Effects of temperature on adsorption mechanism and adsorption selectivity of C3H6 and C3H8 on MOF-74(Ni)

doi:10.11949/j.issn.0438-1157.20151519

Abstract

Abstract:

MOF-74(Ni) was synthesized by solvothermal synthesis method and then characterized by PXRD and pore size analysis. Isotherms of C₃H₆ and C₃H₈ on the synthesized MOF-74(Ni) were measured at different temperatures. The temperature programmed desorption experiments were conducted to estimate the desorption activation energies of C₃H₆ and C₃H₈ on the MOF-74(Ni). IAST theory was applied to predict the adsorption selectivity of C₃H₆/C₃H₈ mixture. The effects of temperature on adsorption mechanism and adsorption selectivity were also discussed. Results showed that the as-synthesized MOF-74(Ni) had BET surfaces of 1306 m²·g^-1, and its C₃H₆ adsorption capacity was up to 7.4 mmol·g^-1 at 298 K. With rising temperature, the adsorption capacity of C₃H₈ on MIL-74(Ni) decreased sharply, while that of C₃H₆ decreased slightly, resulting in improvement of C₃H₆/C₃H₈ adsorption selectivity of MOF-74(Ni). It could be attributed to p-complexation bonding between C₃H₆ and MOF-74(Ni), which was stronger than the interaction of C₃H₈ with MOF-74(Ni). TPD results indicated that the desorption activation energy of C₃H₆ on MOF-74(Ni) was higher than that of C₃H₈, which were 68.92 kJ·mol^-1 and 50.80 kJ·mol^-1, respectively.

Key words: MOF-74(Ni), propylene, propane, adsorption isotherms, adsorption selectivity, temperature

摘要：

采用水热法成功制备了MOF-74(Ni),使用PXRD、孔径分析对材料进行了表征,测定了材料在不同温度下的C₃H₆和C₃H₈吸附等温线,应用程序升温脱附技术估算了脱附活化能,并使用IAST理论预测了材料对C₃H₆/C₃H₈二元体系的吸附选择性。讨论了温度对吸附机理和吸附选择性的影响。结果显示,MOF-74(Ni)的BET比表面积高达1306 m²·g^-1。在298 K下,C₃H₆的吸附量高达7.4 mmol·g^-1。随着温度升高,C₃H₈的吸附量大幅降低,而C₃H₆的吸附量下降程度较小,导致材料对C₃H₆/C₃H₈吸附选择性升高。当温度为328K时,MOF-74(Ni)对C₃H₆/C₃H₈二元气体混合物的吸附选择接近12。程序升温脱附的实验结果显示,C₃H₆在MOF-74(Ni)上的脱附活化能大于C₃H₈,分别为68.92 kJ·mol^-1和50.80 kJ·mol^-1。C₃H₆是通过与MOF-74(Ni)的不饱和金属位点Ni²⁺以p络合作用方式吸附,作用力较强,而C₃H₈与Ni²⁺之间的作用力较弱。根据吸附机理不同的特点,适当提高温度,将有助于提高MOF-74(Ni)吸附分离C₃H₆/C₃H₈混合物体系的吸附选择性。

关键词: MOF-74(Ni), 丙烯, 丙烷, 吸附等温线, 吸附选择性, 温度

CLC Number:

TQ028.1
TB34

LIU Jiang, WU Yufang, XU Feng, XIAO Jing, XIA Qibin, LI Zhong. Effects of temperature on adsorption mechanism and adsorption selectivity of C₃H₆ and C₃H₈ on MOF-74(Ni)[J]. CIESC Journal, 2016, 67(5): 1942-1948.

刘江, 吴玉芳, 许峰, 肖静, 夏启斌, 李忠. 温度对MOF-74(Ni)吸附分离丙烯丙烷机理和选择性的影响[J]. 化工学报, 2016, 67(5): 1942-1948.

References 32

[1]	王卅. 我国丙烯下游产业产品市场情况[J]. 化工进展, 2014, 33(9): 2517-2520. DOI: 10.3969/j.issn.1000-6613.2014.09.048. WANG S. Domestic markets in propylene downstream industries [J]. Chem. Ind. Eng. Prog., 2014, 33(9): 2517-2520. DOI: 10.3969/j.issn.1000-6613.2014.09.048
[2]	Eldridge R B. Olefin/paraffin separation technology: a review [J]. Ind. Eng. Chem. Res., 1993, 32(10): 2208-2212.
[3]	Van Miltenburg A, Gascon J, Zhu W D, et al. Propylene/propane mixture adsorption on faujasite sorbents [J]. Adsorption, 2008, 14: 309-321.
[4]	Da Silva F A, Rodrigues A E. Adsorption equilibria and kinetics for propylene and propane over 13X and 4A zeolite pellets [J]. Ind. Eng. Chem. Res., 1999, 38(5): 2051-2057.
[5]	季丰, 苏宝根, 邢华斌, 等. 干气中乙烯丙烯在活性炭上的动态吸附和脱附特性研究[J]. 高校化学工程学报, 2013, 27(4): 547-554. DOI: 10.3969/j.issn.1003-9015.2013.07.09.08 Ji F, Su B G, Xing H B, et al. Dynamic adsorption-desorption characteristics of ethylene and propylene in dry gas on activated carbon [J]. Journal of Chemical Engineering of Chinese University, 2013, 27(4): 547-554. DOI: 10.3969/j.issn.1003-9015.2013.07.09.08
[6]	Rege S U, Padin J, Yang R T. Olefin/paraffin separations by adsorption: π-complexation vs. kinetic separation [J]. AIChE Journal, 1998, 44(4): 799-809.
[7]	Yang R T, Kikkinides E S. New sorbents for olefin/paraffin separations by adsorption via π-complexation [J]. AIChE Journal, 1995, 41(3): 509-517.
[8]	马士珍, 苏宝根, 鲍宗必, 等. 干气中烷烃、烯烃新型分离吸附剂的研究进展[J]. 化工学报, 2014, 65(2): 396-405. DOI: 10.3969/j.issn.0438-1157.2014.02.005 Ma S Z, Su B G, Bao Z B, et al. Advances in new type adsorbent for separating alkene from dry gas [J]. CIESC Journal, 2014, 65(2): 396-405. DOI: 10.3969/j.issn.0438-1157.2014.02.005
[9]	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: 109-119.
[10]	Yoon J W, Seo Y-K, Hwang Y K, et al. Controlled reducibility of a metal-organic framework with coordinatively unsaturated sites for preferential gas sorption [J]. Angew. Chem. Int. Edit., 2010, 49(34): 5949-5952.
[11]	Li K H, Olson D H, Seidel J, et al. Zeolitic imidazolate frameworks for kinetic separation of propane and propene [J]. J. Am. Chem. Soc., 2009, 131(30): 10368-10369.
[12]	Lou W L, Yang J F, Li L B, et al. Adsorption and separation of CO2 on Fe(Ⅱ)-MOF-74: Effect of the open metal coordination site [J]. J. Solid State Chem., 2014, 213: 224-228.
[13]	Adhikari A K, Lin K S. Synthesis, fine structural characterization, and CO2 adsorption capacity of metal organic frameworks-74 [J]. J. Nanosci. Nanotechnol., 2014, 14(4): 2709-2717.
[14]	Bloch E D, Hudson M R, Mason J A, et al. Reversible CO binding enables tunable CO/H2 and CO/N2 separations in metal-organic frameworks with exposed divalent metal cations [J]. J. Am. Chem. Soc., 2014, 136(30): 10752-10761.
[15]	刘有毅, 黄艳, 何嘉杰, 等. CO/N2/CO2 在MOF-74(Ni)上吸附相平衡和选择性[J]. 化工学报, 2015, 66(11): 4469-4475. DOI: 10.11949/j.issn.0438-1157.20150504 Liu Y Y, Huang Y, He J J, et al. Adsorption isotherms and selectivity of CO/N2/CO2 on MOF-74(Ni) [J]. CIESC Journal, 2015, 66(11): 4469-4475. DOI: 10.11949/j.issn.0438-1157.20150504
[16]	Mundstock A, Boehme U, Barth B, et al. Propylene/propane separation in fixed-bed adsorber and membrane permeation [J]. Chem. Ing. Tech., 2013, 85(11): 1694-1699.
[17]	Chen D L, Shang H, Zhu W, et al. Transient breakthroughs of CO2/CH4 and C3H6/C3H8 mixtures in fixed beds packed with Ni-MOF-74 [J]. Chem. Eng. Sci., 2014, 117: 407-415.
[18]	BÖhme U, Barth B, Paula C, et al. Ethene/ethane and propene/propane separation via the olefin and paraffin selective metal-organic framework adsorbents CPO-27 and ZIF-8 [J]. Langmuir, 2013, 29(27): 8592-8600.
[19]	Caskey S R, Wong-Foy A G, Matzger A J. Dramatic tuning of carbon dioxide uptake via metal substitution in a coordination polymer with cylindrical pores [J]. J. Am. Chem. Soc., 2008, 130(33): 10870-10871.
[20]	Walton K S, Snurr R Q. Applicability of the BET method for determining surface areas of microporous metal-organic frameworks [J]. J. Am. Chem. Soc., 2007, 129(27): 8552-8556.
[21]	Wu X, Bao Z, Yuan B, et al. Microwave synthesis and characterization of MOF-74 (M = Ni, Mg) for gas separation [J]. Micropor. Mesopor. Mater., 2013, 180: 114-122.
[22]	李玉洁, 苗晋朋, 孙雪娇, 等. 机械化学法合成金属有机骨架材料HKUST-1及其吸附苯性能[J]. 化工学报, 2015, 66(2):793-799. DOI: 10.11949/j.issn.0438-1157.20141127. Li Y J, Miao J P, Sun X J, et al. Mechano-chemical synthesis of HKUST-1 with high capacity of benzene adsorption [J].CIESC Journal, 2015, 66(2): 793-799. DOI: 10.11949/j.issn.0438-1157. 20141127
[23]	Bae Y S, Lee C Y, Kim K C, et al. High propene/propane selectivity in isostructural metal-organic frameworks with high densities of open metal sites [J]. Angew. Chem. Int. Edit., 2012, 51(8): 1857-1860.
[24]	Plaza M G, Ribeiro A M, Ferreira A, et al. Separation of C3/C4 hydrocarbon mixtures by adsorption using a mesoporous iron MOF: MIL-100(Fe) [J]. Micropor. Mesopor. Mater., 2012, 153: 178-190.
[25]	Jorge M, Lamia N, Rodrigues A E. Molecular simulation of propane/propylene separation on the metal-organic framework Cu-BTC [J]. Colloids and Surfaces A: Physicochem. Eng. Aspects, 2010, 357: 27-34.
[26]	Huang H Y, Yang R T, Chen N. Anion effects on the adsorption of acetylene by Nickel Halides [J]. Langmuir, 1999, 15(22): 7647-7652.
[27]	Yang R T. Adsorbents: Fundamentals and Applications [M]. New Jersey: John Wiley & Sons Inc, 2003: 208-211
[28]	MYERS A, PRAUSNITZ J. Thermodynamics of mixed-gas adsorption [J]. AIChE Journal, 1965, 11(1): 121-127.
[29]	Duan J G, Higuchi M, Horike S, et al. High CO2/CH4 and C2 hydrocarbons/CH4 selectivity in a chemically robust porous coordination polymer [J]. Adv. Funct. Mater., 2013, 23(28): 3525-3530.
[30]	Krishna R, Calero S, Smith B. Investigation of entropy effects during sorption of mixtures of alkanes in MFI zeolite [J]. Chem. Eng. J., 2002, 88: 81-94.
[31]	Li J, Li Z, Liu B, et al. Effect of relative humidity on adsorption of formaldehyde on modified activated carbons [J]. Chin. J. Chem. Eng., 2008, 16(6): 871-875.
[32]	潘红艳, 李忠, 夏启斌, 等. 金属离子改性活性炭对二氯甲烷脱附活化能的影响[J]. 化工学报, 2007, 58(9): 2259-2265. Pan H Y, Li Z, Xia Q B, et al. Effect of metal ions loaded onto activated carbons on desorption activation energy of dichloromethane [J]. Journal of Chemical Industry and Engineering(China), 2007, 58(9): 2259-2265.

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Effects of temperature on adsorption mechanism and adsorption selectivity of C₃H₆ and C₃H₈ on MOF-74(Ni)

温度对MOF-74(Ni)吸附分离丙烯丙烷机理和选择性的影响

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