Investigation of the Ethanol Dehydration to Ethene Reaction on H-SSZ-13 Molecular Sieve by in situ Solid-state NMR Spectroscopy

doi:10.11938/cjmr20212946

Abstract

Abstract:

In situ solid-state nuclear magnetic resonance (ssNMR) techniques under continuous flow and batch-like conditions as well as 2D ¹³C-¹³C dipolar-based COmbined R2 Driven (CORD) spin diffusion NMR experiments were utilized to investigate the dehydration process of ethanol on molecular sieve H-SSZ-13. Kinds of intermediate species including ethanol with different adsorption orientation, diethyl ether under activated state, the surface ethoxy, triethyloxonium ion and even ethene were captured directly, and the evolution process of these intermediate species was also revealed in this paper. Moreover, it can be emphasized that the ethene species were observed in situ by ssNMR for the first time. These results enriched the fundamental research of ethanol dehydration reaction.

Key words: in situ solid-state nuclear magnetic resonance, ethanol dehydration, zeolite catalysis

CLC Number:

O482.53

Shu ZENG, Shu-tao XU, Ying-xu WEI, Zhong-min LIU. Investigation of the Ethanol Dehydration to Ethene Reaction on H-SSZ-13 Molecular Sieve by in situ Solid-state NMR Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2022, 39(2): 123-132.

Figures/Tables 7

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References 40

1	FARRELL A E, PLEVIN R J, TURNER B T, et al Ethanol can contribute to energy and environmental goals[J]. Science, 2006, 311 (5760):506-508. doi: 10.1126/science.1121416
2	TIAN P, WEI Y X, YE M, et al Methanol to olefins (MTO): From fundamentals to commercialization[J]. ACS Catal, 2015, 5 (3):1922-1938. doi: 10.1021/acscatal.5b00007
3	BI J D, GUO X W, LIU M, et al High effective dehydration of bio-ethanol into ethylene over nanoscale HZSM-5 zeolite catalysts[J]. Cataly Today, 2010, 149 (1, 2):143-147.
4	ARAI H, SAITOY, YONEDA Y Ethanol dehydration on alumina catalysts Ⅱ. The infrared study on adsorption of diethyl ether over alumina[J]. J Catal, 1968, 10, 128-133. doi: 10.1016/0021-9517(68)90164-4
5	GAYUBO A G, TARRIO A M, AGUAYO A T, et al Kinetic modelling of the transformation of aqueous ethanol into hydrocarbons on a HZSM-5 zeolite[J]. Ind Eng Chem Res, 2001, 40 (16):3467-3474. doi: 10.1021/ie001115e
6	KWAK J H, MEI D H, PEDEN C H F, et al (100) facets of γ-Al₂O₃: The active surfaces for alcohol dehydration reactions[J]. Catal Lett, 2011, 141 (5):649-655. doi: 10.1007/s10562-010-0496-8
7	TRET'YAKOV V F, MAKARFI Y I, TRET'YAKOV K V, et al The catalytic conversion of bioethanol to hydrocarbon fuel: A review and study[J]. Catalysis in Industry, 2011, 2 (4):402-420.
8	SONG Z X, TAKAHASHI A, NAKAMURA I, et al Phosphorus-modified ZSM-5 for conversion of ethanol to propylene[J]. Appl Catals A-Gen, 2010, 384 (1, 2):201-205.
9	DAI W L, SUN X M, TANG B, et al Verifying the mechanism of the ethene-to-propene conversion on zeolite H-SSZ-13[J]. J Catal, 2014, 314, 10-20. doi: 10.1016/j.jcat.2014.03.006
10	XU S T, ZHI Y C, HAN J F, et al Advances in catalysis for methanol-to-olefins conversion[J]. Adv Catal, 2017, 61, 37-122.
11	ALEXOPOULOS K, JOHN M, VAN DER BORGHT K, et al DFT-based microkinetic modeling of ethanol dehydration in H-ZSM-5[J]. J Catal, 2016, 339, 173-185. doi: 10.1016/j.jcat.2016.04.020
12	KIM S, ROBICHAUD D J, BECKHAM G T, et al Ethanol dehydration in HZSM-5 studied by density functional theory: Evidence for a concerted process[J]. J Phys Chem A, 2015, 119 (15):3604-3614. doi: 10.1021/jp513024z
13	PHUNG T K, BUSCA G Diethyl ether cracking and ethanol dehydration: Acid catalysis and reaction paths[J]. Chem Eng J, 2015, 272, 92-101. doi: 10.1016/j.cej.2015.03.008
14	CHIANG H, BHAN A Catalytic consequences of hydroxyl group location on the rate and mechanism of parallel dehydration reactions of ethanol over acidic zeolites[J]. J Catal, 2010, 271 (2):251-261. doi: 10.1016/j.jcat.2010.01.021
15	ZHANG M H, YU Y Z Dehydration of ethanol to ethylene[J]. Ind Eng Chem Res, 2013, 52 (28):9505-9514. doi: 10.1021/ie401157c
16	SUN J, WANG Y Recent advances in catalytic conversion of ethanol to chemicals[J]. Acs Catal, 2014, 4 (4):1078-1090. doi: 10.1021/cs4011343
17	NGUYEN T M, LE VAN MAO R Conversion of ethanol in aqueous solution over ZSM-5 zeolites: Study of the reaction network[J]. Appl Catal, 1990, 58 (1):119-129. doi: 10.1016/S0166-9834(00)82282-4
18	KONDO J N, ITO K, YODA E, et al An ethoxy intermediate in ethanol dehydration on bronsted acid sites in zeolite[J]. J Phy Chem B, 2005, 109 (21):10969-10972. doi: 10.1021/jp050721q
19	WANG W, JIAO J, JIANG Y J, et al Formation and decomposition of surface ethoxy species on acidic zeolite Y[J]. Chem Phys Chem, 2005, 6 (8):1467-1469. doi: 10.1002/cphc.200500262
20	ZHOU X, WANG C, CHU Y Y, et al Observation of an oxonium ion intermediate in ethanol dehydration to ethene on zeolite[J]. Nat Commun, 2019, 10 (1):1961-1961. doi: 10.1038/s41467-019-09956-7
21	ZENG S, LI J J, WANG N, et al Investigation of ethanol conversion on H-ZSM-5 zeolite by in situ solid-state NMR[J]. Energ Fuel, 2021, 35 (15):12319-12328. doi: 10.1021/acs.energyfuels.1c02151
22	MOWER P, FRILETTER V, MAATMAN R, et al Catalysis by crystalline aluminosilicates Ⅱ. Molecular-shape selective reactions[J]. J Catal, 1962, 1, 307-312. doi: 10.1016/0021-9517(62)90058-1
23	CSICSERY S M Shape-selective catalysis in zeolites[J]. Zeolites, 1984, 4 (3):202-213. doi: 10.1016/0144-2449(84)90024-1
24	DEGNAN T The implications of the fundamentals of shape selectivity for the development of catalysts for the petroleum and petrochemical industries[J]. J Catal, 2003, 216 (1, 2):32-46.
25	TEKETEL S, LUNDEGARRD L F, SKISTAD W, et al Morphology-induced shape selectivity in zeolite catalysis[J]. J Catal, 2015, 327, 22-32. doi: 10.1016/j.jcat.2015.03.013
26	WU P F, YANG M, SUN L J, et al Synthesis of nanosized SAPO-34 with the assistance of bifunctional amine and seeds[J]. Chem Commun, 2018, 54 (79):11160-11163. doi: 10.1039/C8CC05871G
27	LI J Z, WEI Y X, CHEN J R, et al Cavity controls the selectivity: insights of confinement effects on MTO reaction[J]. ACS Catal, 2014, 5 (2):661-665.
28	ZHANG W N, CHEN J R, XU S T, et al Methanol to olefins reaction over cavity-type zeolite: Cavity controls the critical intermediates and product selectivity[J]. ACS Catal, 2018, 8 (12):10950-10963. doi: 10.1021/acscatal.8b02164
29	ZHOU Y, QI L, WEI Y, et al Comparative investigation of the MTH induction reaction over HZSM-5 and HSAPO-34 catalysts[J]. Mol Catal, 2017, 433, 20-27. doi: 10.1016/j.mcat.2017.02.018
30	WANG L Y, ZHU D L, WANG J, et al Embryonic zeolite-assisted synthesis of SSZ-13 with superior efficiency and their excellent catalytic performance[J]. J Mater Chem A, 2021, 9, 15238-15245. doi: 10.1039/D1TA01452H
31	YANG Y N, WANG X L, YAO Y F The effects of reaction environment on photocatalytic methanol reforming studied by operando nuclear magnetic resonance spectroscopy[J]. Chinese J Magn Reson, 2020, 37 (1):104-113.
	杨以宁, 王雪路, 姚叶峰原位核磁共振技术研究反应环境对光催化甲醇重整过程的影响[J]. 波谱学杂志, 2020, 37 (1):104-113.
32	LIU W Q, SONG Y H, WANG X L, et al In operando nuclear magnetic resonance spectroscopy study on photocatalytic methanol reforming[J]. Chinese J Magn Reson, 2019, 36 (3):298-308.
	刘文卿, 宋艳红, 王雪璐, 等光催化甲醇重整机理的原位核磁共振研究[J]. 波谱学杂志, 2019, 36 (3):298-308.
33	HUNGER M, HORVATH T Conversion of propan-2-ol on zeolite LaNaY and HY investigated by gas chromatography and in situ MAS NMR spectroscopy under continuous-flow conditions[J]. J Catal, 1997, 167 (1):187-197. doi: 10.1006/jcat.1997.1562
34	WANG W, JIANG Y J, HUNGER M Mechanistic investigations of the methanol-to-olefin (MTO) process on acidic zeolite catalysts by in situ solid-state NMR spectroscopy[J]. Catal Today, 2006, 113 (1, 2):102-114.
35	HAW J F, NICHOLAS J B, SONG W G, et al Roles for cyclopentenyl cations in the synthesis of hydrocarbons from methanol on zeolite catalyst HZSM-5[J]. J Am Chem Soc, 2000, 122 (19):4763-4775. doi: 10.1021/ja994103x
36	THURBER K R, TYCKO R Measurement of sample temperatures under magic-angle spinning from the chemical shift and spin-lattice relaxation rate of ⁷⁹Br in KBr powder[J]. J Magn Reson, 2009, 196 (1):84-87. doi: 10.1016/j.jmr.2008.09.019
37	HOU G J, YAN S, TREBOSC J, et al Broadband homonuclear correlation spectroscopy driven by combined R2(n)(v) sequences under fast magic angle spinning for NMR structural analysis of organic and biological solids[J]. J Magn Reson, 2013, 232, 18-30. doi: 10.1016/j.jmr.2013.04.009
38	SUN T, CHEN W, XU S, et al The first carbon-carbon bond formation mechanism in methanol-to-hydrocarbons process over chabazite zeolite[J]. Chem, 2021, doi: 10.1016/j.chempr.2021.05.023
39	STEPANOV A G, LUZGIN M V, ROMANNIKOV V N, et al The nature, structure, and composition of adsorbed hydrocarbon products of ambient temperature oligomerization of ethene on acidic zeolite H-ZSM-5[J]. J Catal, 1998, 178, 466-477. doi: 10.1006/jcat.1998.2172
40	FRIDGEN T D, MCMAHON T B The reaction of protonated dimethyl ether with dimethyl Ether: temperature and isotope effects on the methyl cation transfer reaction forming trimethyloxonium cation and methanol[J]. J Am Chem Soc, 2001, 123 (17):3980-3985. doi: 10.1021/ja002972c

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