Research on the Uranium ion Removal Performance of Polyethyleneimine/Ramie Fiber Self-Supporting Membranes
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摘要: 为应对日益严重的能源和环境污染问题，含铀废水的处理已成为当务之急。为了高效便捷地处理含铀废水，通过低共熔溶剂(DES，氯化胆碱-草酸体系)处理苎麻纤维后接枝聚乙烯亚胺(PEI)制备聚乙烯亚胺/苎麻纤维自撑膜(PEI/RAM)，并将其用于水溶液中铀酰离子(UO22+)的去除。研究了UO22+初始浓度、溶液pH值、吸附时间、温度等条件对吸附剂性能的影响。当铀酰离子初始浓度为20 mg/L、溶液pH为6时，铀酰离子吸附平衡容量达到302 mg·g−1；PEI/RAM的铀吸附过程更接近Langmuir模型和准二级动力学模型。在干扰金属离子(Ca2+、K+、Mg2+、Na+)存在时，聚乙烯亚胺/苎麻纤维自撑膜(PEI/RAM)吸附剂表现出对铀酰离子较好的选择性，对UO22+(20 mg/L)的吸附能力将近其他金属离子(20 mg/L)的70倍。
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关键词:
- 聚乙烯亚胺(PEI) /
- 苎麻纤维 /
- 吸附 /
- 铀 /
- 低共熔溶剂(DES)
Abstract: In order to deal with the increasingly serious energy and environmental pollution problems, the treatment of uranium containing wastewater has become an urgent matter. In order to treat uranium containing wastewater efficiently and conveniently, polyethylenimide/ramie fiber self-sustaining membrane (PEI/RAM) was prepared by grafting polyethylimide (PEI) onto ramie fiber after treatment with low eutic solvent (DES, choline chloride-oxalic acid system), and was used to remove uranyl ion (UO22+) in aqueous solution. The effects of initial concentration of UO22+, pH value of solution, adsorption time and temperature on the properties of the adsorbent were studied. When the initial concentration of uranyl ion is 20 mg/L and the solution pH is 6, the adsorption equilibrium capacity of uranium reaches 302 mg·g−1. The uranium adsorption process of PEI/RAM is closer to Langmuir model and quasi-second-order kinetic model. In the presence of interfering metal ions (Ca2+, K+, Mg2+, Na+), the polyethylenimide/Ramie fiber self-supported film (PEI/RAM) adsorbent showed good selectivity for uranyl ions, and its adsorption capacity for UO22+ (20 mg/L) was nearly 70 times that of other metal ions (20 mg/L).-
Key words:
- polyethylenimide(PEI) /
- ramie fiber /
- adsorb /
- uranium /
- deep eutectic solvent(DES)
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图 1 聚乙烯亚胺/苎麻纤维自撑膜(PEI/RAM)流程示意图(a)，接枝不同PEI浓度的SEM图像: 0% (b)、5% (c)、10% (d)、15% (e)， 15% PEI/RAM的EDS图(f)、XRD图(g)、XPS全谱(h)、FTIR光谱(i)
Figure 1. Polythylenimide/Ramie fiber self-supporting film (PEI/RAM) process diagram (a); SEM visuals of ramie fibers incorporated with varying PEI concentrations: 0% (b), 5% (c), 10% (d), 15% (e), EDS spatial distribution for 15% PEI/RAM (f), XRD spectral analysis of PEI-infused ramie fibers (g), Comprehensive XPS survey spectra (h), FTIR spectral representations (i)
图 2 PEI浓度图(a)，pH与铀吸附容量的关系图(b)
Figure 2. PEI content (a), Relationship between pH and uranium adsorption capacity (b)
图 3 PEI/RAM吸附等温线(a)，Langmuir模型拟合结果图(b)，Freundlich模型拟合结果图(c)
Figure 3. PEI/RAM Adsorption isotherm (a), Langmuir model (b), Freundlich isotherm (c)
qe-Euilibrium adsorption capacity；Ce- Balance uranium ion concentration
图 4 PEI/RAM吸附动力学(a)、准一级拟合(b)、和准二级拟合(c)
Figure 4. PEI/RAM Adsorption kinetics (a),Pseudo-first-order model and (b),Pseudo-second-order model (c)
qt- Adsorption capacity at equilibrium at time t of adsorption
图 5 PEI/RAM温度对吸附的影响图(a)，lnKd与1/T的关系(b)，解吸和再生循环图(c)
Figure 5. PEI/RAM Uranium uptake capacity versus temperature (a), Relationship between lnKd 1/T (b), desorption and regeneration cycles (c)
图 6 PEI/RAM铀吸附后的EDS图(a)、吸附前后FTIR光谱图(b)、吸附后的XPS全谱图(c)和(d)
Figure 6. EDS mapping with PEI/RAM (a), FTIR spectra PEI/RAM (b), XPS survey spectra of ramie fibers grafted with PEI/RAM after uranium adsorption (c) and (d)
图 7 UO22+和干扰金属离子的分布系数(a)，有无金属离子对铀吸附能力的影响(b)
Figure 7. Distribution coefficient among uranyl and interfering metal ions (a), uranium uptake capacity with and without metal ions(b)
表 1 Langmuir模型和Freundlich模型的拟合参数
Table 1. Fitting parameters of Langmuir model and Freundlich model.
Material Langmuir isotherm Freundlich isotherm KL/(L·mg−1) qm /(mg·g−1) R2 N KF/(mg1−1/n·g−1·L−1/n ) R2 Ramie fibers
grafted with PEI7.966×10-2 613 0.9905 2.251 94.343 0.9747 Notes: qm–Constants for adsorption capacity of Langmuir model; kL–Constants for affinity of Langmuir model; kF−Constant of Freundlich model; N−Favorability factor of the adsorption; R2−Fittingconstant 
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表 2 准一级模型和准二级模型的拟合参数
Table 2. Kinetic parameters of pseudo-first-order and pseudo-second-order models
Material Pseudo-first-order model Pseudo-second-order model q1,cal/(mg·g−1) k1/(min−1) R2 q2,cal/(mg·g−1) k2/(mg·g−1·min−1) R2 Ramie fibers
grafted with PEI278.281 0.262 0.9827 347 9.78×10-3 0.9934 Notes: qm–Constants for adsorption capacity of Langmuir model; kL–Constants for affinity of Langmuir model; kF−Constant of Freundlich model; N−Favorability factor of the adsorption; R2−Fittingconstant
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