金属有机骨架材料Cu-BTC的成型及储甲烷性能研究
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摘要
为探索Cu-BTC材料在天然气吸附存储中的应用,采用滚动成型法对Cu-BTC粉末进行成型,考察了成型前后样品的晶体结构、孔结构和甲烷吸附量,并与活性炭小球进行对比。结果表明,虽然成型后Cu-BTC小球损失了部分比表面积、孔容和23%的甲烷吸附量,但比表面积和总孔容仍高达1 259 m2/g和0. 56 cm~3/g。在298 K、3. 5 MPa下,Cu-BTC小球的甲烷质量吸附量为161 cm~3/g,高于活性炭小球的114 cm~3/g,体积吸附量为110 cm~3/cm~3,可交付使用的甲烷量为145 cm~3/g。
To explore the application prospects of Cu-BTC materials in adsorbing and storing natural gas,Cu-BTC powders are shaped via roll forming method.The crystal structure,pore structure and methane adsorption capacity of the samples before and after shaping are examined and compared with activated carbon spheres.The results show that Cu-BTC pellet after the shaping process losses some specific surface area,some pore volume and 23% of CH4 uptake,however,its specific surface area and total pore volume are still as high as 1,259 m~2·g~(-1) and 0. 56 cm~3·g~(-1),respectively.At 298 K and 3. 5 MPa,the gravimetric CH_4 adsorption amount by Cu-BTC pellets reaches 161 cm~3·g~(-1),which is higher than 114 cm~3·g~(-1) by activated carbon pellets,and its volumetric adsorption amount can reach 110 V/V and the usable CH_4 capacity is 145 cm~3·g~(-1).
To explore the application prospects of Cu-BTC materials in adsorbing and storing natural gas,Cu-BTC powders are shaped via roll forming method.The crystal structure,pore structure and methane adsorption capacity of the samples before and after shaping are examined and compared with activated carbon spheres.The results show that Cu-BTC pellet after the shaping process losses some specific surface area,some pore volume and 23% of CH4 uptake,however,its specific surface area and total pore volume are still as high as 1,259 m~2·g~(-1) and 0. 56 cm~3·g~(-1),respectively.At 298 K and 3. 5 MPa,the gravimetric CH_4 adsorption amount by Cu-BTC pellets reaches 161 cm~3·g~(-1),which is higher than 114 cm~3·g~(-1) by activated carbon pellets,and its volumetric adsorption amount can reach 110 V/V and the usable CH_4 capacity is 145 cm~3·g~(-1).
引文
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[2]王协琴.回收边远油田放空天然气的撬装设计[J]天然气工业,2007,1(2):72-75.
[3]Yaghi O M,Ockwig N W O,Keeffe M,et al.Reticular synthesis and the design of new materials[J]. Nature,2003,423(6941):705-714.
[4]Yang Q Y,Liu D H,Zhong C L,et al.Development of computational methodologies for metal-organic frameworks and their application in gas separations[J].Chem Rev,2013,113(10):8261-8323.
[5]Shen J M,Dailly A,Beckner M.Natural gas sorption evaluation on microporous materials[J].Micro Meso Mater,2016,235:170-177.
[6]Li H,Lin Z D,Zhou X,et al.Ultrafast room temperature synthesis of novel composites Imi@Cu-BTC with improved stability against moisture[J].Chem Eng J,2017,307:537-543.
[7]Tate K L,Li Shiguang,Yu Miao,et al. Zeolite adsorbent-MOF layered nanovalves for CH4storage[J]. Adsorption,2017,23(1):19-24.
[8]Plaza M G,Ribeiro A M,Ferreira A,et al.Propylene/propane separation by vacuum swing adsorption using Cu-BTC spheres[J]. Sep Purif Technol.2012,90(5),109-119.
[9]LüY Q,Tan X Y,Svec F. Preparation and applications of monolithic structures containing metal-organic frameworks[J].J Sep Sci,2017,40(1):1-16.
[10]Hesse M,Müller U,Yaghi O M.shaped bodies containing metal-organic frameworks:Germany:WO,2006/050898 A1[P].2006-05-18.
[11]赵亮,高伟,张瑛,等.成型方式对铜基金属有机骨架材料甲烷吸附性能的影响[J].2017,46(10):1278-1282.
[12]宋佳,王刚,赵亮,等.程序升温处理对HKUST-1吸附甲烷性能的影响[J].石油化工,2015,44(5):586-589.
[13]张英,马蕊英,赵亮,等.金属有机骨架材料HKUST-1的制备及其甲烷吸附性能[J].石油化工,2017,46(7):884-887.
[14]陈进富,娄世松,陆绍信.天然气吸附剂的开发及其储气性能的研究[J].燃料化学学报,1997,27(5):399-402.
[15]Mason J A,Veenstra M,Long J R.Evaluating metal-organic frameworks for natural gas storage[J].Chem Sci,2014,5(1):32-51.