本文選題：納米多孔材料 + MOFs��； 參考：《北京化工大學(xué)》2017年博士論文

【摘要】：氣體分離和水處理是關(guān)系生產(chǎn)和生活的兩個(gè)重要分離方面。高效分離技術(shù)在其中發(fā)揮著重要作用,膜分離技術(shù)因簡(jiǎn)單高效、節(jié)能環(huán)保、易于產(chǎn)業(yè)化等特點(diǎn),具有廣闊的發(fā)展前景。膜材料的開發(fā)是膜分離技術(shù)發(fā)展的核心,其中聚合物膜和無機(jī)膜得到了廣泛的研究。聚合物膜具有優(yōu)異的成膜性能,但是難以得到兼具高的通量和選擇性的膜材料。無機(jī)膜可以兼具高的通量和選擇性,但是生產(chǎn)大面積無缺陷膜比較困難。為此以聚合物為基底,無機(jī)物為添加物制備混合基質(zhì)膜(mixed matrix membranes, MMMs )是結(jié)合兩者優(yōu)勢(shì),彌補(bǔ)不足的有效方法。納米多孔材料如金屬-有機(jī)骨架材料(metal-organic frameworks,MOFs),金屬-有機(jī)多面體(metal-organic polyhedron, MOP)等材料具有多樣的化學(xué)性質(zhì)、結(jié)構(gòu)可調(diào)性等,作為添加物制備MMMs具有獨(dú)特的優(yōu)勢(shì)。本文從MMMs分離應(yīng)用角度出發(fā),在新型納米多孔添加物材料的設(shè)計(jì)、MMMs制備及其性能研究方面做了系統(tǒng)的研究。主要的研究?jī)?nèi)容為:1、采用具有大的孔尺寸、空金屬位、豐富-NH2官能團(tuán)及高穩(wěn)定性的NH2-MIL-101(Cr)作為添加物,自具微孔聚合物(PIM-1)為基底,制備了不同 NH2-MIL-101(Cr)添加量的 NH2-MIL-10I(Cr)/PIM-1 MMMs,研究了NH2-MIL-101(Cr)添加量及其添加時(shí)的干燥狀態(tài)對(duì)膜氣體分離性能影響。在CO2/N2的分離中,NH2-MIL-101(Cr)在低添加量5 wt %時(shí),NH2-MIL-101(Cr)/PIM-1 MMM 的 C02通量較 PIM-1 膜的 C02通量達(dá)到了39.0 %的提高量,同時(shí)C02/N2選擇性也有了一定增加。主要原因是NH2-MIL-101(Cr)大的孔道結(jié)構(gòu)在膜中形成了更多的的氣體通道,從而使膜的氣體通量得到了有效提高,同時(shí)NH2-MIL-101(Cr)自身對(duì)C02的親和作用也有利于CO2通過膜材料,對(duì)分離效果具有積極作用。2、離子液體的結(jié)構(gòu)及化學(xué)性質(zhì)具有多樣性,其中一些功能化的離子液體(task-specific ionic liquid, TSIL)具有優(yōu)異的CO2分離性能,然而離子液體粘度大,易泄露的特點(diǎn)限制了其應(yīng)用范圍。在MOFMMMs的研究中,對(duì)MOFs的改性修飾可以賦予其更多的功能性。本工作中以MOF材料作為TSIL的多孔載體,TSIL作為MOF的功能修飾物,制備了 TSIL在MOF孔道中分布的TSIL與MOF的復(fù)合材料(TSIL@MOF),進(jìn)一步以TSIL@MOF為添加物制備了 MMMs,研究了膜的氣體分離性能。結(jié)果顯示,TSIL@MOF添加量為5 wt%時(shí),MMM的C02通量和C02/N2分離選擇性得到了同時(shí)提高,成功跨越了 Robeson限制。3、對(duì)于MMMs而言,添加物團(tuán)聚沉降一直是阻礙其發(fā)展的關(guān)鍵問題。為此,我們選用了功能化的金屬-有機(jī)多面體作為添加物,聚砜(PSF)為基底,制備了新型混合基質(zhì)膜(MOP/PSFMMMs)。MOP可以和PSF—樣溶于制膜溶劑,有效緩解了膜制備過程中的團(tuán)聚沉降問題。同時(shí)功能化的MOP材料可有效增強(qiáng)分離效果,在對(duì)C02/CH4混合氣的分離中,當(dāng)MOP添加量為12 wt %時(shí),膜的C02通量和CO2/CH4分離因子得到了同時(shí)提高,與純PSF的分離性能相比其提高量分別為81 %和60 %。4、UiO-66(Zr)具有良好的親水性,孔尺寸為6.0A,可有效進(jìn)行染料廢水的分離,同時(shí)具有優(yōu)異的穩(wěn)定性。工作中以UiO-66作為添加物制備了不同UiO-66添加量的膜材料(UiO-66/PES MMMs),并進(jìn)行了全面的膜水處理性能測(cè)試。在UiO-66添加量為1.0wt%時(shí),UiO-66/PES膜水通量較PES膜水通量提高了 60 %,同時(shí)膜的染料截留率及膜抗污染性能也得到了提升。5、氧化石墨烯(GO)具有良好的親水及化學(xué)性質(zhì),作為添加物制備水處理膜具有巨大的應(yīng)用價(jià)值。為了使GO性能得到最大限度的發(fā)揮,同時(shí)賦予其更多的功能性,本工作中將UiO-66負(fù)載至GO層間制備了具有多孔分子篩性質(zhì)的UiO-66與GO復(fù)合材料(UiO-66@GO),并以UiO-66@GO為添加物制備了一系列不同添加物添加量的混合基質(zhì)膜(UiO-66@GO/PES MMMs),系統(tǒng)研究了膜的水處理性能。結(jié)果表明,在UiO-66@GO添加量為3.0 wt %時(shí),UiO-66@GO/PES膜的水通量較PES和GO/PES膜的水通量分別提高了 351 %和78 %,同時(shí)具有良好的染料截留性能和膜抗污染性能,性能均優(yōu)于相應(yīng)的PES和GO/PES膜性能。
[Abstract]:Gas separation and water treatment are two important separation aspects of production and life. High efficiency separation technology plays an important role. Membrane separation technology has a broad development prospect because of its simple efficiency, energy saving and environmental protection, easy industrialization and so on. The development of membrane materials is the core of membrane separation technology, in which polymer membrane and no Film has been widely studied. Polymer films have excellent film forming properties, but it is difficult to obtain high flux and selective membrane materials. Inorganic membranes can have high flux and selectivity. However, it is difficult to produce large area without defect films. Polymer as the substrate and inorganic additives are used to prepare the mixed matrix film (mixe D matrix membranes, MMMs) is an effective method to combine the two advantages. The nano porous material, such as metal organic skeleton material (metal-organic frameworks, MOFs), metal organic polyhedron (metal-organic polyhedron, MOP), has a variety of chemical properties, structure tunability, etc. as additive, MMMs has a unique method. Special advantages. From the point of view of MMMs separation application, this paper makes a systematic study on the design of new nano porous additive materials, MMMs preparation and its properties. The main research contents are as follows: 1, using large pore size, empty metal position, rich -NH2 functional group and high stability NH2-MIL-101 (Cr) as additives. NH2-MIL-10I (Cr) /PIM-1 MMMs with different amounts of NH2-MIL-101 (Cr) added to the pore polymer (PIM-1) was prepared. The effect of NH2-MIL-101 (Cr) addition and the drying state on the performance of the membrane gas separation was studied. The flux of NH2-MIL-101 (Cr) at a low addition of 5% in the separation of CO2/N2 was compared. The C02 flux of PIM-1 film reached 39%, and the selectivity of C02/N2 also increased. The main reason was that the large pore structure of NH2-MIL-101 (Cr) formed more gas channels in the membrane, so that the gas flux of the membrane was improved effectively, and the affinity of NH2-MIL-101 (Cr) to C02 was also beneficial to CO2 through. The membrane material has a positive effect on the separation effect.2, the structure and chemical properties of ionic liquids have diversity, and some of the functional ionic liquids (task-specific ionic liquid, TSIL) have excellent CO2 separation properties. However, the ionic liquid viscosity is large and the leaking characteristics limit its application range. In the study of MOFMMMs, it is necessary The modified modification of MOFs can give it more functional properties. In this work, MOF is used as a porous carrier of TSIL and TSIL as a functional modifier of MOF. The TSIL and MOF (TSIL@MOF) of TSIL in the MOF channel is prepared. The MMMs is prepared by TSIL@MOF additive. The gas separation performance of the membrane is studied. The results show that the gas separation performance of the membrane is obvious. When the amount of TSIL@MOF is 5 wt%, the C02 flux and C02/N2 separation selectivity of MMM have been improved simultaneously, and the Robeson restriction.3 has been successfully crossed. For MMMs, the accumulation of additive agglomeration has been a key problem that hinders its development. Therefore, we have chosen the functionalized metal organic polyhedron as the additive and polysulfone (PSF) as the base, A new mixed matrix film (MOP/PSFMMMs).MOP can be used to solve the aggregation problem in the process of membrane preparation, which can effectively alleviate the agglomeration of the membrane in the preparation process. Meanwhile, the functionalized MOP material can effectively enhance the separation effect. In the separation of C02/CH4 mixture, the C02 flux and CO2/CH4 separation factor of the membrane are obtained when the addition of MOP is 12 wt%. At the same time, compared with the separation performance of pure PSF, the improvement amount is 81% and 60%.4 respectively. UiO-66 (Zr) has good hydrophilic property and the pore size is 6.0A. It can effectively separate the dye wastewater and have excellent stability. In the work, the membrane materials with different UiO-66 additions (UiO-66/PES MMMs) are prepared with UiO-66 as additives. When the amount of UiO-66 was 1.0wt%, the water flux of UiO-66/PES membrane was increased by 60% than that of PES membrane. Meanwhile, the dye interception and membrane fouling performance of the membrane were increased by.5, and graphene oxide (GO) had good hydrophilic and chemical properties. As an additive, the water treatment membrane was huge. In order to maximize the performance of the GO and give it more functionality, the UiO-66 and GO composites (UiO-66@GO) with the properties of porous molecular sieve (UiO-66@GO) were prepared from the GO layer to the GO layer, and a series of mixed matrix membranes (U) with different additives were prepared with UiO-66@GO as additives. IO-66@GO/PES MMMs), the water treatment performance of the membrane was studied systematically. The results showed that the water flux of UiO-66@GO/PES film increased by 351% and 78% than that of PES and GO/PES film when the amount of UiO-66@GO was 3 wt%, and the performance of the membrane was better than that of the corresponding PES and GO/PES membrane.

【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ051.893

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 童敏曼;趙旭東;解麗婷;劉大歡;陽慶元;仲崇立;;金屬-有機(jī)骨架材料用于廢水處理[J];化學(xué)進(jìn)展;2012年09期

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本文編號(hào)：1789253