Dehydration of Alcohols to Olefins Catalyzed by ZrAPSO-34 Molecular Sieve
DOI:
https://doi.org/10.31699/IJCPE.2024.2.10Keywords:
SAPO-34 zeolite catalyst; Zr metal incorporation; microwave irradiation; MTO, selectivityAbstract
The lower olefins (Ethylene, propylene, and butylene) are considered the key to the polymeric and petrochemical industries. Dehydration of alcohols to produce light olefins (Methanol-to-olefins reaction) over SAPO-34 molecular sieve has attractedintoigh attention. Modified SAPO-34 zeolite catalyst with Zr metal was successfully prepared under microwave irradiation using morpholine as a structure direct agent. The microwave energy power used was 800 w and the crystallization time was 200 min. The catalyst sample was characterized by XRD, SEM, EDX, BET, FTIR, and TGA analysis. XRD analysis exhibited a typical chabazite structure with high crystallinity. The analysis showed macrocrystalline particles with moderate distribution of silica in the framework structure and a low surface area of 77 m2/g. The vibration peaks of the prepared catalyst showed agreement with the SAPO-34 CHA structure. Catalyst performance towards methanol-to-olefins conversion was performed in a trickle bed reactor with temperatures of 350, 400, 450, and 500 oC at a weight hourly space velocity of 7.7 h-1. The results also reveal at a temperature of 400 oC , that the best olefins selectivity was obtained, reaching 70%, with a longer lifetime of 500 min. methanol conversion was almost 100% at all reaction temperatures. In addition, the effect of methanol concentration was investigated and the results showed that increasing of water content plays a role in increasing catalyst lifetime and preventing coke depositions in pores.
References
Y. Zhou, H. Shi, B. Wang, G. Chen, J. Yi, and J. Li, "The synthesis of SAPO-34 zeolite for an improved MTO performance: tuning the particle size and an insight into the formation mechanism," Inorganic Chemistry Frontiers, vol. 8, no. 9, pp. 2315-2322, 2021, https://doi.org/10.1039/D1QI00016K
F. Shakir, H. Q. Hussein, and Z. T. Abdulwahhab, "Influence of Nanosilica on Solvent Deasphalting for Upgrading Iraqi Heavy Crude Oil," Baghdad Science Journal, vol. 20, no. 1, pp. 0144-56, 2023, https://doi.org/10.21123/bsj.2022.6895
A. N. Hammadi and I. K. Shakir, "Adsorption Behavior of Light Naphtha Components on Zeolite (5A) and Activated Carbon," Iraqi Journal of Chemical and Petroleum Engineering, vol. 20, no. 4, pp. 27-33, 2019, https://doi.org/10.31699/IJCPE.2019.4.5
A. S. Abbas and R. N. Abbas, "Preparation and characterization of NaY zeolite for biodiesel production," Iraqi Journal of Chemical and Petroleum Engineering, vol. 16, no. 2, pp. 19-29, 2015, https://doi.org/10.31699/IJCPE.2015.2.3
J. W. Jun, J. Jeon, C.-U. Kim, K.-E. Jeong, S.-Y. Jeong, and S. H. Jhung, "Synthesis of mesoporous SAPO-34 molecular sieves and their applications in dehydration of butanols and ethanol," Journal of Nanoscience and Nanotechnology, vol. 13, no. 4, pp. 2782-2788, 2013, https://doi.org/10.1166/jnn.2013.7387
G. H. A. Razzaq and N. S. Majeed, "Pyrolysis of scrap tire by utilizing zeolite as catalyst," Materials Today: Proceedings, vol. 45, pp. 4606-4611, 2021, https://doi.org/10.1016/j.matpr.2020.12.1232
M. J. Ahmed, A. H. A. K. Mohammed, and A. A. H. Kadhum, "Experimental and theoretical studies of equilibrium isotherms for pure light hydrocarbons adsorption on 4A zeolite," Korean Journal of Chemical Engineering, vol. 27, pp. 1801-1804, 2010, https://doi.org/10.1007/s11814-010-0302-8
H. Aljendeel and H. Q. Hussein, "Advanced Study of Promoted Pt/SAPO-11 Catalyst for Hydroisomerization of the n-Decane Model and Lube Oil," Iraqi Journal of Chemical and Petroleum Engineering, vol. 22, no. 2, pp. 17-26, 2021, https://doi.org/10.31699/IJCPE.2021.2.3
S. M. Al-Jubouri, H. A. Al-Jendeel, S. A. Rashid, and S. Al-Batty, "Antibiotics adsorption from contaminated water by composites of ZSM-5 zeolite nanocrystals coated carbon," Journal of Water Process Engineering, vol. 47, p. 102745, 2022, https://doi.org/10.1016/j.jwpe.2022.102745
S. F. Alam, M.-Z. Kim, D. Arepalli, P. Sharma, and C. H. Cho, "Synthesis of SAPO-34 nanoplates with high Si/Al ratio and improved acid site density," Nanomaterials, vol. 11, no. 12, p. 3198, 2021, https://doi.org/10.3390/nano11123198
G. Jabaar and H. Al-Jendeel, "Synthesis and characterization of SAPO-11 using carbon nanotubes," in AIP Conference Proceedings, 2023, vol. 2806, no. 1: AIP Publishing, https://doi.org/10.1063/5.0163114
Q. Sun, Z. Xie, and J. Yu, "The state-of-the-art synthetic strategies for SAPO-34 zeolite catalysts in methanol-to-olefin conversion," National Science Review, vol. 5, no. 4, pp. 542-558, 2018, https://doi.org/10.1093/nsr/nwx103
E. Kianfar, "Investigation of the effect of crystallization temperature and time in synthesis of SAPO-34 catalyst for the production of light olefins," Petroleum Chemistry, vol. 61, pp. 527-537, 2021, http://dx.doi.org/10.1134/S0965544121050030
D. Zapater, J. Lasobras, J. Soler, J. Herguido, and M. Menendez, "MTO with SAPO-34 in a Fixed-Bed Reactor: Deactivation Profiles," Industrial & Engineering Chemistry Research, vol. 60, no. 45, pp. 16162-16170, 2021, https://doi.org/10.1021/acs.iecr.1c02718
M. Sedighi, M. Ghasemi, M. Sadeqzadeh, and M. Hadi, "Thorough study of the effect of metal-incorporated SAPO-34 molecular sieves on catalytic performances in MTO process," Powder Technology, vol. 291, pp. 131-139, 2016, https://doi.org/10.1016/j.powtec.2015.11.066
J. Yao, Y. Rong, Z. Gao, X. Tang, F. Zha, H. Tian, Y. Chang, and X. Guo, "Metal–organic framework-assisted synthesis of Zr-modified SAPO-34 zeolites with hierarchical porous structure for the catalytic transformation of methanol to olefins," Catalysis Science & Technology, vol. 12, no. 3, pp. 894-905, 2022, https://doi.org/10.1039/D1CY01838H
J.-W. Jun, J.-S. Lee, H.-Y. Seok, J.-S. Chang, J.-S. Hwang, and S.-H. Jhung, "A facile synthesis of SAPO-34 molecular sieves with microwave irradiation in wide reaction conditions," Bulletin of the Korean Chemical Society, vol. 32, no. 6, pp. 1957-1964, 2011, http://dx.doi.org/10.5012/bkcs.2011.32.6.1957
F. M. Shalmani, R. Halladj, and S. Askari, "Effect of contributing factors on microwave-assisted hydrothermal synthesis of nanosized SAPO-34 molecular sieves," Powder Technology, vol. 221, pp. 395-402, 2012, https://doi.org/10.1016/j.powtec.2012.01.036
A. A. Eslami, M. Haghighi, and P. Sadeghpour, "Short time microwave/seed-assisted synthesis and physicochemical characterization of nanostructured MnAPSO-34 catalyst used in methanol conversion to light olefins," Powder Technology, vol. 310, pp. 187-200, 2017, https://doi.org/10.1016/j.powtec.2017.01.017
S. Askari, A. B. Siahmard, R. Halladj, and S. M. Alipour, "Different techniques and their effective parameters in nano SAPO-34 synthesis: A review," Powder Technology, vol. 301, pp. 268-287, 2016, https://doi.org/10.1016/j.powtec.2016.06.018
K. Mirza, M. Ghadiri, M. Haghighi, and A. Afghan, "Hydrothermal synthesize of modified Fe, Ag and K-SAPO-34 nanostructured catalysts used in methanol conversion to light olefins," Microporous and Mesoporous Materials, vol. 260, pp. 155-165, 2018, https://doi.org/10.1016/j.micromeso.2017.10.045
F. Huang, J. Cao, L. Wang, X. Wang, and F. Liu, "Enhanced catalytic behavior for methanol to lower olefins over SAPO-34 composited with ZrO2," Chemical Engineering Journal, vol. 380, p. 122626, 2020, https://doi.org/10.1016/j.cej.2019.122626
O. D. A. Salah Aldeen, M. Z. Mahmoud, H. S. Majdi, D. A. Mutlak, K. Fakhriddinovich Uktamov, and E. Kianfar, "Investigation of Effective Parameters Ce and Zr in the Synthesis of H-ZSM-5 and SAPO-34 on the Production of Light Olefins from Naphtha," Advances in Materials Science and Engineering, vol. 2022, pp. 1-22, 2022, https://doi.org/10.1155/2022/6165180
J. Chen, X. Wang, D. Wu, J. Zhang, Q. Ma, X. Gao, X. Lai, H. Xia, S. Fan, and T.-S. Zhao, "Hydrogenation of CO2 to light olefins on CuZnZr@(Zn-) SAPO-34 catalysts: Strategy for product distribution," Fuel, vol. 239, pp. 44-52, 2019, https://doi.org/10.1016/j.fuel.2018.10.148
N. Najafi, S. Askari, and R. Halladj, "Hydrothermal synthesis of nanosized SAPO-34 molecular sieves by different combinations of multi templates," Powder technology, vol. 254, pp. 324-330, 2014, http://dx.doi.org/10.1016/j.powtec.2014.01.037
C. Wang, J. Wang, J. Wang, and M. Shen, "Promotional effect of ion-exchanged K on the low-temperature hydrothermal stability of Cu/SAPO-34 and its synergic application with Fe/Beta catalysts," Frontiers of Environmental Science & Engineering, vol. 15, pp. 1-13, 2021, https://doi.org/10.1007/s11783-020-1322-1
T. Álvaro-Muñoz, E. Sastre, and C. Márquez-Álvarez, "Microwave-assisted synthesis of plate-like SAPO-34 nanocrystals with increased catalyst lifetime in the methanol-to-olefin reaction," Catalysis Science & Technology, vol. 4, no. 12, pp. 4330-4339, 2014, https://doi.org/10.1039/C4CY00775A
S. Lin, J. Li, R. P. Sharma, J. Yu, and R. Xu, "Fabrication of SAPO-34 crystals with different morphologies by microwave heating," Topics in Catalysis, vol. 53, pp. 1304-1310, 2010, https://doi.org/10.1007/s11244-010-9588-3
M. Tong, L. G. Chizema, X. Chang, E. Hondo, L. Dai, Y. Zeng, C. Zeng, H. Ahmad, R. Yang, and P. Lu, "Tandem catalysis over tailored ZnO-ZrO2/MnSAPO-34 composite catalyst for enhanced light olefins selectivity in CO2 hydrogenation," Microporous and Mesoporous Materials, vol. 320, p. 111105, 2021, https://doi.org/10.1016/j.micromeso.2021.111105
A. M. Rahman, M. H. Salman, and K. W. Hammed, "Catalytic Cracking of Iraqi Vacuum Gasoil Using Large and Medium Pore Size of Zeolite Catalysts," Al-Khwarizmi Engineering Journal, vol. 11, no. 1, pp. 73-83, 2015.
H.-J. Chae, S. S. Park, Y. H. Shin, and M. B. Park, "Synthesis and characterization of nanocrystalline TiAPSO-34 catalysts and their performance in the conversion of methanol to light olefins," Microporous and Mesoporous Materials, vol. 259, pp. 60-66, 2018, https://doi.org/10.1016/j.micromeso.2017.09.035
P. Tian, Y. Wei, M. Ye, and Z. Liu, "Methanol to olefins (MTO): from fundamentals to commercialization," Acs Catalysis, vol. 5, no. 3, pp. 1922-1938, 2015, https://doi.org/10.1021/acscatal.5b00007
X. Wu and R. Anthony, "Effect of feed composition on methanol conversion to light olefins over SAPO-34," Applied Catalysis A: General, vol. 218, no. 1-2, pp. 241-250, 2001, https://doi.org/10.1016/S0926-860X(01)00651-2
M. S. Ahmad, C. K. Cheng, P. Bhuyar, A. Atabani, A. Pugazhendhi, N. T. L. Chi, T. Witoon, J. W. Lim, and J. C. Juan, "Effect of reaction conditions on the lifetime of SAPO-34 catalysts in methanol to olefins process–A review," Fuel, vol. 283, p. 118851, 2021, https://doi.org/10.1016/j.fuel.2020.118851
Downloads
Published
Issue
Section
License
Copyright (c) 2024 The Author(s). Published by College of Engineering, University of Baghdad.
![Creative Commons License](http://i.creativecommons.org/l/by/4.0/88x31.png)
This work is licensed under a Creative Commons Attribution 4.0 International License.