H-SAPO-34分子筛催化醇类转化的差异性研究

doi:10.11938/cjmr20222981

摘要/Abstract

摘要：

本文研究了H-SAPO-34催化甲醇和丁醇转化反应及其产物分布的差异，结合气相色谱-质谱（GC-MS）联用、¹³C交叉极化魔角旋转核磁共振（¹³C CP MAS NMR）技术捕获了反应过程中生成的重要反应中间物种.甲醇转化过程以乙烯、丙烯和丁烯为主要产物；而丁醇转化过程中主要产物是丁醇脱水生成的丁烯，反应初期以丙烯和丁烯作为主要产物.两种醇类转化均以低碳烯烃作为主要产物，且存留物种和¹³C CP MAS NMR分析均观察到芳烃物种，说明H-SAPO-34催化甲醇和丁醇转化存留在催化剂上的有机物种相近.虽然起始于不同的醇类反应，但H-SAPO-34上限域空间的酸催化环境都能引导甲醇和丁醇制取低碳烯烃的反应过程.

关键词: ¹³C交叉极化魔角旋转核磁共振(¹³C CP MAS NMR), 醇类转化, 分子筛催化, 反应中间物种

Abstract:

In this paper, the conversion of methanol and butanol and the differences in product distribution over H-SAPO-34 were investigated. Some important reaction intermediates were captured during the reaction process by using gas chromatography-mass spectrometry (GC-MS) and ¹³C cross polarization magic angle spinning nuclear magnetic resonance (¹³C CP MAS NMR) spectroscopy. In the methanol conversion process, ethene, propene and butene are the main products, while in the butanol conversion process, butanol is mainly dehydrated to form butene, and propene and butene are the main products in the initial stage. Light olefins are generated from both methanol and butanol conversion over H-SAPO-34. Furthermore, the aromatic species were observed in both retained species analysis and ¹³C CP MAS NMR, indicating that similar organic species confined in the H-SAPO-34 during the conversion of alcohols. Starting from different kinds of alcohols, the acid-catalysis environment in the confined space of H-SAPO-34 can catalyze the methanol and butanol conversion to produce light olefins.

Key words: ¹³C CP MAS NMR, alcohol conversion, molecular sieve catalysis, reaction intermediate species

中图分类号:

O482.53

顾雅婷, 张雯娜, 韩晶峰, 楼才溢, 陈慧慧, 徐舒涛, 魏迎旭, 刘中民. H-SAPO-34分子筛催化醇类转化的差异性研究[J]. 波谱学杂志, 2022, 39(4): 428-438.

Ya-ting GU, Wen-na ZHANG, Jing-feng HAN, Cai-yi LOU, Hui-hui CHEN, Shu-tao XU, Ying-xu WEI, Zhong-min LIU. Investigation on the Differences of the Alcohols Conversion over H-SAPO-34 Zeolite[J]. Chinese Journal of Magnetic Resonance, 2022, 39(4): 428-438.

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参考文献 46

1	MASCAL M Chemicals from biobutanol: technologies and markets[J]. Biofuel Bioprod Bior, 2012, 6 (4): 483- 493. doi: 10.1002/bbb.1328
2	TRINDADE W R D, DOS SANTOS R G Review on the characteristics of butanol, its production and use as fuel in internal combustion engines[J]. Renew Sust Energ Rev, 2017, 69, 642- 651. doi: 10.1016/j.rser.2016.11.213
3	VARGAS J M, MORELATO L H T, ORTEGA J O, et al Upgrading 1-butanol to unsaturated, carbonyl and aromatic compounds: a new synthesis approach to produce important organic building blocks[J]. Green Chem, 2020, 22 (8): 2365- 2369. doi: 10.1039/D0GC00254B
4	JOHN M, ALEXOPOULOS K, REYNIERS M F, et al First-principles kinetic study on the effect of the zeolite framework on 1-butanol dehydration[J]. ACS Catal, 2016, 6 (7): 4081- 4094. doi: 10.1021/acscatal.6b00708
5	PALLA V C S, SHEE D, MAITY S K Conversion of n-butanol to gasoline range hydrocarbons, butylenes and aromatics[J]. Appl Catal A-Gen, 2016, 526, 28- 36. doi: 10.1016/j.apcata.2016.07.026
6	JOHN M, ALEXOPOULOS K, REYNIERS M F, et al Mechanistic insights into the formation of butene isomers from 1-butanol in H-ZSM-5: DFT based microkinetic modelling[J]. Catal Sci Technol, 2017, 7 (5): 1055- 1072. doi: 10.1039/C6CY02474B
7	PALLA V C S, SHEE D, MAITY S K Production of aromatics from n-butanol over H-ZSM-5, H-beta, and gamma-Al₂O₃: Role of silica/alumina mole ratio and effect of pressure[J]. ACS Sustain Chem Eng, 2020, 8 (40): 15230- 15242. doi: 10.1021/acssuschemeng.0c04888
8	MAKAROVA M A, PAUKSHTIS E A, THOMAS J M, et al Dehydration of n-butanol on zeolite H-ZSM-5 and amorphous aluminosilicate-detailed mechanistic study and the effect of pore confinement[J]. J Catal, 1994, 149 (1): 36- 51. doi: 10.1006/jcat.1994.1270
9	JOHN M, ALEXOPOULOS K, REYNIERS M F, et al Reaction path analysis for 1-butanol dehydration in H-ZSM-5 zeolite: Ab initio and microkinetic modeling[J]. J Catal, 2015, 330, 28- 45. doi: 10.1016/j.jcat.2015.07.005
10	PHUNG T K, HERNANDEZ L P, LAGAZZO A, et al Dehydration of ethanol over zeolites, silica alumina and alumina: Lewis acidity, Bronsted acidity and confinement effects[J]. Appl Catal A-Gen, 2015, 493, 77- 89. doi: 10.1016/j.apcata.2014.12.047
11	GUNST D, ALEXOPOULOS K, VAN DER BORGHT K, et al Study of butanol conversion to butenes over H-ZSM-5: Effect of chemical structure on activity, selectivity and reaction pathways[J]. Appl Catal A-Gen, 2017, 539, 1- 12. doi: 10.1016/j.apcata.2017.03.036
12	SMIT B, MAESEN T L M Towards a molecular understanding of shape selectivity[J]. Nature, 2008, 451 (7179): 671- 678. doi: 10.1038/nature06552
13	SMIT B, MAESEN T L M Molecular simulations of zeolites: Adsorption, diffusion, and shape selectivity[J]. Chem Rev, 2008, 108 (10): 4125- 4184. doi: 10.1021/cr8002642
14	MOLINER M, MARTINEZ C, CORMA A Multipore zeolites: Synthesis and catalytic applications[J]. Angew Chem Int Edit, 2015, 54 (12): 3560- 3579. doi: 10.1002/anie.201406344
15	ZHONG J W, HAN J F, WEI Y X, et al Catalysts and shape selective catalysis in the methanol-to-olefin (MTO) reaction[J]. J Catal, 2021, 396, 23- 31. doi: 10.1016/j.jcat.2021.01.027
16	OLSBYE U, SVELLE S, BJORGEN M, et al Conversion of methanol to hydrocarbons: How zeolite cavity and pore size controls product selectivity[J]. Angew Chem Int Edit, 2012, 51 (24): 5810- 5831. doi: 10.1002/anie.201103657
17	CHU Y, JI P, YI X, et al Strong or weak acid, which is more efficient for Beckmann rearrangement reaction over solid acid catalysts[J]. Catal Sci Technol, 2015, 5 (7): 3675- 3681. doi: 10.1039/C5CY00619H
18	高树树, 徐舒涛, 魏迎旭, 等固体核磁共振技术在甲醇制烯烃反应中的应用[J]. 波谱学杂志, 2021, 38 (4): 433- 447.
	GAO S S, XU S T, WEI Y X, et al Applications of solid-state nuclear magnetic resonance spectroscopy in methanol-to-olefins reaction[J]. Chinese J Magn Reson, 2021, 38 (4): 433- 447.
19	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.
	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.
20	ATKINS M P. Process for the production of olefins: WO, 21139[P]. 1993-10-28.
21	MADEIRA F F, GNEP N S, MAGNOUX P, et al Ethanol transformation over HFAU, HBEA and HMFI zeolites presenting similar Bronsted acidity[J]. Appl Catal A-Gen, 2009, 367 (1-2): 39- 46. doi: 10.1016/j.apcata.2009.07.033
22	MADEIRA F F, BEN TAYEB K, PINARD L, et al Ethanol transformation into hydrocarbons on ZSM-5 zeolites: Influence of Si/Al ratio on catalytic performances and deactivation rate. Study of the radical species role[J]. Appl Catal A-Gen, 2012, 443, 171- 180.
23	NGUYEN T M, LEVANMAO 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
24	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
25	MENTZEL U V, SHUNMUGAVEL S, HRUBY S L, et al High yield of liquid range olefins obtained by converting i-propanol over zeolite H-ZSM-5[J]. J Am Chem Soc, 2009, 131 (46): 17009- 17013. doi: 10.1021/ja907692t
26	ZHANG D Z, AL-HAJRI R, BARRI S A I, et al One-step dehydration and isomerisation of n-butanol to iso-butene over zeolite catalysts[J]. Chem Commun, 2010, 46 (23): 4088- 4090. doi: 10.1039/c002240c
27	ZHANG D Z, BARRI S A I, CHADWICK D n-Butanol to iso-butene in one-step over zeolite catalysts[J]. Appl Catal A-Gen, 2011, 403 (1-2): 1- 11. doi: 10.1016/j.apcata.2011.05.037
28	KNöZINGER H, BüHL H, KOCHLOEFL K The dehydration of alcohols on alumina: XIV. Reactivity and mechanism[J]. J Catal, 1972, 24 (1): 57- 68. doi: 10.1016/0021-9517(72)90007-3
29	CHEN J R, LI J Z, WEI Y X, et al Spatial confinement effects of cage-type SAPO molecular sieves on product distribution and coke formation in methanol-to-olefin reaction[J]. Catal Commun, 2014, 4636- 40.
30	WU X Q, XU S T, WEI Y X, et al Evolution of C-C bond formation in the methanol-to-olefins process: From direct coupling to autocatalysis[J]. ACS Catal, 2018, 8 (8): 7356- 7361. doi: 10.1021/acscatal.8b02385
31	GUISNET M, COSTAL L, RIBEIRO F R Prevention of zeolite deactivation by coking[J]. J Mol Catal A: Chem, 2009, 305 (1-2): 69- 83. doi: 10.1016/j.molcata.2008.11.012
32	HAN J F, LIU Z Q, LI H, et al Simultaneous evaluation of reaction and diffusion over molecular sieves for shape-selective catalysis[J]. ACS Catal, 2020, 10 (15): 8727- 8735. doi: 10.1021/acscatal.0c02054
33	ILIAS S, KHARE R, MALEK A, et al A descriptor for the relative propagation of the aromatic- and olefin-based cycles in methanol-to-hydrocarbons conversion on H-ZSM-5[J]. J Catal, 2013, 303, 135- 140. doi: 10.1016/j.jcat.2013.03.021
34	WANG C M, WANG Y D, XIE Z K Verification of the dual cycle mechanism for methanol-to-olefin conversion in HSAPO-34: a methylbenzene-based cycle from DFT calculations[J]. Catal Sci Technol, 2014, 4 (8): 2631- 2638. doi: 10.1039/C4CY00262H
35	ZHANG W N, ZHI Y C, HUANG J D, et al Methanol to olefins reaction route based on methylcyclopentadienes as critical intermediates[J]. ACS Catal, 2019, 9 (8): 7373- 7379. doi: 10.1021/acscatal.9b02487
36	SONG W G, FU H, HAW J F Supramolecular origins of product selectivity for methanol-to-olefin catalysis on H-SAPO-34[J]. J Am Chem Soc, 2001, 123 (20): 4749- 4754. doi: 10.1021/ja0041167
37	WANG C, XU J, QI G D, et al Methylbenzene hydrocarbon pool in methanol-to-olefins conversion over zeolite H-ZSM-5[J]. J Catal, 2015, 332, 127- 137. doi: 10.1016/j.jcat.2015.10.001
38	YU B W, ZHANG W N, WEI Y X, et al Capture and identification of coke precursors to elucidate the deactivation route of the methanol-to-olefin process over H-SAPO-34[J]. Chem Commun, 2020, 56 (58): 8063- 8066. doi: 10.1039/D0CC02408B
39	MUNSON E J, KHEIR A A, LAZO N D, et al In situ solid-state NMR study of methanol-to-gasoline chemistry in zeolite H-ZSM-5[J]. J Phys Chem, 1993, 97 (16): 4248- 4248. doi: 10.1021/j100118a051
40	XU S T, ZHENG A M, WEI Y X, et al Direct observation of cyclic carbenium ions and their role in the catalytic cycle of the methanol-to-olefin reaction over chabazite zeolites[J]. Angew Chem Int Edit, 2013, 52 (44): 11564- 11568. doi: 10.1002/anie.201303586
41	WANG W, JIAO J, JIANG Y J, et al Formation and decomposition of surface ethoxy species on acidic zeolite Y[J]. Chemphyschem, 2005, 6 (8): 1467- 1469. doi: 10.1002/cphc.200500262
42	JIANG Y, HUANG J, REDDY MARTHALA V R, et al In situ MAS NMR–UV/Vis investigation of H-SAPO-34 catalysts partially coked in the methanol-to-olefin conversion under continuous-flow conditions and of their regeneration[J]. Micropor Mesopor Mater, 2007, 105 (1-2): 132- 139. doi: 10.1016/j.micromeso.2007.05.028
43	DAI W L, WANG C M, DYBALLA M, et al Understanding the early stages of the methanol-to-olefin conversion on H-SAPO-34[J]. ACS Catal, 2015, 5 (1): 317- 326. doi: 10.1021/cs5015749
44	ZHANG W N, ZHANG M Z, XU S T, et al Methylcyclopentenyl cations linking initial stage and highly efficient stage in methanol-to-hydrocarbon process[J]. ACS Catal, 2020, 10 (8): 4510- 4516. doi: 10.1021/acscatal.0c00799
45	STEPANOV A G, SIDELNIKOV V N, ZAMARAEV K I In situ ¹³C solid-state NMR and ex situ GC-MS analysis of the products of tert-butyl alcohol dehydration on H-ZSM-5 zeolite catalyst[J]. Chem-Eur J, 1996, 2 (2): 157- 167. doi: 10.1002/chem.19960020207
46	WANG C, WANG Q, XU J, et al Direct detection of supramolecular reaction centers in the methanol-to-olefins conversion over zeolite H-ZSM-5 by ¹³C-²⁷Al solid-state NMR spectroscopy[J]. Angew Chem Int Ed, 2016, 55 (7): 2507- 2511. doi: 10.1002/anie.201510920