Citation: LI Jun-Nan, PU Min, SU Yong, HE Jing, EVANS David G.. Theoretical Study on the Synthesis of Ethyl Tertiary Butyl Ether over HZSM-5 Zeolite[J]. Acta Physico-Chimica Sinica, ;2012, 28(07): 1630-1636. doi: 10.3866/PKU.WHXB201204171 shu

Theoretical Study on the Synthesis of Ethyl Tertiary Butyl Ether over HZSM-5 Zeolite

1.
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China

Received Date: 1 December 2011
Available Online: 17 April 2012

The formation mechanism of ethyl tertiary butyl ether (ETBE) from ethanol and isobutene catalyzed by HZSM-5 has been investigated using the ONIOM (B3LYP/6-31G(d,p):UFF) method. The calculation results of the reactants adsorbability reveal that the interaction between ethanol and the acidic sites on HZSM-5 leads to the formation of hydrogen bonds. The interaction between isobutene and Brönsted acidic sites leads to the formation of a π-complex. It is subsequently found that the mechanism of the ETBE formation from ethanol and isobutene catalyzed by HZSM-5 is a concerted reaction, and that the order of reactant adsorption onto HZSM-5 affected the reaction. The favorable pathway is based on the complex formed by the simultaneous adsorption of ethanol and isobutene, in which the H atom of the π-complex is transferred to the C atom of the C＝C in isobutene, and the O atom of the adsorbed ethanol is transferred to the other C atom of the C＝C to form the C－O bond. In this process, the proton of the acidic sites adds to the C＝C bond forming the C－H bond, and the H atom of the ethanol hydroxyl interacts with acidic sites, generating a new proton. The corresponding lowest energy barrier was 25.14 kJ·mol^-1.
- Ethanol,
- Isobutene,
- HZSM-5 zeolite,
- ONIOM,
- Ethyl tertiary butyl ether
1. [1]
  
  (1) Nadim, F.; Zack, P.; Hoag, G. E.; Liu, S. Energ. Policy 2001,29, 1. doi: 10.1016/S0301-4215(00)00099-9
2. [2]
  (2) Oktar, N.; Murtezaoglu, K.; Dogu, G.; nderten, I.; Dogu, T.J. Chem. Technol. Biotechnol. 1999, 74, 155. doi: 10.1002/(SICI)1097-4660(199902)74:2<155::AID-JCTB982>3.0.CO;2-T
3. [3]
  (3) VanWezel, A.; Puijker, L.; Vink, C.; Versteegh, A.; De Voogt, P.Chemosphere 2009, 76, 672. doi: 10.1016/j.chemosphere.2009.03.073
4. [4]
  (4) Hernandez-Perez, G.; Fayolle, F.; Vandecasteele, J. P. Appl. Microbiol. Biot. 2001, 55, 117. doi: 10.1007/s002530000482
5. [5]
  (5) Kharoune, M.; Pauss, A.; Lebeault, J. Water Res. 2001, 35,1665. doi: 10.1016/S0043-1354(00)00448-6
6. [6]
  (6) Davidson, J. M.; Creek, D. N. J. Environ. Monitor. 2000, 1, 31.
7. [7]
  (7) Rosell, M.; Lacorte, S.; Barcelo, D. TrAC-Trend. Anal. Chem.2006, 25, 1016. doi: 10.1016/j.trac.2006.06.011
8. [8]
  (8) Puziy, A.; Poddubnaya, O.; Kochkin, Y. N.; Vlasenko, N.;Tsyba, M. Carbon 2010, 48, 706. doi: 10.1016/j.carbon.2009.10.015
9. [9]
  (9) Kadi, B. E.; Baronnet, F. J. Chim. Phys. 1995, 92, 706.
10. [10]
  (10) Vlasenko, N. V.; Kochkin, Y. N.; Topka, A. V.; Strizhak, P. E.Appl. Catal. A-Gen. 2009, 362, 82. doi: 10.1016/j.apcata.2009.04.021
11. [11]
  (11) Bielanski, A.; Dziembaj, R.; Malechka-Lubanska, A.;Pozniczek, J.; Hasik, M.; Drozdek, M. J. Catal. 1999, 185,363. doi: 10.1006/jcat.1999.2501
12. [12]
  (12) Kovalchuk, T.; Kochkin, J. N.; Sfihi, H.; Zaitsev, V.; Fraissard,J. J. Catal. 2009, 263, 247. doi: 10.1016/j.jcat.2009.02.016
13. [13]
  (13) Corma, A. J. Catal. 2003, 216, 298. doi: 10.1016/S0021-9517(02)00132-X
14. [14]
  (14) Vlasenko, N.; Kochkin, Y. N.; Puziy, A. J. Mol. Catal. A-Chem.2006, 253, 192. doi: 10.1016/j.molcata.2006.03.041
15. [15]
  (15) Collignon, F.; Poncelet, G. J. Catal. 2001, 202, 68. doi: 10.1006/jcat.2001.3280
16. [16]
  (16) Li, Z. Y.; Zhu, Y.; Xiang, S. H. Chin. J. Catal. 2003, 24, 294.[李自运, 朱岩, 项寿鹤. 催化学报, 2003, 24, 294.]
17. [17]
  (17) Liu, Y.; Zhang,W.; Pinnavaia, T. J. Angew. Chem. Int. Edit.2001, 40, 1255. doi: 10.1002/1521-3773(20010401)40:7<1255:AID-ANIE1255>3.0.CO;2-U
18. [18]
  (18) Oudshoorn, O.; Janissen, M.; Van Kooten,W.; Jansen, J.; VanBekkum, H.; Van den Bleek, C.; Calis, H. Chem. Eng. Sci.1999, 54, 1413. doi: 10.1016/S0009-2509(99)00081-0
19. [19]
  (19) Alcontara, R.; Alcontara, E.; Canoira, L.; Franco, M. J.; Martan,I.; Navarro, A. React. Kinet. Catal. Lett. 2000, 69, 239. doi: 10.1023/A:1005631313062
20. [20]
  (20) Habenicht, C.; Kam, L. C.;Wilschut, M. J. Ind. Eng. Chem. Res. 1995, 34, 3784. doi: 10.1021/ie00038a015
21. [21]
  (21) Larsen, G.; Lotero, E.; Morquez, M.; Silva, H. J. Catal. 1995,157, 645. doi: 10.1006/jcat.1995.1330
22. [22]
  (22) Sola, L.; Pericos, M. A.; Cunill, F.; Izquierdo, J. F. Ind. Eng. Chem. Res. 1997, 36, 2012. doi: 10.1021/ie960753n
23. [23]
  (23) Bohm, H.; Baronnet, F.; EloKadi, B. Phys. Chem. Chem. Phys.2000, 2, 1929. doi: 10.1039/B000415o
24. [24]
  (24) Bolun, Y.; Sanba, Y.; Ruiqing, Y.; Miaoli, H.; Gaowen, Y.Chem. Eng. (China) 2000, 27, 5. doi: CNKI:SUN:IMIY.02000-05-006
25. [25]
  (25) Boronat, M.; Viruela, P. M.; Corma, A. J. Am. Chem. Soc.2004, 126, 3300. doi: 10.1021/ja039432a
26. [26]
  (26) Parr, R. G.; Yang,W. Density Functional Theory of Atoms and Molecules; Oxford University Press: Oxford, 1989; p 1.
27. [27]
  (27) Becke, A. D. Phys. Rev. A 1988, 38, 3098. doi: 10.1103/PhysRevA.38.3098
28. [28]
  (28) Lee, C.; Yang,W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
29. [29]
  (29) Zheng, A. M.;Wang, L.; Chen, L.; Yue, Y.; Ye, C. H.; Lu, X.;Deng, F. ChemPhysChem 2007, 8, 231. doi: 10.1002/cphc.200600576
30. [30]
  (30) Zheng, A. M.; Chen, L.; Yang, J.; Zhang, M. J.; Su, Y. C.; Yue,Y.; Ye, C. H.; Deng, F. J. Phys. Chem. B 2005, 109, 24273. doi: 10.1021/jp0527249
31. [31]
  (31) Frisch, M. J.; Trucks,G.W.; Schlegel, H. B. et al. Gaussian 09,Revision B.01; Gaussian Inc.,Wallingford CT, 2010.
32. [32]
  (32) Dogu, T.; Boz, N.; Aydin, E.; Oktar, N.; Murtezaoglu, K.; Dogu,G. Ind. Eng. Chem. Res. 2001, 40, 5044. doi: 10.1021/ie000922a
1. [1]
  Yiping HUANG , Liqin TANG , Yufan JI , Cheng CHEN , Shuangtao LI , Jingjing HUANG , Xuechao GAO , Xuehong GU . Hollow fiber NaA zeolite membrane for deep dehydration of ethanol solvent by vapor permeation. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 225-234. doi: 10.11862/CJIC.20240224
2. [2]
  Tong Zhou , Liyi Xie , Chuyu Liu , Xiyan Zheng , Bao Li . Between Sobriety and Intoxication: The Fascinating Journey of Sauce-Flavored Latte. University Chemistry, 2024, 39(9): 55-58. doi: 10.12461/PKU.DXHX202312048
3. [3]
  Siwei Lv , Tantian Tan , Xinyue Li , Siyan Zhang , Mingyuan Zhang , Minghao Li , Hangshuo Guo , Zhaorong Li , Liangjie Dong , Fengshuo Zhang , Junlong Zhao . Competition of the “King of Transboundary Medicine”. University Chemistry, 2024, 39(9): 102-108. doi: 10.12461/PKU.DXHX202403034
4. [4]
  Yufang GAO , Nan HOU , Yaning LIANG , Ning LI , Yanting ZHANG , Zelong LI , Xiaofeng LI . Nano-thin layer MCM-22 zeolite: Synthesis and catalytic properties of trimethylbenzene isomerization reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1079-1087. doi: 10.11862/CJIC.20240036
5. [5]
  Yong Shu , Xing Chen , Sai Duan , Rongzhen Liao . How to Determine the Equilibrium Bond Distance of Homonuclear Diatomic Molecules: A Case Study of H₂. University Chemistry, 2024, 39(7): 386-393. doi: 10.3866/PKU.DXHX202310102
6. [6]
  Yuhao SUN , Qingzhe DONG , Lei ZHAO , Xiaodan JIANG , Hailing GUO , Xianglong MENG , Yongmei GUO . Synthesis and antibacterial properties of silver-loaded sod-based zeolite. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 761-770. doi: 10.11862/CJIC.20230169
7. [7]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-. doi: 10.3866/PKU.WHXB202406012
8. [8]
  Jiali CHEN , Guoxiang ZHAO , Yayu YAN , Wanting XIA , Qiaohong LI , Jian ZHANG . Machine learning exploring the adsorption of electronic gases on zeolite molecular sieves. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 155-164. doi: 10.11862/CJIC.20240408
9. [9]
  Shengbiao Zheng , Liang Li , Nini Zhang , Ruimin Bao , Ruizhang Hu , Jing Tang . Metal-Organic Framework-Derived Materials Modified Electrode for Electrochemical Sensing of Tert-Butylhydroquinone: A Recommended Comprehensive Chemistry Experiment for Translating Research Results. University Chemistry, 2024, 39(7): 345-353. doi: 10.3866/PKU.DXHX202310096
10. [10]
  Shanghua Li , Malin Li , Xiwen Chi , Xin Yin , Zhaodi Luo , Jihong Yu . 基于高离子迁移动力学的取向ZnQ分子筛保护层实现高稳定水系锌金属负极的构筑. Acta Physico-Chimica Sinica, 2025, 41(1): 2309003-. doi: 10.3866/PKU.WHXB202309003
11. [11]
  Linbao Zhang , Weisi Guo , Shuwen Wang , Ran Song , Ming Li . Electrochemical Oxidation of Sulfides to Sulfoxides. University Chemistry, 2024, 39(11): 204-209. doi: 10.3866/PKU.DXHX202401009
12. [12]
  Zhilian Liu , Wengui Wang , Hongxiao Yang , Yu Cui , Shoufeng Wang . Ideological and Political Education Design for the Synthesis of Irinotecan Drug Intermediate 7-Ethyl Camptothecin. University Chemistry, 2024, 39(2): 89-93. doi: 10.3866/PKU.DXHX202306012
13. [13]
  Tingbo Wang , Yao Luo , Bingyan Hu , Ruiyuan Liu , Jing Miao , Huizhe Lu . Quantitative Computational Study on the Claisen Rearrangement Reaction of Allyl Phenyl Ethers: An Introduction to a Computational Chemistry Experiment. University Chemistry, 2024, 39(11): 278-285. doi: 10.12461/PKU.DXHX202403082
14. [14]
  Huanhuan XIE , Yingnan SONG , Lei LI . Two-dimensional single-layer BiOI nanosheets: Lattice thermal conductivity and phonon transport mechanism. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 702-708. doi: 10.11862/CJIC.20240281
15. [15]
  Hao Ren , Wen Zhao , Fangna Dai , Wenyue Guo . Finite Difference Solution of One-Dimensional Quantum Systems: (1) Fundamental Concepts and Infinite Square Well. University Chemistry, 2025, 40(3): 124-131. doi: 10.12461/PKU.DXHX202405145
16. [16]
  Aimin Fu , Chunmei Chen , Qin Li , Nanjin Ding , Jiaxin Dong , Yu Chen , Mengsha Wei , Weiguang Sun , Hucheng Zhu , Yonghui Zhang . Niduenes A−F, six functionalized sesterterpenoids with a pentacyclic 5/5/5/5/6 skeleton from endophytic fungus Aspergillus nidulans. Chinese Chemical Letters, 2024, 35(9): 109100-. doi: 10.1016/j.cclet.2023.109100
17. [17]
  Chenye An , Abiduweili Sikandaier , Xue Guo , Yukun Zhu , Hua Tang , Dongjiang Yang . 红磷纳米颗粒嵌入花状CeO₂分级S型异质结高效光催化产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2405019-. doi: 10.3866/PKU.WHXB202405019
18. [18]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
19. [19]
  Zehua Zhang , Haitao Yu , Yanyu Qi . 多重共振TADF分子的设计策略. Acta Physico-Chimica Sinica, 2025, 41(1): 2309042-. doi: 10.3866/PKU.WHXB202309042
20. [20]
  Jia Huo , Jia Li , Yongjun Li , Yuzhi Wang . Ideological and Political Design of Physical Chemistry Teaching: Chemical Potential of Any Component in an Ideal-Dilute Solution. University Chemistry, 2024, 39(2): 14-20. doi: 10.3866/PKU.DXHX202307075

Get Citation

PDF

XML

Metrics

PDF Downloads(874)
Abstract views(1938)
HTML views(8)

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