Citation: Zhao Shu-Fang, Yao Xu-Ting, Yan Bing-Hui, Li Li, Liu Yue-Ming, He Ming-Yuan. Flexible regulation of C₃⁼/C₂⁼ ratio in methanol-to-hydrocarbons by delicate control of acidity of ZSM-5 catalyst[J]. Chinese Chemical Letters, ;2017, 28(6): 1318-1323. doi: 10.1016/j.cclet.2017.03.023 shu

Flexible regulation of C₃⁼/C₂⁼ ratio in methanol-to-hydrocarbons by delicate control of acidity of ZSM-5 catalyst

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China

Corresponding author: Liu Yue-Ming, ymliu@chem.ecnu.edu.cn
Received Date: 7 March 2017
Revised Date: 14 March 2017
Accepted Date: 14 March 2017
Available Online: 14 June 2017

Figures(4)

A very wide range of the C₃⁼/C₂⁼ ratio from 0.72 to 7.56 with high C₂⁼+C₃⁼ selectivity of around 66% in the methanol-to-hydrocarbons process can be realized over ZSM-5 catalyst in a fixed-bed reactor. We firstly conduct a single factor experiment of acidity, demonstrating that the acidity control of MTH catalyst is crucial to adjusting light olefins selectivity. Weak Brønsted acid sites favor to high C₃⁼ selectivity (59.0%) due to the suppression of the conversion reactions from the alkene-based to arene-based cycle, while Lewis acid sites conduce to high C₂⁼ selectivity (39.6%) due to the promotion of the conversion reactions for the aromatics formation and steric constraints of Lewis acid sites making the aromatics crack more efficiently to C₂⁼.
- Acidity,
- Methanol-to-hydrocarbons,
- Lewis acidity,
- Olefins,
- Zeolites
1. [1]
  (a) H.M. Torres Galvis, K.P. de Jong, Catalysts for production of lower olefins from synthesis gas:a review, ACS Catal. 3(2013) 2130-2149;
  (b) K. Cheng, B. Gu, X. Liu, et al., Direct and highly selective conversion of synthesis gas into lower olefins:design of a bifunctional catalyst combining methanol synthesis and carbon-carbon coupling, Angew. Chem. Int. Ed. 55(2016) 4725-4728.
2. [2]
  (a) S. Xu, A. Zheng, Y. Wei, et al., Direct observation of cyclic carbenium ions and their role in the catalytic cycle of the methanol-to-olefin reaction over chabazite zeolites, Angew. Chem. 52(2013) 11564-11568;
  (b) U. Olsbye, S. Svelle, K.P. Lillerud, et al., The formation and degradation of active species during methanol conversion over protonated zeotype catalysts, Chem. Soc. Rev. 44(2015) 7155-7176.
3. [3]
  Tian P., Wei Y., Ye M., Liu Z.. Methanol to olefins (MTO):from fundamentals to commercialization[J]. ACS Catal., 2015,5:1922-1938. doi: 10.1021/acscatal.5b00007
4. [4]
  (a) J. Liu, C.X. Zhang, Z.H. Shen, et al., Methanol to propylene:effect of phosphorus on a high silica HZSM-5 catalyst, Catal. Commun. 10(2009) 1506-1509;
  (b) Y.J. Lee, Y.W. Kim, N. Viswanadham, K.W. Jun, J.W. Bae, Novel aluminophosphate (AlPO) bound ZSM-5 extrudates with improved catalytic properties for methanol to propylene (MTP) reaction, Appl. Catal. A:Gen. 374(2010) 18-25;
  (c) U. Olsbye, S. Svelle, M. Bjørgen, et al., Conversion of methanol to hydrocarbons:how zeolite cavity and pore size controls product selectivity, Angew. Chem. Int. Ed. 51(2012) 5810-5831.
5. [5]
  (a) S. Svelle, S. Kolboe, O. Swang, U. Olsbye, Methylation of alkenes and methylbenzenes by dimethyl ether or methanol on acidic zeolites, J. Phys. Chem. B 109(2005) 12874-12878;
  (b) S. Svelle, F. Joensen, J. Nerlov, et al., Conversion of methanol into hydrocarbons over zeolite H-ZSM-5:ethene formation is mechanistically separated from the formation of higher alkenes, J. Am. Chem. Soc. 128(2006) 14770-14771;
  (c) M. Bjørgen, S. Svelle, F. Joensen, et al., Conversion of methanol to hydrocarbons over zeolite H-ZSM-5:on the origin of the olefinic species, J. Catal. 249(2007) 195-207;
  (d) V. Van Speybroeck, J. Van der Mynsbrugge, M. Vandichel, et al., First principle kinetic studies of zeolite-catalyzed methylation reactions, J. Am. Chem. Soc. 133(2011) 888-899;
  (e) S. Ilias, R. Khare, A. Malek, A. Bhan, A descriptor for the relative propagation of the aromatic-and olefin-based cycles in methanol-to-hydrocarbons conversion on H-ZSM-5, J. Catal. 303(2013) 135-140.
6. [6]
  (a) D. Mores, J. Kornatowski, U. Olsbye, B.M. Weckhuysen, Coke formation during the methanol-to-olefin conversion:in situ microspectroscopy on individual H-ZSM-5 crystals with different Brønsted acidity, Chem. Eur. J. 17(2011) 2874-2884;
  (b) S.M. Almutairi, B. Mezari, E.A. Pidko, P.C. Magusin, E.J. Hensen, Influence of steaming on the acidity and the methanol conversion reaction of HZSM-5 zeolite, J. Catal. 307(2013) 194-203.
7. [7]
  Wang C., Xu J., Qi G.. Methylbenzene hydrocarbon pool in methanol-toolefins conversion over zeolite H-ZSM-5[J]. J. Catal., 2015,332:127-137. doi: 10.1016/j.jcat.2015.10.001
8. [8]
  (a) F. Bleken, M. Bjørgen, L. Palumbo, et al., The effect of acid strength on the conversion of methanol to olefins over acidic microporous catalysts with the CHA topology, Top. Catal. 52(2009) 218-228;
  (b) M.W. Erichsen, S. Svelle, U. Olsbye, The influence of catalyst acid strength on the methanol to hydrocarbons (MTH) reaction, Catal. Today 215(2013) 216-223;
  (c) M.W. Erichsen, S. Svelle, U. Olsbye, H-SAPO-5 as methanol-to-olefins (MTO) model catalyst:Towards elucidating the effects of acid strength, J. Catal. 298(2013) 94-101;
  (d) M.W. Erichsen, K. De Wispelaere, K. Hemelsoet, et al., How zeolitic acid strength and composition alter the reactivity of alkenes and aromatics towards methanol, J. Catal. 328(2015) 186-196.
9. [9]
  Zhao S.F., Yang D., Zhang X.W.. ZSM-5 with controllable acidity as an efficient catalyst for a highly adjustable propene/ethene ratio in the 1-butene cracking[J]. Chem. Commun., 2016,52:11191-11194. doi: 10.1039/C6CC04680K
10. [10]
  Borghèse S., Haouas M., Sommer J., Taulelle F.. Activation energy of hydride transfer between isobutane molecules on USY zeolite. First direct experimental measurement by in situ MAS NMR using mixtures of isotopomers[J]. J. Catal., 2013,305:130-134. doi: 10.1016/j.jcat.2013.05.004
11. [11]
  Schallmoser S., Ikuno T., Wagenhofer M.F.. Impact of the local environment of Brønsted acid sites in ZSM-5 on the catalytic activity in npentane cracking[J]. J. Catal., 2014,316:93-102. doi: 10.1016/j.jcat.2014.05.004
12. [12]
  (a) L.F. Lin, C.F. Qiu, Z.X. Zhuo, et al., Acid strength controlled reaction pathways for the catalytic cracking of 1-butene to propene over ZSM-5, J. Catal. 309(2014) 136-145;
  (b) L.F. Lin, S.F. Zhao, D.W. Zhang, et al., Acid strength controlled reaction pathways for the catalytic cracking of 1-pentene to propene over ZSM-5, ACS Catal. 5(2015) 4048-4059.
13. [13]
  Guo W., Wu W., Luo M., Xiao W.. Modeling of diffusion and reaction in monolithic catalysts for the methanol-to-propylene process[J]. Fuel Process. Technol., 2013,108:133-138. doi: 10.1016/j.fuproc.2012.06.005
14. [14]
  Svelle S., Olsbye U., Joensen F., Bjørgen M.. Conversion of methanol to alkenes over medium-and large-pore acidic zeolites:steric manipulation of the reaction intermediates governs the ethene/propene product selectivity[J]. J. Phys. Chem. C, 2007,111:17981-17984. doi: 10.1021/jp077331j
15. [15]
  Gounder R., Jones A.J., Carr R.T., Iglesia E.. Solvation and acid strength effects on catalysis by faujasite zeolites[J]. J. Catal., 2012,286:214-223. doi: 10.1016/j.jcat.2011.11.002
16. [16]
  Huang J., Jiang Y., Marthala V.R.. Characterization and acidic properties of aluminum-exchanged zeolites X and Y[J]. J. Phys. Chem. C, 2008,112:3811-3818. doi: 10.1021/jp7103616
17. [17]
  Arudra P., Bhuiyan T.I., Akhtar M.N.. Silicalite-1 as efficient catalyst for production of propene from 1-butene[J]. ACS Catal., 2014,4:4205-4214. doi: 10.1021/cs5009255
1. [1]
  Runze Liu , Yankai Bian , Weili Dai . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: A combined probe-assisted 1H MAS NMR and NH3-TPD investigation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100250-100250. doi: 10.1016/j.cjsc.2024.100250
2. [2]
  Ruijing Wang , Shixuan Wang , Chenghui Zhu , Jianze Zhang , Richard N. Zare , Chongqin Zhu , Xinxing Zhang . Increased acidity of nitrogen heterocyclic compounds on water microdroplets facilitates CO₂ capture. Chinese Chemical Letters, 2026, 37(4): 111547-. doi: 10.1016/j.cclet.2025.111547
3. [3]
  Huimin Luan , Qinming Wu , Jianping Wu , Xiangju Meng , Feng-Shou Xiao . Templates for the synthesis of zeolites. Chinese Journal of Structural Chemistry, 2024, 43(4): 100252-100252. doi: 10.1016/j.cjsc.2024.100252
4. [4]
  Jiaze Wang , Rui Lin , Yurong Hu , Lin Li , Wenfu Yan , Yi Li . Topology-based pore matching for rapid screening of candidate zeolites. Chinese Chemical Letters, 2026, 37(12): 112613-. doi: 10.1016/j.cclet.2026.112613
5. [5]
  Jie Ma , Jianxiang Wang , Jianhua Yuan , Xiao Liu , Yun Yang , Fei Yu . The regulating strategy of hierarchical structure and acidity in zeolites and application of gas adsorption: A review. Chinese Chemical Letters, 2024, 35(11): 109693-. doi: 10.1016/j.cclet.2024.109693
6. [6]
  Junpu Yang , Yaoyao Bai , Huangjie Lu , Jingqi Ma , Jian Xie , Jie Qiu , Xiaofeng Guo , Yaxing Wang , Shuao Wang , Jian Lin . Emergence of acidity modulation as a new strategy for eliciting stable radicals in multi-stimuli-responsive metal-oxo clusters. Chinese Chemical Letters, 2026, 37(11): 111702-. doi: 10.1016/j.cclet.2025.111702
7. [7]
  Haiying Wei , Daqing Yang , Mingtao Run , Guoyan Huo . Examination and Analysis on Rationality of Experimental Design: Based on Reaction of Potassium Permanganate with Potassium Bormide. University Chemistry, 2024, 39(10): 283-288. doi: 10.12461/PKU.DXHX202404068
8. [8]
  Ruikang Su , Muyan Bai , Zhiqing Liu , Fang Fang , Yuena Yu . Wittig反应与可见光氧化还原催化融合构建烯烃. University Chemistry, 2026, 41(8): 370-379. doi: 10.12461/PKU.DXHX202507075
9. [9]
  Xinyu You , Xin Zhang , Shican Jiang , Yiru Ye , Lin Gu , Hexun Zhou , Pandong Ma , Jamal Ftouni , Abhishek Dutta Chowdhury . Efficacy of Ca/ZSM-5 zeolites derived from precipitated calcium carbonate in the methanol-to-olefin process. Chinese Journal of Structural Chemistry, 2024, 43(4): 100265-100265. doi: 10.1016/j.cjsc.2024.100265
10. [10]
  Ning LI , Siyu DU , Xueyi WANG , Hui YANG , Tao ZHOU , Zhimin GUAN , Peng FEI , Hongfang MA , Shang JIANG . Preparation and efficient catalysis for olefins epoxidation of a polyoxovanadate-based hybrid. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 799-808. doi: 10.11862/CJIC.20230372
11. [11]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
12. [12]
  Junhua Li , Tianci Shen , Yahui Zhuang , Yu Fu , Yian Shi . Pd-Catalyzed highly regioselective migratory hydroesterification of internal olefins with formates. Chinese Chemical Letters, 2025, 36(7): 110599-. doi: 10.1016/j.cclet.2024.110599
13. [13]
  Yuhang Li , Yang Ling , Yanhang Ma . Application of three-dimensional electron diffraction in structure determination of zeolites. Chinese Journal of Structural Chemistry, 2024, 43(4): 100237-100237. doi: 10.1016/j.cjsc.2024.100237
14. [14]
  Qinming Wu , Xiangju Meng . New zeolites with extra-stable extra-large-pore. Chinese Journal of Structural Chemistry, 2024, 43(6): 100310-100310. doi: 10.1016/j.cjsc.2024.100310
15. [15]
  Teng-Yu Huang , Junliang Sun , De-Xian Wang , Qi-Qiang Wang . Recent progress in chiral zeolites: Structure, synthesis, characterization and applications. Chinese Chemical Letters, 2024, 35(12): 109758-. doi: 10.1016/j.cclet.2024.109758
16. [16]
  Cui Xin , Wei-Min He . Direct asymmetric α-alkylation of β-ketocarbonyl compounds with simple olefins by photoredox-nickel-hydrogen atom transfer triple catalysis. Chinese Chemical Letters, 2026, 37(6): 112351-. doi: 10.1016/j.cclet.2025.112351
17. [17]
  Jun-Xian Chen , Xian-Xian Xiao , Libo Li , Jinping Li , Rui-Biao Lin , Xiao-Ming Chen . Fine-tuning of Hofmann-type metal-organic frameworks for highly efficient separation of C4 olefins. Chinese Journal of Structural Chemistry, 2025, 44(12): 100744-100744. doi: 10.1016/j.cjsc.2025.100744
18. [18]
  Kun Yang , Anhui Li , Peng Zhang , Guilin Liu , Liusai Huang , Yumeng Fo , Luyuan Yang , Xiangyang Ji , Jian Liu , Weiyu Song . Hierarchical zeolites stabilized cobalt(Ⅱ) as propane dehydrogenation catalyst: Enhanced activity and coke tolerance via alkaline post-treatment. Chinese Chemical Letters, 2025, 36(5): 110663-. doi: 10.1016/j.cclet.2024.110663
19. [19]
  Meichen Jiao , Sitong Liu , Chunmin Jia , Hao Xu , Zhiguo Zhu , Peng Wu , Xian-Ming Zhang . Convenient transformation of FAU zeolites to IWV aluminosilicates with adjustable Al sites for Baeyer-Villiger oxidation. Chinese Journal of Structural Chemistry, 2025, 44(9): 100654-100654. doi: 10.1016/j.cjsc.2025.100654
20. [20]
  Basem E. Keshta , Lingyao Wang , Yuanbin Zhang . Accelerated discovery of stable and extra-large-pore nano zeolites: A paradigm shift in catalytic materials. Chinese Journal of Structural Chemistry, 2025, 44(12): 100720-100720. doi: 10.1016/j.cjsc.2025.100720

Get Citation

PDF

XML

Metrics

PDF Downloads(3)
Abstract views(3246)
HTML views(96)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Flexible regulation of C3=/C2= ratio in methanol-to-hydrocarbons by delicate control of acidity of ZSM-5 catalyst

Metrics

通讯作者: 陈斌, bchen63@163.com

Flexible regulation of C₃⁼/C₂⁼ ratio in methanol-to-hydrocarbons by delicate control of acidity of ZSM-5 catalyst