湿法纺丝偕胺肟复合纤维的制备及其铀吸附性能研究

Preparation of Wet Spinning Poly(amidoxime) Composite Fibers and Their Uranium Adsorption Properties

  • 摘要: 为获得低成本、高吸附率且可工业化应用的铀吸附材料,本文将聚丙烯腈溶液和偕胺肟聚丙烯腈溶液共混,然后借助湿法纺丝技术批量制备了新型聚丙烯腈-偕胺肟聚丙烯腈(PAN-PAO)复合纤维,并用于水溶液中铀的吸附性能研究。结果表明:PAN-PAO复合纤维在298 K、pH=6.0、m/V= 0.2 g/L条件下,吸附平衡时间为1 200 min,理论最大吸附量达到638.0 mg/g。准二级动力学、粒子内扩散、液膜扩散和Langmuir模型均可以较好地解释该吸附过程。以0.5 mol/L NaHCO3和0.25 mol/L Na2CO3+0.025 mol/L H2O2为洗脱剂,对纤维进行6次吸附-脱附循环后,吸附量均保持在初始值的85%以上,而脱附率保持在90%以上,表现出良好的循环再生能力。同时,PAN-PAO复合纤维在铀加标海水中对铀的吸附率均超过90%,铀钒吸附选择性系数达4.4,具有很高的吸附选择性,表明PAN-PAO复合纤维有望应用于海水提铀。

     

    Abstract: At present, there are numerous materials used for uranium adsorption, in order to obtain adsorption materials with high uranium adsorption performance, excellent regeneration performance, inexpensive production costs and simple preparation methods, the polyacrylonitrile solution was modified with hydroxylamine hydrochloride using dimethyl sulfoxide as a solvent to obtain the amidoxime polyacrylonitrile solution. Then, the polyacrylonitrile solution was mixed with the amidoxime polyacrylonitrile solution in a certain proportion, and the polyacrylonitrile- poly(amidoxime) (PAN-PAO) composite fibers were obtained by wet spinning technology. Finally, it was treated with hot alkali before adsorption. The changes in the chemical structure and surface morphology of the fibers before and after adsorption and desorption were analyzed using various characterization methods such as Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS). The effects of various factors such as pH, adsorption time, temperature, initial uranium concentration and competing ions on the adsorption behavior of U(Ⅵ) were investigated and the process was fitted using kinetics and thermodynamics models. At the same time, different eluents such as acid, alkali, salt and mixture were selected to investigate the recycling and regeneration ability of the fibers. The results show that under the conditions of 25 ℃, pH=6.0 and m/V=0.2 g/L, the adsorption reaches equilibrium for 1 200 min. The actual and theoretical maximum adsorption capacities are 480.3 mg/g and 638.0 mg/g, respectively. The pseudo-second-order kinetics, intra-particle diffusion, liquid film diffusion and Langmuir models can well explain the adsorption process, which is a spontaneous chemical adsorption process controlled by entropy increase. With 0.5 mol/L of NaHCO3 and 0.25 mol/L of Na2CO3+0.025 mol/L of H2O2 as eluents, the desorption equilibrium time is 60 min. At the same time, after 6 adsorption-desorption cycles on the fibers, the adsorption capacity remains above 85% of the initial value, while the desorption rate can still be maintained above 90%. In addition, the eluent volume can be reduced to 40% of the solution volume during adsorption while maintaining the desorption effect. The fibers exhibit excellent uranium adsorption and recycling abilities, making it a promising and efficient engineered adsorption material for the treatment of waste liquids containing uranium. At the same time, the uranium to vanadium adsorption distribution coefficient ratio of the fibers can reach 4.4, and the adsorption rate of uranium in spiked seawater exceeds 90%, indicating high selectivity for uranium and potential application in uranium extraction from seawater.

     

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