纳米碳酸钙调控制备的多孔再生纤维素纳滤膜用于离子液体高效回收

Porous regenerated cellulose nanofiltration membrane enabled by nano calcium carbonate modulation for high-efficiency ionic liquid recovery

摘要

【目的】离子液体（ILs）作为纤维素的良溶剂，其高效回收是绿色循环利用的关键。现有纳滤回收技术存在ILs截留率低且膜强度差，不可降解等问题。本研究通过在高强度再生纤维素膜基础上造孔，优化孔隙结构，开发绿色可降解纳滤膜，旨在实现ILs高效回收。【方法】本研究以纤维素为原料、ILs为溶剂，引入纳米碳酸钙（NCC）作为致孔剂，利用溶解再生耦合气体原位发泡技术制备多孔再生纤维素基底膜（PRCMs）。通过调控界面聚合条件，在PRCMs表面构建聚酰胺分离层，制备多孔再生纤维素基纳滤膜（PRC-NFs），进而分析膜材料的孔径、比表面积、化学结构、表面形貌、力学性能、表面电荷特性与ILs回收性能。【结果】（1）NCC添加量可有效调控PRCMs的孔隙结构、力学性能与水通量，当添加量为0.30%时，得到的多孔基底膜PRCM2综合性能最优（拉伸强度52.5 MPa，水通量5.41 L/（m²·h））。（2）在PRCM2表面进行界面聚合，构筑了PRC-NFs。在无水哌嗪（PIP）质量分数为0.5%、1,3,5-均苯三甲酰氯（TMC）质量分数为0.30%、聚合时间为3 min的条件下，PRC-NF6表面呈现出致密均匀的褶皱网状结构、孔径最小（1.65 nm）且表面电负性最强。（3）PRC-NF6对ILs的截留率为49.22%，水通量为4.25 L/（m²·h），优于已报道的未造孔高强度再生纤维素纳滤膜（截留率提高1.88倍）。【结论】本研究采用溶解再生–气体发泡–界面聚合法，成功制备了孔隙结构可控、高ILs截留率的多孔再生纤维素基纳滤膜，实现了ILs绿色高效回收。

Abstract

[Objective] As an effective solvent for cellulose, ionic liquids (ILs) play a crucial role in green recycling through efficient recovery. However, current nanofiltration recovery technologies face challenges such as low ILs retention rates, poor membrane strength, and non-biodegradability. This study focuses on pore formation based on high-strength regenerated cellulose membranes to optimize pore structure and develop green, biodegradable nanofiltration membranes, aiming to achieve efficient ILs recovery. [Method] This study utilized cellulose as the raw material and ILs as the solvent, incorporating nano calcium carbonate (NCC) as a porogen to prepare porous regenerated cellulose substrate membranes (PRCMs) through dissolution-regeneration coupled with gas in-situ foaming technology. By regulating the interface polymerization conditions, a polyamide separation layer was constructed on the surface of PRCMs to prepare porous regenerated cellulose-based nanofiltration membranes (PRC-NFs). The pore size, specific surface area, chemical composition, surface morphology, mechanical properties, surface charge characteristics and ILs recovery performance of the membrane materials were analyzed. [Result] (1) The addition amount of NCC can effectively regulate the pore structure, mechanical properties, and water flux of PRCMs. When the addition amount is 0.30%, the porous basement membrane PRCM2 exhibits optimal comprehensive performance (tensile strength of 52.5 MPa, water flux of 5.41 L/(m²·h)). (2) Interface polymerization was conducted on the surface of PRCM2 to construct PRC-NFs. Under conditions of 0.5% anhydrous piperazine (PIP) by mass fraction, 0.30% trimesoyl chloride (TMC) by mass fraction, and a polymerization time of 3 minutes, the PRC-NF6 surface exhibited a dense and uniform wrinkled network structure with the smallest pore size (1.65 nm) and the strongest surface electronegativity. (3) The retention rate of PRC-NF6 for ILs was 49.22%, with a water flux of 4.25 L/(m²·h), demonstrating superior performance compared to previously reported non-porous high-strength regenerated cellulose nanofiltration membranes (with a rejection rate increase of 1.88-fold). [Conclusion] In this study, a porous regenerated cellulose-based nanofiltration membrane with controllable pore structure and high ILs rejection rate was successfully prepared by dissolution regeneration-gas foaming-interfacial polymerization method, and the green and efficient recovery of ILs was realized.

关键词

绿色可降解纳滤膜 / 多孔再生纤维素 / 纳米碳酸钙致孔 / 气体原位发泡 / 界面聚合 / 孔隙结构调控 / 离子液体回收

Key words

green degradable nanofiltration membrane / porous regenerated cellulose / nano-calcium carbonate pore-forming / in-situ gas foaming / interfacial polymerization / pore structure regulation / ionic liquid recovery

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基金资助

国家重点研发课题(2023YFD2201903)

国家自然科学基金项目(U22A20422)

国家自然科学基金项目(22308027)

北京林业大学“5·5工程”科研创新团队项目(BLRC2023B01)