本文關(guān)鍵詞： 界面多重作用 超薄膜 復(fù)合膜 雜化膜 溶解-擴(kuò)散機(jī)制 醇水分離　出處：《天津大學(xué)》2015年博士論文　論文類型：學(xué)位論文

【摘要】：高性能膜材料是提高膜技術(shù)競爭力的關(guān)鍵,而膜內(nèi)界面作用調(diào)控是優(yōu)化膜結(jié)構(gòu)、強(qiáng)化膜傳質(zhì)機(jī)制,進(jìn)而獲得高性能膜材料的重要手段。本研究面向燃料乙醇生產(chǎn)這一能源環(huán)境領(lǐng)域的重大問題,以超薄膜制備及其醇水分離性能強(qiáng)化為目標(biāo),提出了針對膜內(nèi)不同類型界面的相互作用調(diào)控方法及通過界面多重作用調(diào)控實現(xiàn)膜傳質(zhì)機(jī)制集成優(yōu)化的策略,采用簡便、溫和的方法制備了一系列具有適宜化學(xué)結(jié)構(gòu)和拓?fù)浣Y(jié)構(gòu)的超薄復(fù)合膜/超薄雜化膜,實現(xiàn)了乙醇/水的高效分離,以期為高性能醇水分離膜的規(guī)�；苽涮峁├碚摶A(chǔ)與技術(shù)支持。主要研究結(jié)果如下:分離層-支撐層界面多重作用調(diào)控:基于仿生粘合法,將多巴胺和聚乙烯亞胺(PEI)共沉積于支撐層表面后涂覆海藻酸鈉制備超薄復(fù)合膜。界面區(qū)大量的靜電引力和氫鍵作用位點使界面親水性提高,膜自由體積特性得到改善,實現(xiàn)溶解機(jī)制與擴(kuò)散機(jī)制的集成優(yōu)化,所制備的復(fù)合膜滲透通量為1196 g/m2h,分離因子為1807,分離因子較支撐層未改性的復(fù)合膜提高29.6倍。分離層-分離層界面多重作用調(diào)控:(1)受茶多酚沉淀蛋白質(zhì)生物現(xiàn)象的啟發(fā),基于蛋白質(zhì)(明膠)和多酚(單寧酸)間的疏水及氫鍵作用,通過層層自組裝過程制備超薄復(fù)合膜。界面多重作用的引入可優(yōu)化膜表面化學(xué)組成及多層膜自由體積特性,實現(xiàn)溶解機(jī)制與擴(kuò)散機(jī)制的集成優(yōu)化,所制備的多層膜滲透通量為1336 g/m2h,分離因子為658。在高水含量下可獲得更高的分離性能,在原料液水含量為30 wt%時,滲透通量可達(dá)2696 g/m2h,透過液中水含量可達(dá)99.43 wt%。(2)選擇結(jié)構(gòu)匹配的明膠和氧化石墨烯作為組裝材料,通過多重作用(靜電引力、氫鍵和疏水作用)驅(qū)動的層層自組裝過程制備超薄雜化膜。通過調(diào)控界面作用強(qiáng)度可優(yōu)化多層膜拓?fù)浣Y(jié)構(gòu),實現(xiàn)擴(kuò)散機(jī)制優(yōu)化,所制備的多層膜相比于純明膠膜可實現(xiàn)滲透通量和分離因子的同時提高。高分子-填充劑界面多重作用調(diào)控:(1)基于自由基聚合方法制備兩性離子接枝改性的氧化石墨烯作為填充劑制備超薄共混雜化膜。兩性離子基團(tuán)的引入可優(yōu)化雜化膜親疏性,界面靜電引力及氫鍵的多重作用可優(yōu)化雜化膜自由體積特性及結(jié)晶度,實現(xiàn)溶解機(jī)制與擴(kuò)散機(jī)制的集成優(yōu)化,所制備的雜化膜相比于純海藻酸鈉膜可實現(xiàn)滲透通量和分離因子的同時提高,滲透通量為2140 g/m2h,分離因子為1370。(2)基于金屬-兒茶酚螯合作用在TiCl4溶膠凝膠過程中加入改性劑同步改性制備超薄原位雜化膜。改性劑的引入可提高界面親水基團(tuán)含量以優(yōu)化雜化膜親疏性,可調(diào)控界面共價鍵及氫鍵作用數(shù)量以優(yōu)化雜化膜自由體積特性及界面結(jié)構(gòu)形態(tài),實現(xiàn)溶解機(jī)制與擴(kuò)散機(jī)制的集成優(yōu)化,所制備的雜化膜滲透通量為1403 g/m2h,分離因子為730。
[Abstract]:High performance membrane material is the key to improve the competitiveness of membrane technology, and the regulation of interfacial action is to optimize the membrane structure and enhance the membrane mass transfer mechanism. In this study, the preparation of ultrathin films and the enhancement of the separation performance of alcohol and water are the main problems in the field of energy environment, especially in the field of fuel ethanol production. In this paper, a method for regulating the interaction between different types of interfaces in the membrane and a strategy for optimizing the mechanism of mass transfer through the regulation of multiple interfacial interactions are put forward, which are simple and convenient. A series of ultrathin composite membranes / ultrathin hybrid membranes with suitable chemical structure and topological structure were prepared by mild method, and the high efficiency separation of ethanol and water was realized. In order to provide theoretical basis and technical support for the large-scale preparation of high performance alcohol-water separation membrane, the main results are as follows: the interface of separation layer and support layer is regulated by multiple interaction: based on bionic bonding method, The ultrathin composite films were prepared by co-deposition of dopamine and polyvinyleneimine (PEI) on the surface of the support layer and then coated with sodium alginate. A large number of electrostatic gravity and hydrogen bond sites in the interface region improved the hydrophilicity of the interface and the free volume characteristics of the membrane. Realize the integration optimization of dissolution mechanism and diffusion mechanism, The permeation flux of the composite membrane was 1196 g / m ~ (2) h, the separation factor was 1807, and the separation factor was 29.6 times higher than that of the unmodified composite membrane. Based on the hydrophobic and hydrogen bond interaction between protein (gelatin) and polyphenol (tannic acid), ultrathin composite films were prepared by layer by layer self-assembly process. The permeation flux of the multilayer membrane was 1336 g / m ~ (2) h, and the separation factor was 658. A higher separation performance could be obtained under the condition of high water content, when the water content of the feedstock liquid was 30 wt%. The permeation flux can reach 2696 g / m ~ 2 h, and the water content in the permeation solution can reach 99.43 wt. t ~ (2).) the structurally matched gelatin and graphene oxide are selected as assembly materials through multiple interactions (electrostatic force, electrostatic force, electrostatic force). The layer by layer self-assembly process driven by hydrogen bond and hydrophobic interaction can be used to prepare ultrathin hybrid films. The topological structure of multilayer films can be optimized and the diffusion mechanism can be optimized by regulating the interfacial interaction strength. The permeation flux and separation factor of the prepared multilayer membrane are higher than that of the pure rubber membrane. Preparation of Amphoteric Ion Graft Modification Oxidation based on Free radical Polymerization. Ultrathin blend hybrid membranes were prepared by using graphene as filler. The introduction of amphoteric groups can optimize the affinity of hybrid membranes. The free volume characteristics and crystallinity of hybrid membranes can be optimized by the interaction of interfacial electrostatic force and hydrogen bond, and the integration of dissolution mechanism and diffusion mechanism can be realized. Compared with the pure sodium alginate membrane, the hybrid membrane can realize the increase of permeation flux and separation factor at the same time. The permeation flux was 2140g / m ~ (2 h) and the separation factor was 1370.2.Based on the metal-catechol chelation process, the ultrathin in-situ hybrid membrane was prepared by simultaneous modification with modifier in the process of TiCl4 sol gel. The introduction of modifier can increase the content of hydrophilic group at the interface. In order to optimize the affinity of hybrid membrane, The amount of interfacial covalent bond and hydrogen bond can be adjusted to optimize the free volume characteristic and interface structure of hybrid membrane, and to realize the integration optimization of dissolution mechanism and diffusion mechanism. The permeation flux of the hybrid membrane is 1403 g / m ~ (2) h and the separation factor is 730 g / m ~ (2) h.
【學(xué)位授予單位】：天津大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TQ051.893
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本文編號：1533316