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聚碳硅烷诱导的复合陶瓷膜的制备及其油水分离研究

作者：张迪，贾海琦，朱家明，张昭乾，李星，刘怀珠，廖明佳，龚耿浩

单位： 1. 天津工业大学材料科学与工程学院，先进分离膜材料全国重点实验室，天津 300387； 2. 重庆化工职业学院化学工程学院，重庆 401228； 3. 冀东油田唐山冀油瑞丰化工有限公司，唐山 063500

关键词：陶瓷膜；聚碳硅烷；油水分离；相转化/烧结

DOI号： 10.16159/j.cnki.issn1007-8924.2025.05.003

分类号： TQ028.8

出版年,卷(期):页码： 2025,45(5):19-32

摘要：

针对传统陶瓷膜制备工艺复杂、能耗高、分离性能受限等关键问题，本研究提出一种基于聚碳硅烷（PCS）衍生陶瓷与相转化/烧结工艺协同优化的复合陶瓷膜制备策略。以聚砜（PSf）为聚合物基质，氧化铝（Al2O3）为基体材料，PCS为陶瓷前驱体，通过优化N-甲基吡咯烷酮/四氢呋喃（NMP/THF）混合溶剂体系，构建铸膜液。在1 450 ℃烧结过程中，PCS热解生成的二氧化硅（SiO2）与Al2O3原位反应形成莫来石（3Al2O3·2SiO2）晶相，该晶相显著改善了膜材料的微观结构和力学性能。本研究系统探究了溶剂配比及凝固浴组成对膜性能的影响。研究表明，在不同凝固浴条件下制备的复合陶瓷膜具有以下显著优势：具有多孔结构特征；高孔隙率（52%~73%）,优异的抗压强度（18.5~38.2 MPa）以及孔径可调控（90~320 nm）；在处理1 000 mg/L油水乳液时，展现出卓越的分离性能[渗透率13 240~20 540 L/(m2·h·MPa），除油率98.1%~99.4%]；具有突出的抗污染性能，经简易化学清洗即可实现90%的通量恢复率。相较于传统纯Al2O3膜，最优条件下制备的PCS-Al2O3复合陶瓷膜在孔隙率提升54%的同时，抗压强度并未发生明显衰减，其力学性能与纯Al2O3膜相当，成功突破了传统陶瓷膜“高孔隙率与高强度难以兼得”的技术瓶颈。

To address the critical challenges of complex fabrication processes, high energy consumption, and limited separation performance in conventional ceramic membranes, this study proposed a novel composite ceramic membrane fabrication strategy based on synergistic optimization of polycarbosilane (PCS)-derived ceramics and phase inversion/sintering processes. Using polysulfone (PSf) as the polymer matrix, alumina (Al2O3) as the base material, and PCS as the ceramic precursor, a casting solution by optimizing the N-methyl-pyrrolidone/tetrahydrofuran (NMP/THF) mixed solvent system was developed. During sintering at 1 450 ℃, the silica (SiO2) generated from PCS pyrolysis reacts in situ with Al2O3 to form mullite (3Al2O3·2SiO2) crystals, which significantly enhanced the microstructure and mechanical properties of the membrane material. This study systematically investigated the effects of solvent composition and coagulation bath conditions on membrane performance. The results demonstrated that the composite ceramic membranes prepared under various coagulation bath conditions exhibited the following outstanding advantages: porous structure characteristics with high porosity (52%~73%) and excellent compressive strength (18.5~38.2 MPa), along with tunable pore sizes (90~320 nm);exceptional separation performance for 1 000 mg/L oil-in-water emulsions [permeance: 13 240~20 540 L/(m2·h·MPa）,oil rejection: 98.1%~99.4%]; and remarkable antifouling properties, achieving 90% flux recovery through simple chemical cleaning. Compared to pure Al2O3 membrane, the PCS-Al2O3 composite ceramic membrane fabricated under optimized conditions exhibited a 54% increase in porosity while its compressive strength did not significantly degrade, maintaining mechanical performance comparable to that of pure Al2O3 membranes, successfully overcoming the technical challenge in conventional ceramic membranes of balancing high porosity with high mechanical strength.

基金项目：

重庆市教委科学技术研究计划项目（KJQN202404521）；长寿区科技计划项目（CSKJ2024010）

作者简介：

张迪（1998-），男，山东威海人，硕士研究生，研究方向为油水分离陶瓷膜

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