Comprehensive analysis on anomalous phenomenon of ethanol-soluble poly(vinyl butyral) membrane for ethanol recovery via pervaporation

Poly(vinyl butyral) (PVB) is selected as a promising ethanol-permselective membrane based on the solubility parameter theory; however, it exhibits anomalous water perm-selectivity in practical pervaporation (PV) process. Comprehensive analysis based on experimental and theoretical methods were carried out to explore the inherent mechanism of the anomalous performance. Firstly, sum frequency generation vibrational spectra and contact angle were developed to quantify the surface reconstruction of membrane in air and ethanol, which indicated that hydrophilic hydroxyl tended to expose on membrane surface with ethanol thus improving the membrane affinity to water. Meanwhile, swelling behaviors proved more water would accumulate in the ethanol swollen membrane. Furthermore, theoretical analysis in terms of sorption and diffusion process, based on the UNIFAC-FV model and Fujita free-volume theory, confirmed the mechanism of anomalous phenomenon of PVB membrane. The comprehensive investigation was expected to provide insights into the basic separation mechanism of PV process.     

来瓦希尔骨架材料MIL-53(Al)填充PEBA膜渗透汽化分离水中苯胺

将来瓦希尔骨架材料MIL-53(Al)引入到聚醚共聚酰胺（PEBA-2533）高分子相中制备了不同填充量的PEBA/MIL-53(Al)杂化膜并用于渗透汽化分离水中微量苯胺。X-射线衍射结果证实MIL-53(Al)被成功合成。扫描电镜和激光粒度分析结果表明所制备MIL-53(Al)颗粒粒径在纳米尺度范围内。采用扫描电镜、红外光谱、X-射线衍射、差示扫描量热和水接触角对杂化膜进行了表征，并考察了杂化膜的溶胀行为和分离性能。结果表明，所得杂化膜的热稳定性较好。当MIL-53(Al)质量分数小于20%时，MIL-53(Al)在高分子相中分散均匀，继续增大填充量出现团聚现象。杂化膜的结晶度随MIL-53(Al)填充量的增加而降低。MIL-53(Al)的引入增强了杂化膜的疏水性和溶胀度。在料液温度为60℃、膜下游压力400Pa、料液苯胺质量分数为3.6%时，MIL-53(Al)质量分数为20%的杂化膜（M-20）综合分离性能最优，渗透通量达到2.15kg/(m²·h)，分离因子为264。12天的稳定性测试结果表明所得杂化膜分离性能无显著变化，能够满足渗透汽化应用要求。     

PDMS复合膜回收酯化反应废水中的异丁醇

乙酸与异丁醇酯化反应生产乙酸异丁酯，产生大量含异丁醇的废水，常规生化处理负荷重，浪费资源。采用PDMS复合膜分离回收酯化废水中的异丁醇，考察了异丁醇浓度对PDMS复合膜溶胀度及分离性能的影响，优化渗透汽化过程操作参数，研究了乙酸异丁酯对PDMS复合膜回收异丁醇效果的影响。结果表明，随着异丁醇浓度从1%增大到3%(质量)，PDMS复合膜溶胀度先增大后趋于平稳，异丁醇的渗透通量呈增大趋势，分离因子保持在15左右；操作温度从30℃升至60℃时，渗透通量增大，异丁醇的分离因子下降，总表观活化能为33.87 kJ/mol；流速增加，Reynolds数增大，异丁醇渗透通量变化不大，但分离因子略有增大；微量乙酸异丁酯的存在可促进渗透汽化膜回收异丁醇。采用PDMS复合膜分离酯化废水中的异丁醇，回收率大于94.0%，渗余液中异丁醇浓度可降至0.1%(质量)左右。研究结果可为PDMS复合膜处理低浓度有机溶剂废水提供依据。     

渗透汽化膜分离技术在石化企业中的应用

渗透汽化膜分离技术适合应用于有机溶剂中水的脱除、废水处理与溶剂回收等。。文中根据渗透汽化膜分离的技术特点,对其在石油化工领域的应用进行了分析,该技术能够降低生产过程中的能耗,设备投资费用少,且经济环保。     

ZSM-5沸石膜用于生物油的脱水分离及其再生过程研究

在水热条件下通过无模板剂法合成了连续的ZSM-5沸石膜，并将其用于生物油的渗透汽化以进行高效脱水分离。ZSM-5沸石膜在强酸性、多组分的生物油体系中保持了很好的化学稳定性和优异的分离选择性，但在分离过程中面临着较强的膜污染问题，导致了膜通量的大幅下降。ZSM-5沸石膜的再生研究表明，膜的渗透通量随着再生温度的升高而逐渐提高。当再生温度为220℃时，ZSM-5沸石膜的渗透通量可以恢复至初始的88%。再生的机理研究表明，ZSM-5沸石膜中大量的晶内孔在生物油体系中极易被污染，从而导致渗透通量迅速下降；而相对较大的晶间孔却难以被完全堵塞，水分子在被污染的ZSM-5沸石膜中主要通过晶间孔进行渗透。上述结果表明，通过合理调控ZSM-5沸石膜的晶间孔的数量和尺寸大小可有效提升ZSM-5沸石膜在生物油中的渗透汽化脱水分离性能。     

High-performance molecular-separation ceramic membranes derived from oxidative cross-linked polytitanocarbosilane

Polytitanocarbosilane (TiPCS)-derived ceramic membranes were fabricated using a pre-ceramic polymer. Special attention was focused on a process of thermal-oxidative curing that was used to induce cross-linking and the effect of this process on the ceramic yield, thermal stability, oxidation resistance, and microstructure of TiPCS. The cross-linked TiPCS powders showed a ceramic yield and thermal stability that were higher than that from the non-cross-linked version. In addition, the cross-linked TiPCS with uniform micropores showed higher levels of N₂ and CO₂ adsorption capacity, BET surface area, and micropore volume than the non-cross-linked versions, and the cross-linking process enhanced the stability of the pore structure at high temperature. The cross-linked TiPCS membranes showed high H₂ permeance (1.49 × 10⁻⁶ mol/(m² s Pa)) with sub-nanopores (H₂/SF₆ selectivity: 12 000, H₂/N₂: 10), and in addition higher oxidation resistance than their non-cross-linked counterparts. Furthermore, the influence of the concentration of the TiPCS precursor coating solution was optimized and the hydrothermal stability of the membranes at high temperatures was also evaluated. The optimized membrane demonstrated great performance for the pervaporation removal of methanol in binary azeotropic systems of either MeOH/butyl acetate or MeOH/toluene, and it also showed high hydrothermal stability with excellent dehumidification performance under high temperatures.     

APTES改性ZIF-L/PEBA混合基质膜强化渗透汽化分离苯酚研究

渗透汽化(PV)膜分离是一种高效节能、无污染的化工分离技术,在有机废水处理领域的应用潜力巨大。以3-氨丙基三乙氧基硅烷(APTES)改性二维ZIF-L(AZLs),将其引入聚醚嵌段酰胺(PEBA)内制备AZLs/PEBA混合基质膜,用于分离水溶液中的苯酚。系统表征了所制膜的微结构与物化特性,考察了APTES添加量、AZLs填充量、操作温度、料液浓度等对膜分离性能的影响。结果表明：AZLs均匀分散在PEBA基质中,表明两者具有良好的界面相容性。AZLs的加入使得膜疏水性增强而表面自由能降低,从而提高了PEBA膜的选择性。当分离80℃、1000 mg/kg苯酚水溶液时,AZLs/PEBA膜总通量可达2046 g/(m²·h),分离因子为25.4,并且具有一定的稳定性。所制AZLs/PEBA混合基质膜在含酚废水处理方面具有应用前景。     

渗透汽化-隔壁塔精馏耦合初步分离费托合成水的过程研究

费托合成水中含有醇、酮、酸等多种高附加值含氧有机物可提取出来作为高附加值产品,但由于费托合成水处量大,共沸体系复杂,通常需要首先对其进行初步分离。设计了直接两塔精馏、渗透汽化-两塔精馏、直接隔壁塔精馏、渗透汽化-隔壁塔精馏四种可供选择的初步分离工艺。根据渗透汽化实验数据在Aspen Plus中构建渗透汽化过程模型并进行模拟,结合灵敏度分析得到精馏过程的最佳工艺参数和模拟结果,并对四种工艺的能耗和有效能损失进行对比。结果表明,渗透汽化-隔壁塔精馏工艺具有明显的节能优势,其能耗较直接两塔精馏可降低15.85%,有效能损失降低45.74%。经渗透汽化膜预浓缩后,溶液的浓度可进入隔壁塔的适宜分离浓度区间,以充分发挥隔壁塔优势。由于渗透汽化所需能量可由余热等低品位热源提供,在余热充足的煤化工领域中可显著降低有效能损失。对于该过程而言,当渗透汽化膜价格低于438元/m²时,渗透汽化-隔壁塔精馏耦合工艺将会表现出较高的经济性。     

膜生物反应器 CCCF 过程中酵母细胞生长特性研究

渗透汽化膜生物反应器CCCF过程乙醇发酵中酵母细胞的生长表现出五个不同的阶段,即：快速生长期、乙醇抑制期、二次生长期、平衡期和衰亡期。采用摇瓶实验对发酵副产物（主要为有机酸和甘油）的抑制行为进行检测,结果表明随着副产物浓度的增加,抑制作用越来越强,细胞生长表现出较长的迟滞期和较低的细胞浓度。当副产物浓度达到膜生物反应器中发酵后期的浓度时,细胞的比生长速率和得率仅分别为0．061和0．024。