聚乙烯亚胺/苎麻纤维自撑膜对铀酰离子的去除性能

张爽; 唐勇; 安再旭; 陈茜茜; 那兵; 柳和生; 柳玉辉

doi:10.13801/j.cnki.fhclxb.20240204.001

聚乙烯亚胺/苎麻纤维自撑膜对铀酰离子的去除性能

张爽¹,
唐勇²,
安再旭²,
陈茜茜²,
那兵^{1, 2, ,},
柳和生⁴,
柳玉辉^3, ,

1.
东华理工大学　核资源与环境国家重点实验室，南昌 330013
2.
东华理工大学　化学与材料学院，南昌 330013
3.
东华理工大学　核科学与工程学院，南昌 330013
4.
华东交通大学　机电与车辆工程学院，南昌 330013

基金项目: 国家基金委青年科学基金项目(22006013)；国家基金委地区科学基金项目(22266003)；江西省主要学科学术和技术带头人青年人才项目(20225BCJ23020)；中国铀业有限公司-东华理工大学核资源与环境国家重点实验室联合创新基金项目(2023NRE-LH-18)

详细信息

通讯作者:
那兵，博士，教授，硕士生导师，研究方向为环境与能源高分子材料　E-mail: bna@ecut.edu.cn

柳玉辉，博士，副教授，硕士生导师，研究方向为核化学与放射化学、核燃料循环与材料　E-mail: liuyuhui@ecut.edu.cn

中图分类号: X703.1；TB332
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出版历程
- 收稿日期: 2023-12-04
- 修回日期: 2024-01-08
- 录用日期: 2024-01-19
- 网络出版日期: 2024-02-05
- 发布日期: 2024-02-05
- 刊出日期: 2024-11-14

Research on the uranium ion removal performance of polyethyleneimine/ramie fiber self-supporting membranes

ZHANG Shuang¹,
TANG Yong²,
AN Zaixu²,
CHEN Xixi²,
NA Bing^{1, 2, ,},
LIU Hesheng⁴,
LIU Yuhui^3, ,

1.
State Key Laboratory of Nuclear Resources and Environment, East China University of Technology, Nanchang 330013, China
2.
School of Chemistry and Materials Science, East China University of Technology, Nanchang 330013, China
3.
School of Nuclear Science and Engineering, East China University of Technology, Nanchang 330013, China
4.
School of Mechanical and Vehicle Engineering, East China Jiaotong University, Nanchang 330013, China

Funds: National Foundation Committee Youth Science Fund Project (22006013); Regional Science Fund Project of National Foundation Committee (22266003); Jiangxi Provincial Innovation and Entrepreneurship Training Program for College Students (20225BCJ23020); China Uranium Corporation Limited-East China University of Technology State Key Laboratory of Nuclear Resources and Environment Joint Innovation Fund Project (2023NRE-LH-18)

摘要

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( ${\rm{UO}}_2^{2 + }$ )的去除。研究了 ${\rm{UO}}_2^{2 + }$ 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，PEI/RAM吸附剂表现出对铀酰离子较好的选择性，对 ${\rm{UO}}_2^{2 + }$ (20 mg/L)的吸附能力将近其他金属离子(20 mg/L)的70倍。
- 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 PEI onto ramie fiber after treatment with low eutic solvent (DES) (choline chloride-oxalic acid system), and was used to remove uranyl ion ( ${\rm{UO}}_2^{2 + }$ ) in aqueous solution. The effects of initial concentration of ${\rm{UO}}_2^{2 + }$ , 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 poly-ethylenimide/ramie fiber self-supported film (PEI/RAM) adsorbent showed good selectivity for uranyl ions, and its adsorption capacity for ${\rm{UO}}_2^{2 + }$ (20 mg/L) was nearly 70 times that of other metal ions (20 mg/L).
- polyethylenimide (PEI) /
- ramie fiber /
- adsorb /
- uranium /
- deep eutectic solvent (DES)

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图 1 (a)聚乙烯亚胺/苎麻纤维自撑膜(PEI/RAM)流程示意图；接枝不同PEI浓度的SEM图像：(b) 0vol%PEI；(c) 5vol%PEI；(d) 10vol%PEI；(e) 15vol%PEI；15vol%PEI/RAM的EDS图谱(f)、XRD图谱(g)、XPS全谱(h)、FTIR图谱(i)

DES—Deep eutectic solvent

Figure 1. (a) Polythylenimide/ramie fiber self-supporting film (PEI/RAM) process diagram; SEM images of ramie fibers incorporated with varying PEI concentrations: (b) 0vol%PEI; (c) 5vol%PEI; (d) 10vol%PEI; (e) 15vol%PEI; EDS patterns (f), XRD patterns (g), XPS survey spectra (h), FTIR spectra (i) for 15vol%PEI/RAM

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图 2 (a) PEI浓度与铀吸附容量的关系；(b) pH与铀吸附容量的关系

C₀—Initial uranyl ion concentration

Figure 2. (a) Relationship between PEI content and uranium adsorption capacity; (b) Relationship between pH and uranium adsorption capacity

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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 fitting result chart (b), Freundlich model fitting result chart (c)

q_e—Euilibrium adsorption capacity; C_e—Balance uranium ion concentration; R²−Fitting constant

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图 4 PEI/RAM的吸附动力学(a)、准一级拟合(b)和准二级拟合(c)

Figure 4. Adsorption kinetics (a), pseudo-first-order model (b) and pseudo-second-order model (c) of PEI/RAM

q_t—Adsorption capacity at equilibrium at time t of adsorption

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图 5 PEI/RAM的温度对吸附的影响(a)、lnK_d与1/T的关系(b)、解吸和再生循环图(c)

K_d—Distribution coefficient; T—Kelvin temperature

Figure 5. Uranium uptake capacity versus temperature (a), relationship between lnK_d and 1/T (b), desorption and regeneration cycles (c) of PEI/RAM

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图 6 PEI/RAM铀吸附后的EDS图(a)、吸附前后FTIR图谱(b)及吸附后的XPS全谱图((c), (d))

Figure 6. EDS mapping (a), FTIR spectra (b), XPS survey spectra ((c), (d)) of ramie fibers grafted with PEI/RAM before and after uranium adsorption

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图 7 (a) UO₂ ²⁺在干扰金属离子中的分布系数；(b)金属离子对铀吸附能力的影响

Figure 7. (a) Distribution coefficient of uranyl ions in interfering metal ions; (b) Influence of metal ions on uranium adsorption capacity

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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
Material	K_L/(L·mg⁻¹)	q_m/(mg·g⁻¹)	R²	N	K_F/(mg^1−1/n·g⁻¹·L^−1/n )	R²
Ramie fibers grafted with PEI	7.966×10⁻²	613	0.9905	2.251	94.343	0.9747
Notes: q_m—Constants for adsorption capacity of Langmuir model; K_L—Constants for affinity of Langmuir model; K_F—Constant of Freundlich model; N—Favorability factor of the adsorption; R²—Fitting constant.

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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
Material	q_1,cal/(mg·g⁻¹)	k₁/(min⁻¹)	R²	q_2,cal/(mg·g⁻¹)	k₂/(mg·g⁻¹·min⁻¹)	R²
Ramie fibers grafted with PEI	278.281	0.262	0.9827	347	9.78×10^-3	0.9934
Notes: q_1,cal—Calculated equilibrium adsorption capacity; k₁—Rate constants of pseudo-first-order model; k₂—Rate constants of pseudo-second-order model; q_2,cal—Calculated equilibrium adsorption capacity of pseudo-second-order kinetic model.

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参考文献(23)

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长摘要

目的
为了应对日益严重的能源危机和较为严重的环境污染问题，如何处理含铀废水的问题已经成为当务之急。为高效便捷的处理含铀废水，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/苎麻纤维膜(PEI/RAM),并将其运用于水溶液中铀酰离子(UO)的去除。
方法
利用低共熔溶剂的手段，将苎麻纤维成直径更小的纤维并引入羧基，使其纤维化。利用简单的水热接枝法，使聚乙烯亚胺接枝到苎麻纤维上，并制成聚乙烯亚胺/苎麻纤维膜。采用现代表征技术SEM-EDS、XRD、XPS及FTIR对改性前后的材料进行表征分析，探究改性前后材料的微观结构变化。通过批量静态实验探究温度、pH、时间、PEI含量、干扰离子及不同初始铀酰离子(UO)浓度等影响因素对吸附剂去除铀酰离子的影响。通过连续的吸附/脱附实验探究材料的再生和再利用能力。根据表征结构和吸附实验结果探究吸附剂对铀酰离子的机理。
结果
(1)通过SEM-EDS、XPS、XRD及FTIR等表征结果表明在没有破坏原来苎麻纤维的结构的情况下，接枝了聚乙烯亚胺的材料表现出更强的N-H基团结合能，形成了酰胺键(O=C-NH)，表明DES-苎麻纤维的羧基与PEI的氨基发生了缩合，成功将聚乙烯亚胺(PEI)接枝到苎麻纤维上。此外，PEI中大量的氨基与铀酰离子具有较强结合能，能够有效的吸附铀酰离子。(2)批量静态吸附实验表明，当铀酰离子初始浓度为20mg/L、溶液pH为6、饱和吸附时间16h、温度为15℃时，铀酰离子吸附平衡容量达到302mg·g，对铀酰离子具有很好的吸附效果。吸附动力学和等温线分析表明，吸附过程符合准二级动力学模型，表明化学吸附占主导作用，吸附等温线符合Langmuir模型，说明这意味着PEI接枝苎麻纤维膜的吸附行为更接近单分子层吸附机制。(3)采用2 mol·L HNO水溶液对PEI接枝苎麻纤维膜上吸附的铀酰离子进行解吸操作，第一次脱附的效果非常显著，脱附率高达89.8%。在随后的再吸附过程中，吸附容量达到273 mol·g，与初始吸附容量(302 mg·g)相比只有轻微的下降。值得注意的是，即使经过三次的脱附与吸附循环，该膜的吸附容量依然可以保持在114 mg·g的水平。这些数据明确地展示了PEI接枝苎麻纤维膜具有出色的再生和再利用性能。
结论
苎麻纤维有相互连接的粘性成分覆盖在生苎麻上，需将其去除以提取分离的纤维，利用低共熔溶剂手段有效的将苎麻纤维进行分离，并不破坏其结构。所合成的聚乙烯亚胺/苎麻纤维膜(PEI/RAM)，具有显著的铀酰离子吸附性能，在含有Na、Mg、Ca、K等潜在干扰金属离子的环境中仍对铀酰离子具有很好的选择性，并具有很好的循环再生性能。

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聚乙烯亚胺/苎麻纤维自撑膜对铀酰离子的去除性能

通讯作者: 那兵，博士，教授，硕士生导师，研究方向为环境与能源高分子材料 E-mail: bna@ecut.edu.cn 柳玉辉，博士，副教授，硕士生导师，研究方向为核化学与放射化学、核燃料循环与材料 E-mail: liuyuhui@ecut.edu.cn

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Research on the uranium ion removal performance of polyethyleneimine/ramie fiber self-supporting membranes

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出版历程

目录

通讯作者:
那兵，博士，教授，硕士生导师，研究方向为环境与能源高分子材料　E-mail: bna@ecut.edu.cn

柳玉辉，博士，副教授，硕士生导师，研究方向为核化学与放射化学、核燃料循环与材料　E-mail: liuyuhui@ecut.edu.cn