CH4/C2H6/C3H8在MOF-505@5GO上吸附相平衡和选择性

doi:10.11949/j.issn.0438-1157.20170670

摘要/Abstract

摘要：

应用溶剂热法合成了不同氧化石墨烯（GO）负载量的MOF-505@GO复合材料，分别采用全自动表面积吸附仪、P-XRD、SEM和Raman对材料进行了性能表征，测定了CH₄、C₂H₆和C₃H₈在MOF-505@GO上的吸附等温线，并进行Langmuir-Freundlich方程拟合，依据IAST理论模型计算了C₂H₆/CH₄和C₃H₈/CH₄二元混合气在MOF-505@5GO上的吸附选择性。研究结果表明，随着GO负载量增大，MOF-505@GO复合材料的孔容及BET比表面积先增大后减小，当GO负载量为5%（质量）时，复合材料MOF-505@5GO的孔容及BET比表面积达到最大，当GO负载量进一步增大至8%（质量）和10%（质量）时，复合材料的孔容及BET比表面积逐渐降低。在0.1 MPa和298 K条件下，MOF-505@5GO对CH₄、C₂H₆和C₃H₈的吸附容量分别为0.88、4.81和5.17 mmol·g^-1，相比MOF-505分别提高了14.9%、30.7%和13.1%。MOF-505@5GO对C₂H₆/CH₄和C₃H₈/CH₄的吸附选择性分别为40.1和3056.1，其对C₂H₆/CH₄和C₃H₈/CH₄具有极高的吸附选择性。

关键词: MOF-505@GO, 甲烷, 乙烷, 丙烷, 吸附(作用), 二元混合物

Abstract:

MOF-505@GO composites with different ratios of MOF-505 to graphite oxide were synthesized by solvothermal method. They were characterized by powder X-ray diffractions(PXRD), scanning electron microscopy (SEM), Raman and porosity measurement through nitrogen adsorption. The isotherms of CH₄, C₂H₆ and C₃H₈ on the MOF-505@GO and MOF-505 were measured separately. Results showed that MOF-505@5GO had the largest pore volumes and BET surface area. The pore volumes and BET surface areas of MOF-505@GO increased as the GO content increased, when GO contents increased to 8%(mass) and 10%(mass), the opposite trend was observed in which the pore volumes and BET surface areas decreased. Accordingly, MOF-505@5GO exhibited the highest CH₄, C₂H₆ and C₃H₈ uptake of 0.88, 4.81 and 5.17 mmol·g^-1 at 298 K and 0.1 MPa, having an increase of 14.9%, 30.7% and 13.1%, respectively. Moreover, IAST-predicted C₂H₆/CH₄ selectivity of MOF-505@5GO was about 40.1 and C₃H₈/CH₄ selectivity was about 3056.1. It suggests that MOF-505@5GO is a promising candidate for the separation of C₂H₆/CH₄ and C₃H₈/CH₄.

Key words: MOF-505@GO, methane, ethane, propane, adsorption, binary mixture

中图分类号:

TQ028.1
TB34

吴厚晓, 陈永伟, 梁俊杰, 石仁凤, 夏启斌, 李忠. CH₄/C₂H₆/C₃H₈在MOF-505@5GO上吸附相平衡和选择性[J]. 化工学报, 2018, 69(4): 1500-1507.

WU Houxiao, CHEN Yongwei, LIANG Junjie, SHI Renfeng, XIA Qibin, LI Zhong. Adsorption isotherms and selectivity of CH₄/C₂H₆/C₃H₈ on MOF-505@5GO[J]. CIESC Journal, 2018, 69(4): 1500-1507.

参考文献 37

[1]	DUAN X, HE Y B, CUI Y J, et al. Highly selective separation of small hydrocarbons and carbon dioxide in a metal-organic framework with open copper(Ⅱ) coordination sites[J]. RSC Advances, 2014, 4(44):23058-23063.
[2]	HE Y B, KRISHNA B, CHEN B L. Metal-organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons[J]. Energy & Environmental Science, 2012, 5(10):9107-9120.
[3]	DUAN X, ZHANG Q, CAI J F, et al. A new metal-organic framework with potential for adsorptive separation of methane from carbon dioxide, acetylene, ethylene, and ethane established by simulated breakthrough experiments[J]. Journal of Materials Chemistry A, 2014, 2(8):2628-2633.
[4]	PLONKA A M, CHEN X Y, WANG H, et al. Light hydrocarbon adsorption mechanisms in two calcium-based microporous metal organic frameworks[J]. Chemistry of Materials, 2016, 28(6):1636-1646.
[5]	HUANG L, CAO D P. Selective adsorption of olefin-paraffin on diamond-like frameworks:diamondyne and PAF-302[J]. Journal of Materials Chemistry A, 2013, 1(33):9433-9439.
[6]	GEIER S J, MASON J A, BLOCH E D, et al. Selective adsorption of ethylene over ethane and propylene over propane in the metal-organic frameworks M2(dobdc) (M=Mg, Mn, Fe, Co, Ni, Zn)[J]. Chemical Science, 2013, 4(5):2054-2061.
[7]	JIANG J W, SANDLER S I. Monte Carlo simulation for the adsorption and separation of linear and branched alkanes in IRMOF-1[J]. Langmuir, 2006, 22(13):5702-5707.
[8]	沈文龙, 李嘉旭, 杨颖, 等. 基于沸石ZSM-5的CH4/N2/CO2二元体系吸附相平衡研究[J]. 化工学报, 2014, 65(9):3490-3498. SHEN W L, LI J X, YANG Y, et al. Binary adsorption equilibrium of CH4, N2 and CO2 on zeolite ZSM-5[J]. CIESC Journal, 2014, 65(9):3490-3498.
[9]	李明, 涂适, 赵欣, 等. 真实吸附溶液理论预测CH4-C2H6在活性炭上的吸附平衡[J]. 化工学报, 2013, 64(11):4082-4089. LI M, TU S, ZHAO X, et al. Adsorption equilibrium prediction for CH4-C2H6 on activated carbon by real adsorption solution theory[J]. CIESC Journal, 2013, 64(11):4082-4089.
[10]	HOWARTH A J, PETERS A W, VERMEULEN N A, et al. Best practices for the synthesis, activation, and characterization of metal-organic frameworks[J]. Chemistry of Materials, 2017, 29(1):26-39.
[11]	HARTMANN M, BOHME U, HOVESTADT M, et al. Adsorptive separation of olefin/paraffin mixtures with ZIF-4[J]. Langmuir, 2015, 31(45):12382-12389.
[12]	CAI J F, WANG H Z, WANG H L, et al. An amino-decorated NbO-type metal-organic framework for high C2H2 storage and selective CO2 capture[J]. RSC Advances, 2015, 5:77417-77422.
[13]	ZOU R Y, REN X L, HUANG F, et al. A luminescent Zr-based metal-organic framework for sensing/capture of nitrobenzene and high-pressure separation of CH4/C2H6[J]. Journal of Materials Chemistry A, 2015, 3:23493-23500.
[14]	XIA T F, CAI J F, WANG H Z, et al. Microporous metal-organic frameworks with suitable pore spaces for acetylene storage and purification[J]. Microporous and Mesoporous Materials, 2015, 215:109-115.
[15]	LIU K, MA D X, LI B Y, et al. High storage capacity and separation selectivity for C2 hydrocarbons over methane in the metal-organic framework Cu-TDPAT[J]. Journal of Materials Chemistry A, 2014, 2(38):15823-15828.
[16]	HE Y B, XIANG S C, ZHANG Z J, et al. A microporous lanthanide-tricarboxylate framework with the potential for purification of natural gas[J]. Chemical Communications, 2012, 48(88):10856-10858.
[17]	HE Y B, ZHANG Z J, XIANG S C, et al. A microporous metal-organic framework for highly selective separation of acetylene, ethylene, and ethane from methane at room temperature[J]. Chemistry-A European Journal, 2012, 18(2):613-619.
[18]	HE Y B, ZHANG Z J, XIANG S C, et al. High separation capacity and selectivity of C2 hydrocarbons over methane within a microporous metal-organic framework at room temperature[J]. Chemistry-A European Journal, 2012, 18(7):1901-1904.
[19]	CHEN Y W, QIAO Z E, LV D F, et al. Selective adsorption of light alkanes on a highly robust indium based metal-organic framework[J]. Industrial & Engineering Chemistry Research, 2017, 56(15):4488-4495.
[20]	PRASANTH K P, RALLAPALLI P, RAJ M C, et al. Enhanced hydrogen sorption in single walled carbon nanotube incorporated MIL-101 composite metal-organic framework[J]. International Journal of Hydrogen Energy, 2011, 36(13):7594-7601.
[21]	ZHAO Y X, SEREDYCH M, ZHONG Q, et al. Aminated graphite oxides and their composites with copper-based metal-organic framework:in search for efficient media for CO2 sequestration[J]. RSC Advances, 2013, 3(25):9932-9941.
[22]	KAYE S S, DAILLY A, YAGHI O M, et al. Impact of preparation and handling on the hydrogen storage properties of Zn4O(1,4-benzenedicarboxylate)3 (MOF-5)[J]. Journal of the American Chemical Society, 2007, 129(46):14176-14177.
[23]	SUN X J, XIA Q B, ZHAO Z X, et al. Synthesis and adsorption performance of MIL-101(Cr)/graphite oxide composites with high capacities of n-hexane[J]. Chemical Engineering Journal, 2014, 239:226-232.
[24]	PETIT C, BURRESS J, BANDOSZ T J. The synthesis and characterization of copper-based metal-organic framework/graphite oxide composites[J]. Carbon, 2011, 49(2):563-572.
[25]	AMELOOT R, LIEKENS A, ALAERTS L, et al. Silica-MOF composites as a stationary phase in liquid chromatography[J]. European Journal of Inorganic Chemistry, 2010, 24:3735-3738.
[26]	SOMAYAJULU R P B, RAJ M C, PATIL D V, et al. Activated carbon@MIL-101(Cr):a potential metal-organic framework composite material for hydrogen storage[J]. International Journal of Energy Research, 2013, 37(3):746-753.
[27]	LI Y J, MIAO J P, SUN X J, et al. Mechanochemical synthesis of Cu-BTC@GO with enhanced water stability and toluene adsorption capacity[J]. Chemical Engineering Journal, 2016, 298:191-197.
[28]	CHEN B L, OCKWIG N W, MILLWARD A R, et al. High H2 adsorption in a microporous metal-organic framework with open metal sites[J]. Angewandte Chemie International Edition, 2005, 44(30):4745-4749.
[29]	CHEN Y W, LV D F, WU J L, et al. A new MOF-505@GO composite with high selectivity for CO2/CH4 and CO2/N2 separation[J]. Chemical Engineering Journal, 2017, 308:1065-1072.
[30]	KOVTYUKHOVA N I, OLLIVIER P J, MARTIN B R, et al. Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations[J]. Chemistry of Materials, 1999, 11(3):771-778.
[31]	HSIAO M C, LIAO S H, YEN M Y, et al. Preparation of covalently functionalized graphene using residual oxygen-containing functional groups[J]. ACS Applied Materials and Interfaces, 2010, 2(11):3092-2099.
[32]	MYERS A L, PRAUSNITZ J M. Thermodynamics of mixed-gas adsorption[J]. AIChE J., 1965, 11(1):121-127.
[33]	WALTON K S, SHOLL D S. Predicting multicomponent adsorption:50 years of the ideal adsorbed solution theory[J]. AIChE J., 2015, 61(9):2757-2762.
[34]	BLOCH E D, QUEEN W L, KRISHNA R, et al. Hydrocarbon separations in a metal-organic framework with open iron(Ⅱ) coordination sites[J]. Science, 2012, 335:1606.
[35]	PIERS J, PINTO M L, SAINI V K. Ethane selective IRMOF-8 and its significance in ethane-ethylene separation by adsorption[J]. ACS Appl. Mater. Interfaces, 2014, 6:12093-12099.
[36]	BANERJEE D, WANG H, PLONKA A M, et al. Direct structural identification of gas induced gate-opening coupled with commensurate adsorption in a microporous metal-organic framework[J]. Chem. Eur. J., 2016, 22:1-11.
[37]	HE Y B, ZHANG Z J, XIANG S C, et al. A robust doubly interpenetrated metal-organic framework constructed from a novel aromatic tricarboxylate for highly selective separation of small hydrocarbons[J]. Chem. Commun., 2012, 48:6493-6495.

CH₄/C₂H₆/C₃H₈在MOF-505@5GO上吸附相平衡和选择性

Adsorption isotherms and selectivity of CH₄/C₂H₆/C₃H₈ on MOF-505@5GO

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 37

相关文章 15

编辑推荐

Metrics

本文评价

[1]	汤晓玲, 王嘉瑞, 朱玄烨, 郑仁朝. 基于Pickering乳液的卤醇脱卤酶催化合成手性环氧氯丙烷[J]. 化工学报, 2023, 74(7): 2926-2934.
[2]	刘晓洋, 喻健良, 侯玉洁, 闫兴清, 张振华, 吕先舒. 螺旋微通道对掺氢甲烷爆轰传播的影响[J]. 化工学报, 2023, 74(7): 3139-3148.
[3]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.
[4]	牛超, 沈胜强, 杨艳, 潘泊年, 李熠桥. 甲烷BOG喷射器流动过程计算与性能分析[J]. 化工学报, 2023, 74(7): 2858-2868.
[5]	周小文, 杜杰, 张战国, 许光文. 基于甲烷脉冲法的Fe₂O₃-Al₂O₃载氧体还原特性研究[J]. 化工学报, 2023, 74(6): 2611-2623.
[6]	胡晗, 杨亮, 李春晓, 刘道平. 天然烟浸滤液水合物法储甲烷动力学研究[J]. 化工学报, 2023, 74(3): 1313-1321.
[7]	彭晓婉, 郭笑楠, 邓春, 刘蓓, 孙长宇, 陈光进. ZIF-8浆液法分离CH₄/N₂的双吸收-吸附塔工艺流程建模与模拟[J]. 化工学报, 2023, 74(2): 784-795.
[8]	席国君, 刘子涵, 雷广平. FeTPPs-CuBTC协同强化低浓度煤层气吸附分离[J]. 化工学报, 2022, 73(9): 3940-3949.
[9]	沈嘉辉, 王侃宏, 郁达伟, 胡大洲, 魏源送. 游离氨调理污泥厌氧消化优化产甲烷过程与强化有机物释放[J]. 化工学报, 2022, 73(9): 4147-4155.
[10]	廖珊珊, 张少刚, 陶骏骏, 刘家豪, 汪金辉. 竖直射流火撞击障碍管道数值模拟分析[J]. 化工学报, 2022, 73(9): 4226-4234.
[11]	郭丹, 方雨洁, 许一寒, 李致远, 黄守莹, 王胜平, 马新宾. 乙烷和二氧化碳催化转化的研究进展[J]. 化工学报, 2022, 73(8): 3406-3416.
[12]	王婵, 肖国锡, 郭小雪, 徐人威, 岳源源, 鲍晓军. 基于介尺度结构解聚-重组装的Beta分子筛的绿色合成及应用[J]. 化工学报, 2022, 73(6): 2690-2697.
[13]	唐翠萍, 张雅楠, 梁德青, 李祥. 聚乙烯己内酰胺链端改性及其对甲烷水合物形成的抑制作用研究[J]. 化工学报, 2022, 73(5): 2130-2139.
[14]	叶枫, 李刚, 付鑫, 郎雪梅, 王燕鸿, 王盛龙, 张建利, 樊栓狮. 多孔膜反应器中丙烷催化脱氢制丙烯的模拟研究[J]. 化工学报, 2022, 73(5): 2008-2019.
[15]	闫帅, 杨家宝, 龚岩, 郭庆华, 于广锁. CO₂稀释对甲烷反扩散火焰结构的影响研究[J]. 化工学报, 2022, 73(3): 1335-1342.