本文選題：金屬-有機(jī)骨架材料 + 氣體分離膜��； 參考：《北京化工大學(xué)》2016年博士論文

【摘要】：金屬-有機(jī)骨架材料(Metal-Organic Frameworks, MOFs)是由金屬離子和有機(jī)配體通過(guò)自組裝過(guò)程形成的納米多孔材料。MOF材料有諸多優(yōu)點(diǎn),如密度小、比表面積高、不飽和金屬位點(diǎn)和孔尺寸可調(diào)節(jié)性等,目前已經(jīng)應(yīng)用在氣體儲(chǔ)存、分離、催化、吸附等領(lǐng)域。近幾年,MOF材料的其中一個(gè)應(yīng)用—?dú)怏w膜分離,吸引了大批實(shí)驗(yàn)和理論研究學(xué)者。膜分離技術(shù),是工業(yè)生產(chǎn)中從各種尾氣里捕獲二氧化碳的有效方法之一,它低能耗、工藝簡(jiǎn)單、無(wú)相變。在膜分離領(lǐng)域里,新型的膜材料研發(fā)成為了首要的問(wèn)題。本文采用不同的方法制備了 MOF膜材料及其復(fù)合膜材料,并應(yīng)用到氣體分離領(lǐng)域,通過(guò)掃描電子顯微鏡分析、X射線衍射分析、熱重分析、紅外分析等方法,對(duì)合成的膜材料進(jìn)行了表征,進(jìn)而考察其對(duì)透過(guò)氣體的分離性能。主要研究?jī)?nèi)容如下:1、采用常規(guī)原位生長(zhǎng)法合成ZIF-9膜,并研究了偶聯(lián)劑用量、金屬鹽與配體的物料比、反應(yīng)溫度、反應(yīng)時(shí)間等條件對(duì)ZIF-9膜的生長(zhǎng)和氣體分離性能的影響,進(jìn)而得到了最佳合成條件為:偶聯(lián)劑用量為偶聯(lián)劑溶液體積分?jǐn)?shù)的2%,金屬鹽與配體的摩爾比為1:2,反應(yīng)溫度為110℃,反應(yīng)時(shí)間為72小時(shí)。2、本文提出變溫法合成ZIF-9膜的策略,采用掃描電子顯微鏡分析、X射線粉末衍射分析、氣體分離性能測(cè)試等方法,對(duì)變溫法合成的膜與原位生長(zhǎng)法合成的膜進(jìn)行比較。結(jié)果表明,采用變溫法合成的ZIF-9膜,不論在膜的生長(zhǎng)方面,還是在氣體分離性能方面,都要優(yōu)于原位生長(zhǎng)法。這種變溫法的優(yōu)勢(shì)在于:它將MOF膜合成過(guò)程的成核和生長(zhǎng)階段分開,達(dá)到了低溫成核、高溫生長(zhǎng)的目的,實(shí)驗(yàn)的低溫階段選用80℃、高溫階段選用130℃。目前來(lái)看,變溫法在MOF膜合成領(lǐng)域的使用尚屬首次。3、采用層層沉積熱處理的方法,將離子液體(ILs)功能化后的碳納米管(CNTs),附著在已合成的ZIF-9膜的表面,同時(shí),在ZIF-9膜的缺陷處,也填充了離子液體功能化后的碳納米管,合成了CNT@IL/ZIF-9復(fù)合膜。測(cè)試結(jié)果表明,此三元體系膜的氣體分離性能效果要比純ZIF-9膜和IL/ZIF-9、CNT/ZIF-9等二元體系膜更具優(yōu)勢(shì)。此外,還考察了在不同的操作溫度和壓力下,通過(guò)此三元體系復(fù)合膜的氣體分離性能的變化,得出了最佳操作條件。其穩(wěn)定性、可重復(fù)性、良好的氣體分離效果為膜分離領(lǐng)域開辟了新思路。4、成功制備了金屬-有機(jī)骨架材料/嵌段聚醚酰胺(ZIF-8/PEBAX-1074)的混合基質(zhì)膜。實(shí)驗(yàn)探究了添加不同含量的ZIF-8 (0%,5%,10%,15%,20%),并利用流涎法制備混合基質(zhì)膜,在氣體分離性能方面的異同。結(jié)果表明,此混合基質(zhì)膜表現(xiàn)出了很高的CO2/H2、C02/N2、CO2/CH4分離性能。在ZIF-8添加量為15%時(shí),混合基質(zhì)膜表現(xiàn)出最優(yōu)的氣體分離性能。由于嵌段聚醚酰胺是已經(jīng)工業(yè)化和商業(yè)化的聚合物,而ZIF-8的合成成本較低,操作簡(jiǎn)單,兩種材料的復(fù)合對(duì)實(shí)際工業(yè)應(yīng)用具有廣闊的前景。5、本文將兩種MOF材料:MIL-53(A1)和ZIF-9同時(shí)添加到嵌段聚醚酰胺,制備了 ZIF-9/MIL-53(Al)/PEBAX-2533混合基質(zhì)膜材料。通過(guò)氣體分離性能的考察可以看出,此混合基質(zhì)膜對(duì)的二氧化碳有著良好的分離效果。同時(shí),本文還研究了這種膜在氣體分離效果上與ZIF-9/PEBAX-2533 和 MIL-53(Al)/PEBAX-2533 的不同,并且探討了兩種MOF材料添加量不同時(shí),混合基質(zhì)膜的分離效果的變化。該研究為工業(yè)生產(chǎn)中膜分離工藝提供了新思路。
[Abstract]:Metal organic framework material (Metal-Organic Frameworks, MOFs) is a nano porous material.MOF material which is formed by metal ions and organic ligands through self-assembly process. It has many advantages, such as small density, high surface area, unsaturated metal site and pore size, and so on. It has been used in gas storage, separation, catalysis, adsorption and so on. In recent years, one of the applications of MOF material, gas membrane separation, has attracted a large number of experimental and theoretical researchers. Membrane separation technology is one of the effective methods to capture carbon dioxide from all kinds of tail gas in industrial production. It has low energy consumption, simple process and no phase change. In the field of membrane separation, the research and development of new membrane materials has become the first one. In this paper, MOF film materials and their composite membrane materials were prepared by different methods and applied to the field of gas separation. Through scanning electron microscope analysis, X ray diffraction analysis, thermogravimetric analysis, infrared analysis and other methods, the synthetic membrane materials were characterized, and the separation properties of the permeable gases were investigated. The contents are as follows: 1, the ZIF-9 film is synthesized by the conventional in situ growth method. The effects of the amount of coupling agent, the material ratio of the metal salt and the ligand, the reaction temperature and the reaction time on the growth of the ZIF-9 film and the gas separation properties are studied. The optimum synthesis conditions are obtained: the amount of the coupling agent is 2% of the volume fraction of the coupling agent and the metal salt. The molar ratio of the ligand is 1:2, the reaction temperature is 110 C and the reaction time is 72 hours.2. This paper puts forward the strategy of synthesizing ZIF-9 film by the variable temperature method. The methods of scanning electron microscope analysis, X ray powder diffraction analysis and gas separation performance test are used to compare the films synthesized by the variable temperature method and in situ growth method. The results show that the method is used. The ZIF-9 films synthesized by the method of temperature change are better than in situ growth in both the growth of the membrane and the gas separation performance. The advantage of this method is that it separates the nucleation and growth stages of the MOF membrane synthesis process, reaching the target of low temperature nucleation and high temperature growth, the low temperature stage of the experiment is 80 C, and the high temperature stage is selected to choose 1. At present, at present, the use of temperature changing method in the field of MOF film synthesis is still the first.3. By layer deposition heat treatment, the functionalized carbon nanotube (CNTs) after the ionic liquid (ILs) is attached to the surface of the synthesized ZIF-9 film. At the same time, the carbon nanotubes are filled with the functionalized ionic liquids at the defects of the ZIF-9 film, and the CNT@ has been synthesized. The test results show that the gas separation performance of the three element system film is more advantageous than the pure ZIF-9 film and the two element system membrane such as IL/ZIF-9, CNT/ZIF-9 and so on. In addition, the optimum operating conditions are obtained by the change of gas separation performance through the three element composite membrane under different operating temperatures and pressures. The stability, repeatability, and good gas separation effect opened a new idea for the membrane separation field.4. The mixed matrix membrane of metal organic framework material / block polyether amide (ZIF-8/PEBAX-1074) was successfully prepared. The experiment was carried out to investigate the addition of different content of ZIF-8 (0%, 5%, 10%, 15%, 20%), and the mixed matrix membrane was prepared by the salivation method. The results show that the mixed matrix film shows a high separation performance of CO2/H2, C02/N2 and CO2/CH4. When the amount of ZIF-8 is 15%, the mixed matrix film shows the best gas separation performance. As the block polyether amide is a commercialized and commercialized polymer, the synthesis cost of ZIF-8 is low and the operation is simple. The combination of the two materials has a broad prospect for practical industrial applications. In this paper, two kinds of MOF materials, MIL-53 (A1) and ZIF-9 are added to the block polyether amides, and the ZIF-9/MIL-53 (Al) /PEBAX-2533 mixed matrix material is prepared. Through the investigation of gas separation performance, it can be seen that this mixed matrix has good carbon dioxide for the carbon dioxide. At the same time, this paper also studied the difference between ZIF-9/PEBAX-2533 and MIL-53 (Al) /PEBAX-2533 in the gas separation effect, and discussed the change of the separation effect of the mixed matrix membrane of the two kinds of MOF materials, which provided a new idea for the membrane separation process in the industrial production.
【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】：2016
【分類號(hào)】：TQ051.893

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本文編號(hào)：1992027