Highly permeable acid-stable poly (sulfonamide-urea) nanofiltration membrane for purifying phosphoric acid

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology Pub Date : 2025-01-16 DOI:10.1016/j.seppur.2025.131662

Jiandong Wang, Yuxing Jiang, Zhuangzhuang Tian, Jun Li, Yang Jin, Jianjun Chen, Yubin Wang

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引用次数: 0

Abstract

The traditional wet-process phosphoric acid has higher economic benefits than the thermal-process phosphoric acid, but introduces many metal ion impurities, which limits the application of phosphoric acid. In highly concentrated phosphoric acid solutions, phosphoric acid mainly exists in molecular form. Due to the surface charge and appropriate pore size of the nanofiltration (NF) membrane, it exhibits high selectivity for phosphoric acid and its impurities. However, because of the uncontrolled diffusion of monomers and rapid polymerization, the pore size distribution becomes highly uneven. Meanwhile the extremely low pH and high viscosity of the phosphoric acid compromise the stability and permeance of commercial membranes. We identified that the organic monomer benzene-1,3-disulfonyl chloride (BDSC) exhibits a capping effect when reacting with the aqueous phase of branched polyethyleneimine (PEI) which allows the newly formed membrane to regulate the subsequent diffusion and reaction of hexamethylene diisocyanate (HDI), thereby optimizing the membrane structure. By adjusting the concentration of BDSC, the pore size of the membrane layer was optimized. The final average pore size was determined to be 0.33 nm. The membrane exhibited an average ion rejection of over 65 % when tested in a 20 wt% P₂O₅ solution, while maintaining a very low rejection rate of only 1.74 % for phosphorus. The permeance reached 1.21 L/h m² bar, surpassing that of traditional commercial membrane operating at less than 1 L/h m² bar under 10 wt% P₂O₅ conditions. This study employed the capping effect to adjust the membrane structure and pore size, demonstrating that spatial sieving is the main mechanism for ions purification in phosphoric acid. Long-term acid resistance tests confirmed the stability of the poly (sulfonamide-urea) NF membrane during phosphoric acid purification process. This work shows that this new nanofiltration membrane exhibits promising prospects for application within acidic high-viscosity systems.

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磷酸净化用高渗透性稳酸聚磺胺脲纳滤膜

传统的湿法磷酸比热法磷酸具有更高的经济效益，但会引入许多金属离子杂质，限制了磷酸的应用。在高浓度磷酸溶液中，磷酸主要以分子形式存在。由于纳滤膜的表面电荷和适当的孔径，它对磷酸及其杂质具有很高的选择性。然而，由于单体扩散失控和快速聚合，孔径分布变得极不均匀。同时，磷酸极低的 pH 值和高粘度也影响了商用膜的稳定性和渗透性。我们发现，有机单体苯-1,3-二磺酰氯（BDSC）在与支链聚乙烯亚胺（PEI）的水相反应时会产生封盖效应，使新形成的膜能够调节六亚甲基二异氰酸酯（HDI）的后续扩散和反应，从而优化膜结构。通过调整 BDSC 的浓度，优化了膜层的孔径。最终确定的平均孔径为 0.33 纳米。在 20 wt% 的 P2O5 溶液中进行测试时，膜的平均离子抑制率超过 65%，而对磷的抑制率却很低，仅为 1.74%。渗透率达到 1.21 L/h m2 bar，超过了在 10 wt% P2O5 条件下运行时渗透率低于 1 L/h m2 bar 的传统商业膜。这项研究利用封盖效应调整了膜结构和孔径，证明了空间筛分是磷酸中离子净化的主要机制。长期耐酸试验证实了聚磺酰胺脲 NF 膜在磷酸纯化过程中的稳定性。这项工作表明，这种新型纳滤膜在酸性高粘度系统中的应用前景广阔。

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来源期刊

Separation and Purification Technology 工程技术-工程：化工

CiteScore

14.00

自引率

12.80%

发文量

2347

审稿时长

43 days

期刊介绍： Separation and Purification Technology is a premier journal committed to sharing innovative methods for separation and purification in chemical and environmental engineering, encompassing both homogeneous solutions and heterogeneous mixtures. Our scope includes the separation and/or purification of liquids, vapors, and gases, as well as carbon capture and separation techniques. However, it's important to note that methods solely intended for analytical purposes are not within the scope of the journal. Additionally, disciplines such as soil science, polymer science, and metallurgy fall outside the purview of Separation and Purification Technology. Join us in advancing the field of separation and purification methods for sustainable solutions in chemical and environmental engineering.

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Branched polyethyleneimine