自具微孔聚合物磁性混合基質(zhì)膜的制備及其氧氮滲透性能研究
發(fā)布時間：2018-07-29 20:02
【摘要】：氧氣和氮?dú)鈴V泛應(yīng)用于能源、醫(yī)療、食品保鮮等工業(yè)領(lǐng)域。工業(yè)上常采用深冷精餾或變壓吸附分離技術(shù)來獲得氧氮?dú)怏w。與這兩種技術(shù)相比,氣體膜分離技術(shù)具有節(jié)能、環(huán)保等諸多優(yōu)點(diǎn)。近年來,磁性混合基質(zhì)膜因具有獨(dú)特的氧氮分離機(jī)制受到了人們的廣泛關(guān)注。磁性混合基質(zhì)膜是由磁性基元嵌入聚合物中形成的非均相體系。它利用氧氮分子的磁性質(zhì)差異以及磁性基元/聚合物界面間隙的篩分作用,能夠?qū)崿F(xiàn)對氧氮分離過程的強(qiáng)化,因而磁性混合基質(zhì)膜具有良好的應(yīng)用前景。本文分別以四氧化三鐵(Fe_3O_4)、聚多巴胺修飾四氧化三鐵(Fe_3O_4@PDA)和有機(jī)金屬骨架化合物包覆四氧化三鐵(Fe_3O_4@ZIF-8)三種粒子為磁性基元,以自具微孔聚合物(PIM-1)為聚合物基體,采用溶劑揮發(fā)法制備了PIM-1/Fe_3O_4、PIM-1/Fe_3O_4@PDA和PIM-1/Fe_3O_4@ZIF-8三種磁性混合基質(zhì)膜,系統(tǒng)研究了磁性基元的添加量、尺寸、表面修飾層結(jié)構(gòu)以及外加磁場強(qiáng)度等因素對磁性混合基質(zhì)膜的理化結(jié)構(gòu)及其氧氮滲透性能的影響。全文的研究內(nèi)容及結(jié)論如下:(1)以溶劑揮發(fā)法制備了PIM-1/Fe_3O_4和PIM-1/Fe_3O_4@PDA磁性混合基質(zhì)膜。從PIM-1/Fe_3O_4和PIM-1/Fe_3O_4@PDA磁性混合基質(zhì)膜的氧氮滲透性差異可以看出,致密聚多巴胺層的引入能有效改善磁性基元/聚合物界面缺陷,同時增強(qiáng)磁性混合基質(zhì)膜的機(jī)械性能,但導(dǎo)致了磁性混合基質(zhì)膜的氧氮滲透性能的下降。在添加量為2 wt%,外加磁場強(qiáng)度為56 mT時,PIM-1/Fe_3O_4@PDA磁性混合基質(zhì)膜的氣體滲透性能有最大值,此時O2的滲透系數(shù)為616 Barrer,O_2/N_2選擇性為3.48。(2)采用原位生長法合成Fe_3O_4@ZIF-8磁性核殼基元,并將其嵌入PIM-1聚合物中,制備出PIM-1/Fe_3O_4@ZIF-8磁性混合基質(zhì)膜。制備的Fe_3O_4@ZIF-8磁性核殼基元具有微孔結(jié)構(gòu),BET比表面積為552.8 m2/g,SF中值孔徑為0.629 nm。對比PIM-1/Fe_3O_4和PIM-1/Fe_3O_4@ZIF-8磁性混合基質(zhì)膜的氧氮滲透性差異可以看出,Fe_3O_4@ZIF-8磁性核殼基元的多孔ZIF-8層能增加磁性基元/聚合物界面的親和力,同時為O2分子提供高效的滲透通道。當(dāng)Fe_3O_4@ZIF-8磁性核殼基元添加量增加時,PIM-1/Fe_3O_4@ZIF-8磁性混合基質(zhì)膜的機(jī)械性能和氧氮選擇性均呈現(xiàn)先增后減的趨勢,而氣體滲透系數(shù)則不斷增大。在添加量為8 wt%,外加磁場強(qiáng)度為56 mT時,磁性混合基質(zhì)膜的O2滲透系數(shù)達(dá)到967 Barrer,O_2/N_2選擇性達(dá)到3.17,這一結(jié)果接近2008年Robeson上限,表現(xiàn)出優(yōu)良的O_2/N_2滲透性能。(3)將帶有不同F(xiàn)e_3O_4核粒徑和不同ZIF-8殼層厚度的Fe_3O_4@ZIF-8磁性核殼基元嵌入聚合物PIM-1中,制備出粒子核殼結(jié)構(gòu)不同的PIM-1/Fe_3O_4@ZIF-8磁性混合基質(zhì)膜。實(shí)驗(yàn)結(jié)果顯示隨著ZIF-8殼層厚度的增大,磁性混合基質(zhì)膜的機(jī)械性能和氧氮滲透性不斷提高。當(dāng)ZIF-8殼層厚度達(dá)到40 nm,外加磁場強(qiáng)度為56 mT時,磁性混合基質(zhì)膜的O2滲透系數(shù)為831 Barrer,O_2/N_2選擇性為3.78。隨著Fe_3O_4@ZIF-8粒子核粒徑的增加,磁性混合基質(zhì)膜的機(jī)械性能逐漸降低,而氧氮滲透性能逐漸提高。當(dāng)Fe_3O_4@ZIF-8粒子的核粒徑為200 nm,外加磁場強(qiáng)度為56 mT時,磁性混合基質(zhì)膜的O2滲透系數(shù)為744Barrer,O_2/N_2選擇性為3.67。
[Abstract]:Oxygen and nitrogen are widely used in the industrial fields of energy, medical treatment, food preservation and other industrial fields. The technology of cryogenic distillation or pressure swing adsorption separation is often used in industry to obtain oxygen and nitrogen gases. Compared with these two technologies, gas membrane separation technology has many advantages, such as energy saving and environmental protection. In recent years, magnetic mixed matrix membrane has a unique mechanism of oxygen and nitrogen separation. The magnetic mixed matrix film is an heterogeneous system formed by the magnetic matrix element embedded in the polymer. It can be used to strengthen the process of the separation of oxygen and nitrogen by using the difference of magnetic properties of oxygen and nitrogen molecules and the screening effect of the interface gap between the magnetic radical and polymer. Therefore, the magnetic mixed matrix film has good application. In this paper, three particles of iron oxide modified iron oxide (Fe_3O_4), polydopamine modified iron oxide (Fe_3O_4@PDA) and organometallic skeleton compounds coated with iron oxide (Fe_3O_4@ZIF-8) were used as the magnetic radicals, and PIM-1/Fe_3O_4, PIM-1/Fe_3O_4@PDA was prepared by solvent evaporation method with the microporous polymer (PIM-1) as the polymer matrix. And PIM-1/Fe_3O_4@ZIF-8 three kinds of magnetic mixed matrix films, the effects of the addition amount, size, surface modification layer structure and magnetic field strength on the physical and chemical structure and oxygen and nitrogen permeability of the magnetic mixed matrix film are systematically studied. The contents and conclusions of the full text are as follows: (1) PIM-1/Fe is prepared by solvent evaporation method. _3O_4 and PIM-1/Fe_3O_4@PDA magnetic mixed matrix films can be seen from the difference of oxygen and nitrogen permeability between PIM-1/Fe_3O_4 and PIM-1/Fe_3O_4@PDA magnetic mixed matrix. The introduction of dense polydopamine can effectively improve the interfacial defects of magnetic element / polymer and enhance the mechanical properties of magnetic mixed matrix, but it leads to magnetic mixture. The permeability of oxygen and nitrogen in the plasma membrane is decreased. When the addition amount is 2 wt% and the external magnetic field intensity is 56 mT, the gas permeability of the PIM-1/Fe_3O_4@PDA magnetic mixed matrix film has the maximum value. The permeability coefficient of the O2 is 616 Barrer, and the O_2/N_2 selectivity is 3.48. (2) using in situ growth method to synthesize the Fe_3O_4@ZIF-8 magnetic core shell primitives and embed them in P. In the IM-1 polymer, PIM-1/Fe_3O_4@ZIF-8 magnetic mixed matrix is prepared. The Fe_3O_4@ZIF-8 magnetic core element has microporous structure, the specific surface area of BET is 552.8 m2/g, the median pore size of SF is 0.629 nm. and the difference of oxygen and nitrogen permeability of PIM-1/Fe_3O_4 and PIM-1/Fe_3O_4@ZIF-8 magnetic mixed matrix can be seen, Fe_3O_4@ZIF-8 magnetic properties can be seen. The porous ZIF-8 layer of the nuclear shell element can increase the affinity of the magnetic element / polymer interface and provide an efficient permeable channel for the O2 molecules. When the addition of the Fe_3O_4@ZIF-8 magnetic core element is increased, the mechanical properties and the oxygen and nitrogen selectivity of the PIM-1/Fe_3O_4@ZIF-8 magnetic mixed matrix film all increase first and then decrease, and the gas permeation system is used. When the addition amount is 8 wt% and the external magnetic field strength is 56 mT, the O2 permeability coefficient of the magnetic mixed matrix is 967 Barrer and the O_2/N_2 selectivity reaches 3.17. This result is close to the upper limit of Robeson in 2008 and shows excellent O_2/N_2 permeability. (3) there will be Fe_3O_4 with different Fe_3O_4 kernel diameter and different ZIF-8 shell thickness. The @ZIF-8 magnetic core shell element is embedded in the polymer PIM-1, and the PIM-1/Fe_3O_4@ZIF-8 magnetic mixed matrix film with different core shell structure is prepared. The experimental results show that the mechanical properties and oxygen nitrogen permeability of the magnetic mixed matrix film are increasing with the increase of the thickness of the ZIF-8 shell. When the thickness of the ZIF-8 shell reaches 40 nm, the external magnetic field strength is 56. At mT, the O2 permeability coefficient of the magnetic mixed matrix is 831 Barrer, and the selectivity of O_2/N_2 is 3.78. with the increase of the particle size of Fe_3O_4@ZIF-8 particles, the mechanical properties of the magnetic mixed matrix gradually decrease and the oxygen nitrogen permeation performance gradually increases. When the particle size of the Fe_3O_4@ZIF-8 particles is 200 nm and the external magnetic field strength is 56 mT, the magnetic Mixture Base The O2 permeability coefficient of plasma membrane is 744Barrer and O_2/N_2 selectivity is 3.67.
【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ051.893
本文編號：2153839
[Abstract]:Oxygen and nitrogen are widely used in the industrial fields of energy, medical treatment, food preservation and other industrial fields. The technology of cryogenic distillation or pressure swing adsorption separation is often used in industry to obtain oxygen and nitrogen gases. Compared with these two technologies, gas membrane separation technology has many advantages, such as energy saving and environmental protection. In recent years, magnetic mixed matrix membrane has a unique mechanism of oxygen and nitrogen separation. The magnetic mixed matrix film is an heterogeneous system formed by the magnetic matrix element embedded in the polymer. It can be used to strengthen the process of the separation of oxygen and nitrogen by using the difference of magnetic properties of oxygen and nitrogen molecules and the screening effect of the interface gap between the magnetic radical and polymer. Therefore, the magnetic mixed matrix film has good application. In this paper, three particles of iron oxide modified iron oxide (Fe_3O_4), polydopamine modified iron oxide (Fe_3O_4@PDA) and organometallic skeleton compounds coated with iron oxide (Fe_3O_4@ZIF-8) were used as the magnetic radicals, and PIM-1/Fe_3O_4, PIM-1/Fe_3O_4@PDA was prepared by solvent evaporation method with the microporous polymer (PIM-1) as the polymer matrix. And PIM-1/Fe_3O_4@ZIF-8 three kinds of magnetic mixed matrix films, the effects of the addition amount, size, surface modification layer structure and magnetic field strength on the physical and chemical structure and oxygen and nitrogen permeability of the magnetic mixed matrix film are systematically studied. The contents and conclusions of the full text are as follows: (1) PIM-1/Fe is prepared by solvent evaporation method. _3O_4 and PIM-1/Fe_3O_4@PDA magnetic mixed matrix films can be seen from the difference of oxygen and nitrogen permeability between PIM-1/Fe_3O_4 and PIM-1/Fe_3O_4@PDA magnetic mixed matrix. The introduction of dense polydopamine can effectively improve the interfacial defects of magnetic element / polymer and enhance the mechanical properties of magnetic mixed matrix, but it leads to magnetic mixture. The permeability of oxygen and nitrogen in the plasma membrane is decreased. When the addition amount is 2 wt% and the external magnetic field intensity is 56 mT, the gas permeability of the PIM-1/Fe_3O_4@PDA magnetic mixed matrix film has the maximum value. The permeability coefficient of the O2 is 616 Barrer, and the O_2/N_2 selectivity is 3.48. (2) using in situ growth method to synthesize the Fe_3O_4@ZIF-8 magnetic core shell primitives and embed them in P. In the IM-1 polymer, PIM-1/Fe_3O_4@ZIF-8 magnetic mixed matrix is prepared. The Fe_3O_4@ZIF-8 magnetic core element has microporous structure, the specific surface area of BET is 552.8 m2/g, the median pore size of SF is 0.629 nm. and the difference of oxygen and nitrogen permeability of PIM-1/Fe_3O_4 and PIM-1/Fe_3O_4@ZIF-8 magnetic mixed matrix can be seen, Fe_3O_4@ZIF-8 magnetic properties can be seen. The porous ZIF-8 layer of the nuclear shell element can increase the affinity of the magnetic element / polymer interface and provide an efficient permeable channel for the O2 molecules. When the addition of the Fe_3O_4@ZIF-8 magnetic core element is increased, the mechanical properties and the oxygen and nitrogen selectivity of the PIM-1/Fe_3O_4@ZIF-8 magnetic mixed matrix film all increase first and then decrease, and the gas permeation system is used. When the addition amount is 8 wt% and the external magnetic field strength is 56 mT, the O2 permeability coefficient of the magnetic mixed matrix is 967 Barrer and the O_2/N_2 selectivity reaches 3.17. This result is close to the upper limit of Robeson in 2008 and shows excellent O_2/N_2 permeability. (3) there will be Fe_3O_4 with different Fe_3O_4 kernel diameter and different ZIF-8 shell thickness. The @ZIF-8 magnetic core shell element is embedded in the polymer PIM-1, and the PIM-1/Fe_3O_4@ZIF-8 magnetic mixed matrix film with different core shell structure is prepared. The experimental results show that the mechanical properties and oxygen nitrogen permeability of the magnetic mixed matrix film are increasing with the increase of the thickness of the ZIF-8 shell. When the thickness of the ZIF-8 shell reaches 40 nm, the external magnetic field strength is 56. At mT, the O2 permeability coefficient of the magnetic mixed matrix is 831 Barrer, and the selectivity of O_2/N_2 is 3.78. with the increase of the particle size of Fe_3O_4@ZIF-8 particles, the mechanical properties of the magnetic mixed matrix gradually decrease and the oxygen nitrogen permeation performance gradually increases. When the particle size of the Fe_3O_4@ZIF-8 particles is 200 nm and the external magnetic field strength is 56 mT, the magnetic Mixture Base The O2 permeability coefficient of plasma membrane is 744Barrer and O_2/N_2 selectivity is 3.67.
【學(xué)位授予單位】：江南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ051.893
【參考文獻(xiàn)】
相關(guān)期刊論文 前8條
1 王春宇;張晶;張青云;徐炳乾;杜艷;;ZIF-8基多孔碳的制備及吸附性能[J];化工進(jìn)展;2017年01期
2 駱東升;王新靈;;超順磁Fe_3O_4@PDA核-殼結(jié)構(gòu)納米粒子的制備及表征[J];功能高分子學(xué)報(bào);2016年02期
3 周劍;熊云;周賢爵;劉曉;;硅橡膠富氧膜材料研究進(jìn)展[J];化工新型材料;2012年02期
4 丁建芳;姜繼森;;油酸鈉對油相法制備的Fe_3O_4納米粒子的表面改性研究[J];無機(jī)材料學(xué)報(bào);2007年05期
5 楊大令;趙嬋;張守海;高健;蹇錫高;;膜用高乙烯基含量硅橡膠的合成及膜性能研究[J];低溫與特氣;2007年03期
6 沈光林;;膜法富氧在國內(nèi)應(yīng)用新進(jìn)展[J];深冷技術(shù);2006年01期
7 欒吉益,高新運(yùn),蔡漳平,李丙來,邵登山;膜法富氧技術(shù)的應(yīng)用[J];鋼鐵;2005年07期
8 朱硯磬;;物質(zhì)的磁性[J];物理通報(bào);1956年09期
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