$	R²
0.51	4.85	102.12	0.9501
0.98	3.68	67.88	0.9903
1.44	2.95	45.94	0.9769
2.22	3.00	32.46	0.9196

原液浓度/g·L^-1	Q/mg·mL^-1
0.51	49.49
0.98	58.07
1.44	60.03
2.22	64.94

原液流量/mL·min^-1	$V k v$	$V v τ$	R²
25	5.99	57.96	0.8959
20	6.65	72.99	0.8723
15	7.97	94.24	0.9576

原液流量/mL·min^-1	$V k v$	$V v τ$	R²
25	5.99	57.96	0.8959
20	6.65	72.99	0.8723
15	7.97	94.24	0.9576

原液流量/mL·min^-1	Q/mg·mL^-1
15	59.38
20	58.07
25	57.46

循环次数	U/mg·g^-1	Fe/mg·g^-1	PO₄^3-/mg·g^-1	Mo/mg·g^-1	SiO₂/mg·g^-1
5	114.86	0.24	0.20	0.12	0.18
10	106.92	0.42	0.41	0.25	0.24

循环次数	U/mg·g^-1	Fe/mg·g^-1	PO₄^3-/mg·g^-1	Mo/mg·g^-1	SiO₂/mg·g^-1
5	0.36	0.02	0.05	0.06	0.11
10	0.24	0.02	0.09	0.21	0.15

树脂状态	U/mg·g^-1	Fe /mg·g^-1	PO₄^3-/mg·g^-1	Mo /mg·g^-1	SiO₂/mg·g^-1
淋洗后（10次）	0.24	0.02	0.09	0.21	0.15
解毒后（10次）	0.20	0.02	0.02	0.04	0.12

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