氨基改性苯乙烯树脂的合成及其对铼的吸附

doi:10.11949/0438-1157.20191459

化工学报 ›› 2020, Vol. 71 ›› Issue (5): 2109-2117.DOI: 10.11949/0438-1157.20191459

氨基改性苯乙烯树脂的合成及其对铼的吸附

张雨¹(),花榕¹(),寇晓康²,刘付平¹,孔杰¹,张峰¹,何非凡¹,冯宇¹

^1.东华理工大学核科学与工程学院，核资源与环境国家重点实验室，江西南昌 330013
^2.蓝晓科技新材料股份有限公司，陕西西安 710076

收稿日期:2019-12-02 修回日期:2020-03-01 出版日期:2020-05-05 发布日期:2020-05-05
通讯作者: 花榕
作者简介:张雨(1995—)，女，硕士研究生，932659306@qq.com
基金资助:
国家自然科学基金项目(21761002);国防基础科研项目(JCKY2017401C005);江西省质谱科学与仪器重点实验室开发基金项目(JSMS201607);核资源与环境省部共建国家重点实验室项目(NRE1313);核能开发项目(共伴生铀资源采冶技术——以内蒙巴彦乌拉铀铼同采为示范)

Preparation of amino modified styrene-divinylbenzene resin and its adsorption of rhenium

Yu ZHANG¹(),Rong HUA¹(),Xiaokang KOU²,Fuping LIU¹,Jie KONG¹,Feng ZHANG¹,Feifan HE¹,Yu FENG¹

^1.State Key Laboratory of Nuclear Resources and Environment, School of Nuclear Science and Engineering, East China University of Technology, Nanchang 330013, Jiangxi, China
^2.Sunresin New Materials Co. , Ltd, Xi’an 710076, Shaanxi, China

Received:2019-12-02 Revised:2020-03-01 Online:2020-05-05 Published:2020-05-05
Contact: Rong HUA

摘要/Abstract

摘要：

离子交换法因适于低浓度物质的分离富集而被广泛应用于湿法冶金行业，新型高效吸附材料的合成与应用成为该领域的发展趋势。针对铀矿中伴生铼这一稀缺资源需要同步回收的现状，根据新近研发的氨基改性苯乙烯阴离子交换树脂(LSC-Re)，通过静态和动态吸附解吸试验，系统考察了溶液酸度、初始浓度、吸附时间、吸附温度等因素对吸附性能的影响，结果表明：在室温(25℃)下，铼溶液初始浓度为100 mg·L^-1，该树脂6 h达到吸附平衡，酸度对该树脂吸附铼的影响不大，树脂在pH=1.5时铀铼分离效果最佳，分离系数可达到41.68；树脂的饱和吸附容量达到129.3 mg·g^-1；从热力学和动力学角度分析，吸附过程符合Langmuir吸附等温模型和准二级动力学模型，且吸附是自发的吸热过程。动态吸附解吸试验中，控制溶液流速0.5 ml·min^-1，动态饱和吸附容量达到76.17 g·L^-1，饱穿比为2.35，用1 mol·L^-1 氨水进行解吸铼效果较好，8个树脂床体积可将其解吸完全，由此可见富集倍数接近70倍，具有良好的工业应用前景。

关键词: 铼, 分离富集, LSC-Re树脂, 动力学, 吸附, 解吸

Abstract:

The ion exchange method is widely used in the hydrometallurgical industry because it is suitable for the separation and enrichment of low-concentration substances. The synthesis and application of new high-efficiency adsorption materials have become the development trend in this field. In view of the current situation that the associated scarce rhenium minerals in uranium mine need to recover synchronously, the preparation of amino modified styrene-divinylbenzene resin (LSC-Re) was used to recover rhenium in this work. The effect of aqueous acidity, initial concentration, adsorption time and adsorption temperature on the adsorption performance were systematically investigated by static and dynamic adsorption desorption experiments. The results show that 6 h is sufficient up to equilibrium for the LSC-Re anion exchange resin at room temperature, and the acidity has little effect on the adsorption. The LSC-Re anion exchange resin exhibited higher affinity toward Re (Ⅳ) than U(Ⅵ) at pH 1.5, the maximum value of separation factor β_{Re(Ⅳ)/U(Ⅵ)} is 41.68. The saturated adsorption capacity of resins could reach 129.3 mg·g^-1 at present conditions. The adsorption mechanism is in accordance with Langmuir adsorption isotherm model and quasi-second-order kinetic model, and the adsorption process is a spontaneous endothermic from the perspective of thermodynamics and kinetics. The dynamic saturated adsorption capacity could reach 76.17 g·L^-1 and the saturation ratio could reach 2.35 by controlling the solution flow rate to 0.5 ml·min^-1 in the dynamic adsorption experiment. The 8 resin bed volumes can be desorbed completely by 1 mol·L^-1NH₃·H₂O, the enrichment factor is close to 70 times, which means that the LSC-Re anion exchange resin has good industrial application prospects in recovery Re (Ⅳ).

Key words: rhenium, separation and enrichment, LSC-Re resin, kinetics, adsorption, desorption

中图分类号:

O 614.8

张雨, 花榕, 寇晓康, 刘付平, 孔杰, 张峰, 何非凡, 冯宇. 氨基改性苯乙烯树脂的合成及其对铼的吸附[J]. 化工学报, 2020, 71(5): 2109-2117.

Yu ZHANG, Rong HUA, Xiaokang KOU, Fuping LIU, Jie KONG, Feng ZHANG, Feifan HE, Yu FENG. Preparation of amino modified styrene-divinylbenzene resin and its adsorption of rhenium[J]. CIESC Journal, 2020, 71(5): 2109-2117.

图/表 15

图1 聚合反应

Fig.1 Polymerization

图2 氯甲基化反应

Fig.2 Chloromethylation reaction

图3 功能化反应

Fig.3 Functionalization reaction

图4 LSC-Re树脂吸附铼前后的红外光谱图

Fig.4 FT-IR spectra of LSC-Re resin before and after rhenium adsorption

图5 LSC-Re树脂吸附铼前后的SEM图

Fig.5 SEM images of LSC-Re resin before and after rhenium adsorption

图6 LSC-Re树脂吸附前(a)、后(b)的EDS谱图

Fig.6 EDS spectra of LSC-Re resin before(a) and after(b) rhenium adsorption

图7 溶液pH与吸附量的关系曲线

Fig. 7 Relationship between solution pH and adsorption capacityC0(Re)=100 mg·L-1, V=20 ml; m(resin)=0.02 g; t=5 h; T=298 K

表1 LSC-Re树脂在不同pH下铼、铀的分配系数及铼铀分离系数

Table 1 Distribution coefficient and separation coefficient of Re(Ⅶ) and U(Ⅵ) at different pH of LSC-Re resin

pH	D_Re×10²	D_U×10²	β_Re/U
1.5±0.1	20.21	0.48	41.68
2.0±0.1	33.56	1.22	27.62
2.5±0.1	20.02	1.79	11.17
3.0±0.1	15.95	1.35	1.82
3.5±0.1	21.71	2.23	9.74
4.0±0.1	16.9	0.91	18.61
5.0±0.1	16.6	2.83	5.86
6.0±0.1	19.11	2.41	7.93

图8 DU、DRe、βRe/U与pH的关系曲线

Fig. 8 Relationship between DU、DRe、βRe/U and pHC0(Re)=100 mg·L-1, C0(U)=100 mg·L-1, V=20 ml; m(resin)=0.02 g; t=5 h; T=298 K

图9 吸附时间与吸附量的关系曲线

Fig. 9 Relationship between adsorption time and adsorption capacityC0(Re)=100 mg·L-1, pH=2.0, V=20 ml; m(resin)=0.02 g; T=298 K

图10 准一级、准二级动力学曲线

Fig.10 Quasi-first-order, quasi-second-order dynamic curves

图11 溶液浓度与吸附量的关系曲线

Fig. 11 Relationship between solution concentration and adsorption capacityC0(Re)= 10~500 mg·L-1, pH=2.0, V=20 ml; m(resin)=0.02 g; t=6 h,T=298 K

图12 Langmuir、Freundlich吸附等温曲线

Fig.12 Langmuir, Freundlich adsorption isotherm curve

图13 温度与吸附量的关系曲线(a)及热力学拟合曲线(b)

Fig.13 Relationship between temperature and adsorption capacity (a) and thermodynamic fitting curve (b)C0(Re)=100 mg·L-1, pH=2.0, V=20 ml; m(resin)=0.02 g; t=6 h

图14 动态吸附—解吸曲线

Fig.14 Dynamic adsorption-desorption curve

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氨基改性苯乙烯树脂的合成及其对铼的吸附

Preparation of amino modified styrene-divinylbenzene resin and its adsorption of rhenium

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