Stable mixed metal-organic framework for efficient C2H6/C2H4 separation

doi:10.11949/0438-1157.20200463

Abstract

Abstract:

In view of lacking efficient ethane-selective adsorbent for ethane/ethylene separation, a highly stable microporous mixed metal-organic framework, termed as MUV-10(Mn), was synthesized by the solvothermal method and it could efficiently separate C₂H₆/C₂H₄mixture. The structure and morphology of synthesized material was confirmed by XRD, SEM, TGA and BET, etc. Selectivity and corresponding adsorption heat of C₂H₆ and C₂H₄were calculated based on single component adsorption results measured in details. The results show that MUV-10(Mn) features C₂H₆/C₂H₄ selectivity about 1.42 and can absorb more C₂H₆ than C₂H₄ at room temperature. And it has high acid, alkali and water vapor stability. Addtionally, dynamic breakthrough experiment showed MUV-10(Mn) could extracted low concentration of C₂H₆ from C₂H₆/C₂H₄mixture ( $V C 2 H 6 ? / ? V C 2 H 4$ =1∶9 and 1∶15) to collect C₂H₄ gas with high purity, which indicates the promising future of MUV-10(Mn) in C₂H₄purification.

Key words: light hydrocarbons, ethane, ethylene, adsorption, separation, metal-organic frameworks

摘要：

针对乙烷/乙烯分离过程中，缺乏高效稳定的乙烷选择吸附剂，采用溶剂热法合成了一种具有高稳定性的双金属微孔MOF材料MUV-10(Mn)，通过吸附分离的方式，实现了乙烯中低浓度乙烷的高效分离。采用XRD、SEM、TGA、比表面分析等表征手段对所制备材料的结构及形貌进行了确认和分析，详细测试了MUV-10(Mn)对乙烷和乙烯单组分气体的吸附性能，并进行了选择性和吸附热的计算。结果表明，MUV-10(Mn)在室温下的乙烷吸附量高于乙烯对于乙烷/乙烯混合气的选择性为1.42，且具有高的酸、碱和水蒸气稳定性。混合气体穿透实验表明，MUV-10(Mn)能够高效去除乙烯中的低浓度乙烷，得到高纯乙烯气体，在乙烯提纯方面显示出良好的应用前景。

关键词: 低碳烃, 乙烷, 乙烯, 吸附, 分离, 金属有机骨架材料

CLC Number:

TQ 028.1

Puxu LIU, Chaohui HE, Libo LI, Jinping LI. Stable mixed metal-organic framework for efficient C₂H₆/C₂H₄ separation[J]. CIESC Journal, 2020, 71(9): 4211-4218.

刘普旭, 贺朝辉, 李立博, 李晋平. 高稳定双金属MOF材料用于低浓度乙烷的高效分离[J]. 化工学报, 2020, 71(9): 4211-4218.

Figures/Tables 5

Fig.1 The view of MUV-10(Mn) structure along [001] direction

Fig.2 XRD pattern (a)，TGA curve (b)，N2 sorption isotherm (c) and SEM image (d) of MUV-10(Mn)

Fig.3 Adsorption isotherms of C2H6 and C2H4 (a), IAST selectivity (b), adsorption heat of C2H6 and C2H4 (c), fitting curves of C2H6 and C2H4 adsorption isotherms at 298 K based on the single-site Langmuir-Freundlich model (d)

Fig.4 Experimental breakthrough curves of MUV-10(Mn) for C2H6/C2H4 mixture at 298 K and 105 Pa

Fig.5 XRD patterns[(a),(b)] and corresponding adsorption isotherms for C2H6 and C2H4 at 298 K and 105 Pa [(c)—(e)] of MUV-10(Mn) under different experimental conditions

References 41

1	王欣, 庞玉兰. 国内乙烯下游产品商贸发展趋势研究[J]. 石油化工技术与经济, 2018, 34(3): 1-5.
	Wang X, Peng Y L. Research on the trading development trend of ethylene downstream products in China[J]. Technology ＆ Economics in Petrochemicals, 2018, 34(3): 1-5.
2	Zeng C Y, Hu Q L. 2018 petroleum & chemical industry development report[J]. Chinese Journal of Chemical Engineering, 2019, 27(10): 2606-2614.
3	Haghighi S S, Rahimpour M R, Raeissi S, et al. Investigation of ethylene production in naphtha thermal cracking plant in presence of steam and carbon dioxide[J]. Chemical Engineering Journal, 2013, 228: 1158-1167.
4	吴秀章. 煤制低碳烯烃工业示范工程最新进展[J]. 化工进展, 2014, 33(4): 787-794.
	Wu X Z. Latest progress of coal to light olefins industrial demonstration project[J]. Chemical Industry and Engineering Progress, 2014, 33(4): 787-794.
5	López E, Heracleous E, Lemonidou A A, et al. Study of a multitubular fixed-bed reactor for ethylene production via ethane oxidative dehydrogenation[J]. Chemical Engineering Journal, 2008, 145(2): 308-315.
6	Li J R, Kuppler R J, Zhou H C. Selective gas adsorption and separation in metal-organic frameworks[J]. Chemical Society Reviews, 2009, 38(5): 1477-1504.
7	Sholl D S, Lively R P. Seven chemical separations to change the world[J]. Nature, 2016, 532(7600): 435-437.
8	尤成宏, 付裕. 抚顺乙烯装置 HRS 深冷分离技术研究[J]. 乙烯工业, 2015, 27(1): 38-42.
	You C H, Fu Y. Study on HRS cryogenic separation technology applied in Fushun ethylene plant[J]. Ethylene Industry, 2015, 27(1): 38-42.
9	Sircar S. Basic research needs for design of adsorptive gas separation processes[J]. Industrial & Engineering Chemistry Research, 2006, 45(16): 5435-5448.
10	谢丹妍, 邢华斌, 张治国, 等. 多孔氢键金属-有机框架材料对乙炔和二氧化碳的吸附分离[J]. 化工学报, 2017, 68(1): 154-162.
	Xie D Y, Xing H B, Zhang Z G, et al. Porous hydrogen-bonded organometallic frameworks for adsorption separation of acetylene and carbon dioxide[J]. CIESC Journal, 2017, 68(1): 154-162.
11	崔希利, 邢华斌. 金属有机框架材料分离低碳烃的研究进展[J]. 化工学报, 2018, 69(6): 2339-2352.
	Cui X L, Xing H B. Separation of light hydrocarbons with metal-organic frameworks[J]. CIESC Journal, 2018, 69(6): 2339-2352.
12	Zhao X, Wang Y X, Li D S, et al. Metal-organic frameworks for separation[J]. Advanced Materials, 2018, 30(37): 1705189.
13	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(6076): 1606-1610.
14	Bao Z B, Chang G G, Xing H B, et al. Potential of microporous metal-organic frameworks for separation of hydrocarbon mixtures[J]. Energy & Environmental Science, 2016, 9(12): 3612-3641.
15	Li H, Li L B, Lin R B, et al. Porous metal-organic frameworks for gas storage and separation: Status and challenges[J]. Energy Chem., 2019, 1(1): 100006.
16	Cadiau A, Adil K, Bhatt P M, et al. A metal-organic framework-based splitter for separating propylene from propane[J]. Science, 2016, 353(6295): 137-140.
17	Wang H, Dong X L, Colombo V, et al. Tailor‐made microporous metal-organic frameworks for the full separation of propane from propylene through selective size exclusion[J]. Advanced Materials, 2018, 30(49): 1805088.
18	Li L B, Lin R B, Krishna R, et al. Flexible-robust metal-organic framework for efficient removal of propyne from propylene[J]. Journal of the American Chemical Society, 2017, 139(23): 7733-7736.
19	Li L B, Wen H M, He C H, et al. A metal-organic framework with suitable pore size and specific functional sites for the removal of trace propyne from propylene[J]. Angewandte Chemie International Edition, 2018, 57(46): 15183-15188.
20	Yang L F, Cui X L, Yang Q W, et al. A single‐molecule propyne trap: highly efficient removal of propyne from propylene with anion‐pillared ultramicroporous materials[J]. Advanced Materials, 2018, 30(10): 1705374.
21	Cui X L, Chen K J, Xing H B, et al. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene[J]. Science, 2016, 353(6295): 141-144.
22	Xiang S C, Zhang Z J, Zhao C G, et al. Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene[J]. Nature Communications, 2011, 2(1): 1-7.
23	Lin R B, Li L B, Zhou H L, et al. Molecular sieving of ethylene from ethane using a rigid metal-organic framework[J]. Nature Materials, 2018, 17(12): 1128-1133.
24	Bao Z B, Wang J W, Zhang Z G, et al. Molecular sieving of ethane from ethylene through the molecular cross‐section size differentiation in gallate‐based metal-organic frameworks[J]. Angewandte Chemie International Edition, 2018, 57(49): 16020-16025.
25	Wang Y X, Yuan S, Hu Z G, et al. Pore size reduction in zirconium metal-organic frameworks for ethylene/ethane separation[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(7): 7118-7126.
26	Aguado S, Bergeret G, Daniel C, et al. Absolute molecular sieve separation of ethylene/ethane mixtures with silver zeolite A[J]. Journal of the American Chemical Society, 2012, 134(36): 14635-14637.
27	Bachman J E, Kapelewski M T, Reed D A, et al. M₂(m-dobdc)(M= Mn, Fe, Co, Ni) metal-organic frameworks as highly selective, high-capacity adsorbents for olefin/paraffin separations[J]. Journal of the American Chemical Society, 2017, 139(43): 15363-15370.
28	Zhang Y M, Li B Y, Krishna R, et al. Highly selective adsorption of ethylene over ethane in a MOF featuring the combination of open metal site and π-complexation[J]. Chemical Communications, 2015, 51(13): 2714-2717.
29	Zhang L, Li L B, Hu E L, et al. Boosting ethylene/ethane separation within copper (Ⅰ)‐chelated metal-organic frameworks through tailor‐made aperture and specific π‐complexation[J]. Advanced Science, 2019, 7(2): 1901918.
30	Liao P Q, Zhang W X, Zhang J P, et al. Efficient purification of ethene by an ethane-trapping metal-organic framework[J]. Nature Communications, 2015, 6: 8697.
31	兰天昊, 贺朝辉, 杨玲, 等. 金属有机骨架材料(MOFs)用于乙烷/乙烯的高效分离[J]. 石油学报(石油加工), 2019, 35(06): 1219-1227.
	Lan T H, He C H, Yang L, et al. Metal-organic frameworks (MOFs) for efficient ethane/ethylene separation[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2019, 35(6): 1219-1227.
32	Gücüyener C, van den Bergh J, Gascon J, et al. Ethane/ethene separation turned on its head: selective ethane adsorption on the metal- organic framework ZIF-7 through a gate-opening mechanism[J]. Journal of the American Chemical Society, 2010, 132(50): 17704-17706.
33	Wang X J, Wu Y, Zhou X, et al. Novel C-PDA adsorbents with high uptake and preferential adsorption of ethane over ethylene[J]. Chemical Engineering Science, 2016, 155: 338-347.
34	Liang W W, Zhang Y F, Wang X J, et al. Asphalt-derived high surface area activated porous carbons for the effective adsorption separation of ethane and ethylene[J]. Chemical Engineering Science, 2017, 162: 192-202.
35	Lin R B, Wu H, Li L B, et al. Boosting ethane/ethylene separation within isoreticular ultramicroporous metal-organic frameworks[J]. Journal of the American Chemical Society, 2018, 140(40): 12940-12946.
36	Li L B, Lin R B, Krishna R, et al. Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites[J]. Science, 2018, 362(6413): 443-446.
37	Kang I J, Khan N A, Haque E, et al. Chemical and thermal stability of isotypic metal-organic frameworks: effect of metal ions[J]. Chemistry-A European Journal, 2011, 17(23): 6437-6442.
38	Cavka J H, Jakobsen S, Olsbye U, et al. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability[J]. Journal of the American Chemical Society, 2008, 130(42): 13850-13851.
39	Kandiah M, Nilsen M H, Usseglio S, et al. Synthesis and stability of tagged UiO-66 Zr-MOFs[J]. Chemistry of Materials, 2010, 22(24): 6632-6640.
40	Wu H, Yildirim T, Zhou W. Exceptional mechanical stability of highly porous zirconium metal-organic framework UiO-66 and its important implications[J]. The Journal of Physical Chemistry Letters, 2013, 4(6): 925-930.
41	Castells‐Gil J, Padial N M, Almora‐Barrios N, et al. Chemical engineering of photoactivity in heterometallic titanium-organic frameworks by metal doping[J]. Angewandte Chemie International Edition, 2018, 57(28): 8453-8457.

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Stable mixed metal-organic framework for efficient C₂H₆/C₂H₄ separation

高稳定双金属MOF材料用于低浓度乙烷的高效分离

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