【摘要】：高效碳捕集技術(shù)是實現(xiàn)溫室氣體減排和能源氣體凈化的重要途徑。膜技術(shù)以其能耗低、操作彈性高等優(yōu)勢成為最具發(fā)展前景的CO_2捕集技術(shù)之一。開發(fā)高滲透性、高選擇性、高穩(wěn)定性的CO_2分離膜材料是膜技術(shù)成功應(yīng)用的關(guān)鍵。為此,需深入揭示CO_2在膜內(nèi)的傳遞機制,設(shè)計特異性、高效傳遞的膜結(jié)構(gòu)。本研究以PEO基高分子作為多功能改性劑,采用簡便、溫和的制膜方法制備了一系列具適宜親疏性和自由體積特性的CO_2分離膜,提出針對膜主體、界面、表面、通道結(jié)構(gòu)調(diào)控實現(xiàn)膜溶解機制與擴散機制協(xié)同強化的策略,實現(xiàn)了CO_2/N_2、CO_2/CH_4的高效分離,以期為高性能CO_2分離膜的規(guī)�；苽涮峁├碚摶A(chǔ)與技術(shù)支持。研究結(jié)果如下:膜主體結(jié)構(gòu)調(diào)控與傳遞機制強化:通過在橡膠態(tài)高分子Pebax中引入PEG/CNT或含PEG的硅烷凝膠網(wǎng)絡(luò),制備了有機-無機雜化膜,通過PEG對膜主體親和性的調(diào)控強化了膜的溶解機制,無機粒子的引入干擾了膜主體結(jié)晶行為,強化了膜的擴散機制。同時含有PEGDMA和CNT雜化膜的CO_2滲透系數(shù)達743 Barrer,CO_2/N_2的選擇性達108,突破了2008年的Robeson上界。硅凝膠網(wǎng)絡(luò)的引入顯著提升了膜的機械性能。膜界面結(jié)構(gòu)調(diào)控與傳遞機制強化:提出了以有機PEG微球作為填充劑,引入玻璃態(tài)PI中,改善膜界面形態(tài)、強化膜界面?zhèn)鬟f特性的膜設(shè)計制備方法。高分子-填充劑良好的界面形態(tài)和親CO_2特性使膜溶解、擴散機制同時強化,與純PI膜相比,PI PEGSS(20)膜的CO_2滲透速率提高了35%,CO_2/N_2選擇性提高了104%。膜表面結(jié)構(gòu)調(diào)控與傳遞機制強化:提出了以表面偏析技術(shù)構(gòu)建親CO_2非對稱膜表面的方法。以玻璃態(tài)PES為高分子主體,含PEO的嵌段共聚物F68作為改性劑,膜表面富集的PEO增強了膜表面CO_2親和性,膜主體自由體積特性由PPO的引入實現(xiàn)強化,從而實現(xiàn)了溶解-擴散機制協(xié)同強化。含20 wt%F68的非對稱膜相比純PES膜CO_2滲透通量提高了210%,CO_2/N_2選擇性提高了105%。膜通道結(jié)構(gòu)調(diào)控與傳遞機制強化:使用不同分子量PEGDA作為交聯(lián)劑,綜合PEGDA的CO_2親和性和交聯(lián)特性,制備了GO復合膜。通過膜通道CO_2親和性和膜通道尺寸協(xié)同調(diào)控,實現(xiàn)了溶解-擴散機制協(xié)同強化。GO-PEGDA500相比與純GO膜,CO_2滲透通量提高了284%,CO_2/CH_4選擇性提高了294%。
[Abstract]:High-efficiency carbon capture technology is an important way to realize greenhouse gas emission reduction and energy gas purification. The membrane technology is one of the most promising CO _ 2 trapping technologies because of its low energy consumption and high operating elasticity. The development of CO _ 2 separation membrane material with high permeability, high selectivity and high stability is the key to the successful application of membrane technology. To this end, the transfer mechanism of CO _ 2 in the membrane needs to be further revealed, and the membrane structure with specific and high efficiency is designed. In this study, a series of CO _ 2 separation membranes with suitable hydrophobicity and free-volume characteristics were prepared by using PEO-based polymer as a multifunctional modifier. The effective separation of CO _ 2/ N _ 2 and CO _ 2/ CH _ 4 is realized by the strategy of the channel structure regulation and control to realize the synergistic enhancement of the membrane dissolution mechanism and the diffusion mechanism, so as to provide the theoretical basis and technical support for the large-scale preparation of the high-performance CO _ 2 separation membrane. The results of the study are as follows: the structure regulation and transmission mechanism of the membrane main body is strengthened: the organic-inorganic hybrid membrane is prepared by introducing the PEG/ CNT or the PEG-containing silane gel network in the rubbery polymer Pebax, and the dissolution mechanism of the membrane is strengthened through the regulation and control of the affinity of the membrane main body through the PEG, The introduction of inorganic particles interfere with the crystallization behavior of the film main body and strengthen the diffusion mechanism of the film. At the same time, the permeability coefficient of CO _ 2, which contains the PEGDMA and the CNT hybrid membrane, is as high as 743 Barrer, and the selectivity of CO _ 2/ N _ 2 reaches 108, which breaks through the upper bound of the Robeson in 2008. The introduction of a silicon gel network significantly improves the mechanical properties of the film. The control and transmission mechanism of the membrane interface is enhanced by introducing the organic PEG microsphere as a filler, introducing the glass state PI, improving the interface morphology of the membrane, and enhancing the membrane interface transfer characteristic. 楂樺垎瀛，

本文編號：2448646