Cu-BTC@GO复合材料的机械化学合成与成型及其吸附性能研究

发布时间：2018-08-15 19:45

【摘要】：烷烃、烯烃、芳香烃、有机醇类是油气的重要组分,这些气体的挥发不仅会造成经济损失,还会对生态环境和人类的身体健康造成严重危害。因此对油气的回收利用迫在眉睫。近年来,MOFs材料以其超高的比表面积和孔容、骨架结构多样化以及易官能化等特点,在VOCs的吸附分离领域得到广泛应用。本文主要研究Cu-BTC@GO复合材料的机械化学法合成与成型并测定材料的水稳定性和VOCs的吸附性能,论文的工作涉及Cu-BTC@GO复合材料的机械化学法制备和表征,材料的水稳定性测试,甲醇、乙烯、乙烷、丙烯、丙烷、C5、C6和C7正构烷烃、甲苯和苯十种VOCs组分的吸附性能研究,造粒成型和原位生长法制备Cu-BTC和Cu-BTC@GO复合材料成型体并测定材料对甲醇和苯的吸附等温线,本文的研究内容属于环境科学、化学工程和材料成型领域,具有重要的研究价值和工业应用背景。本文研究了合成条件包括球磨参数和纯化试剂对Cu-BTC@GO复合材料的比表面积和孔隙结构的影响。研究表明:球磨珠数量为3颗,球磨时间为60 min,球磨转速为1100 r/min,活化试剂为乙醇时,可合成大比表面积和高孔容的Cu-BTC@GO复合材料,其BET比表面积最高可达1362.0 m2/g,总孔容为0.8536 cm3/g,微孔孔容为0.4397 cm3/g。本文研究了氧化石墨烯复合对Cu-BTC@GO复合材料水稳定性的影响。研究表明:Cu-BTC在水中浸泡5 h后,材料的XRD特征峰的强度明显减弱,BET比表面积下降65%,中孔结构几乎完全消失,微孔孔容减少62%,晶体表面出现很多细小的棒状结构。浸泡10 h后,材料的BET比表面积和孔容几乎完全消失,晶体表面出现大量棒状结构。Cu-BTC@GO复合材料在水中浸泡10 h后BET比表面积仍在1000 m2/g以上,微孔孔容在0.4 cm3/g以上,Cu-BTC@GO复合材料的水稳定性大大高于Cu-BTC。本文研究了Cu-BTC@GO对十种VOCs组分的吸附性能。研究表明:Cu-BTC@GO对这些VOCs组分具有很高的吸附性能,吸附量均大于本文和水热法制备的Cu-BTC的吸附量,远高于传统吸附剂如分子筛、沸石等的吸附量;Cu-BTC@GO对丙烯和乙烯的吸附选择性分别达到4.5和5.46,对C2~C3烷烃烯烃混合气体具有很好的分离效果。本文研究了造粒成型和原位生长法制备Cu-BTC和Cu-BTC@GO成型体,并测定了甲醇和苯的吸附等温线。研究表明:Cu-BTC@GO粒料的BET比表面积最高可达1059.2 m2/g,与成型前的粉末材料相比仅下降2.8%,保留了完整的MOFs粉末的晶体结构和热稳定性能,Cu-BTC@GO粒料对甲醇和苯的饱和吸附量分别为7.27 mmol/g和6.23 mmol/g,相比Cu-BTC@GO粉料,饱和吸附量分别下降12%和26.7%;Cu-BTC粒料对甲醇和苯的饱和吸附量分别为4.85 mmol/g和2.47 mmol/g,相比Cu-BTC粉料,饱和吸附量分别下降70%和58.8%,Cu-BTC@GO粒料对甲醇和苯均有良好的吸附性能。通过原位生长法可将Cu-BTC浸渍在堇青石表面,得到Cu-BTC@堇青石成型体,从SEM上可以看到堇青石表面生长了许多Cu-BTC晶体。
[Abstract]:Alkanes, olefins, aromatic hydrocarbons and organic alcohols are important components of oil and gas. The volatilization of these gases will not only cause economic losses, but also cause serious harm to the ecological environment and human health. Therefore, the recovery and utilization of oil and gas is imminent. In recent years, MOFs have been widely used in the field of adsorption and separation of VOCs due to their high specific surface area and pore volume, diverse skeleton structure and easy functionalization. In this paper, the synthesis and molding of Cu-BTC@GO composites by mechanochemical method and the determination of their water stability and the adsorption properties of VOCs were studied. Study on adsorption properties of ten VOCs components of ethylene, ethane, propylene, propane C _ 5N _ 6 and C _ 7 n-alkanes, toluene and benzene, granulation and in-situ growth method to prepare Cu-BTC and Cu-BTC@GO composite molds and determine the adsorption isotherms of methanol and benzene. The research content of this paper belongs to the field of environmental science, chemical engineering and material forming, which has important research value and industrial application background. The effects of synthesis conditions including ball milling parameters and purification reagents on the specific surface area and pore structure of Cu-BTC@GO composites were studied. The results showed that the Cu-BTC@GO composites with large specific surface area and high pore volume could be synthesized when the number of ball balls was 3, the milling time was 60 minutes, the rotational speed of ball milling was 1100 r / min, and the activation reagent was ethanol. The highest specific surface area of BET is 1362.0 m2 / g, the total pore volume is 0.8536 cm 3 / g, and the micropore volume is 0.4397 cm 3 / g. The effect of graphene oxide composite on the water stability of Cu-BTC@GO composites was studied in this paper. The results show that the specific surface area of XRD decreases by 65%, the mesoporous structure almost disappears, the micropore volume decreases 62%, and many fine rod-like structures appear on the crystal surface after being immersed in water for 5 h. After immersion for 10 h, the BET specific surface area and pore volume of the composites almost disappeared, and a large number of rod-like structure. Cu-BTCCGO composites were immersed in water for 10 hours. The specific surface area of BET was still over 1000 m2 / g. The water stability of Cu-BTCCgo composites with micropore volume above 0.4 cm3/g is much higher than that of Cu-BTC-based composites. In this paper, the adsorption properties of ten VOCs components by Cu-BTC@GO have been studied. The results showed that the adsorptive capacity of VOCs components was higher than that of Cu-BTC prepared by hydrothermal method and higher than that of traditional adsorbents such as molecular sieve, and the adsorption capacity of Cu-BTC was much higher than that of Cu-BTC prepared by hydrothermal method, and the adsorption capacity of these components was much higher than that of traditional adsorbents such as molecular sieve. The adsorption selectivity of Cu-BTCgo on propylene and ethylene reached 4.5 and 5.46 respectively, which showed good separation effect on C2~C3 alkenes. In this paper, Cu-BTC and Cu-BTC@GO molds were prepared by granulation and in situ growth, and the adsorption isotherms of methanol and benzene were determined. The results show that the BET specific surface area of the w / Cu-BTCCgo particles can reach 1059.2 m2 / g, which is only 2.8m / g lower than that of the powder materials before molding. The crystal structure and thermal stability of the whole MOFs powder are preserved. The saturated adsorption of methanol and benzene by Cu-BTCCgo particles are respectively. 7.27 mmol/g and 6.23 mmol / g, compared to Cu-BTC@GO powder, The saturated adsorption capacity of Cu-BTC particles for methanol and benzene was 4.85 mmol/g and 2.47 mmol / g, respectively. Compared with Cu-BTC powder, the saturated adsorption capacity of Cu-BTC particles decreased by 70% and 58.8% respectively. Cu-BTC can be impregnated on cordierite surface by in situ growth method, and Cu-BTC @ cordierite forming body can be obtained. A lot of Cu-BTC crystals can be seen on the surface of cordierite from SEM.
【学位授予单位】：华南理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O647.3;TB33

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