Direct K+ and Ag+ Ion-exchanged into SAPO-34 Prepared via Microwave Irradiation and Its Performance in MTO

Authors

  • mazin jasim mohammed Department of Chemical Engineering, College of Engineering, University of Baghdad, Baghdad, Iraq.
  • najwa saber majeed Department of Chemical Engineering, College of Engineering, University of Baghdad, Baghdad, Iraq.

DOI:

https://doi.org/10.21123/bsj.2024.9017

Keywords:

Ion exchange, Microwave irradiation, MTO, SAPO-34 zeolite catalyst, Selectivity.

Abstract

Recently, light olefins became an important material for industrials, especially plastics. High olefins production cost from oil sources, made the researchers look for other methods. Methanol conversion to olefins over SAPOs was an excellent alternative. SAPO-34 molecular sieve is considered a proper catalyst used in this field. For this purpose, SAPO-34 with morpholine template was prepared under microwave irradiation. K and Ag ions were incorporated successfully by ion exchange method. The samples were analyzed by XRD, SEM, EDX, FT-IR, BET, and TGA techniques. XRD showed higher crystallinity of K-SAPO-34 and smaller crystallite size than Ag-SAPO-34. The SEM and EDX analysis indicated perfect distribution of K and Ag metal ions. Surface area reached to 287.64 and 254.59 m2/g for K-SAPO-34 and Ag-SAPO-34, respectively. TGA analysis showed high thermal stability opposite cracking at high temperature of 1100 oC. The catalyst performance on MTO was performed in trickle bed reactor at temperature of 350, 400, 450 and 500 oC at 7.7 hrs-1. The conversion was 100% for the two samples. At 400 oC, olefins selectivity was 85% of K-SAPO-34. Ag-SAPO-34 showed longer lifetime of 475 min with 74% olefins selectivity. Weight hourly space velocity of 15 and 21.1 hrs-1 at 450 oC for K-SAPO-34 were also investigated. As the velocity increased, the conversion and selectivity decreased. It was found that adding K and Ag by ion exchange to SAPO-34 improve surface area and enlarge the pores diffusion. This might hinder the coke deposition in pores and improve olefin selectivity.

References

Sun C, Wang Y, Zhao A, Wang X, Wang C, Zhang X, et al. Synthesis of nano-sized SAPO-34 with morpholine-treated micrometer-seeds and their catalytic performance in methanol-to-olefin reactions. Appl Catal A: Gen. 2020; 589: 117314. https://doi.org/10.1016/j.apcata.2019.117314.

Shabani M, Haghighi M, Ebrahimi A, Aghamohammadi S. Morphology/crystallographic evolution of nanostructured SAPO-34 using simultaneous surfactant and Si source towards production of lower olefins: enhancement of lifetime and regenerative properties. Res Chem Intermed. 2023; 49(1): 307-27. https://doi.org/10.1007/s11164-022-04874-8.

Akhgar S, Towfighi J, Hamidzadeh M. Investigation of synthesis time and type of seed along with reduction of template consumption in the preparation of SAPO-34 catalyst and its performance in the MTO reaction. RSC Adv. 2020; 10(57): 34474-85. https://doi.org/10.1039/D0RA05673A.

Hammadi AN, Shakir IK. Adsorption Behavior of Light Naphtha Components on Zeolite (5A) and Activated Carbon. J Chem Pet Eng. 2019; 20(4): 27-33. https://doi.org/10.31699/IJCPE.2019.4.5.

Abbas AS, Abbas SM. Kinetic study and simulation of oleic acid esterification in different type of reactors. J Chem Pet Eng. 2013; 14(2): 13-20. http://dx.doi.org/10.31699/IJCPE.2013.2.3.

Razzaq GHA, Majeed NS. Pyrolysis of scrap tire by utilizing zeolite as catalyst. Mater Today: Proc. 2021; 45: 4606-11. https://doi.org/10.1016/j.matpr.2020.12.1232.

Yu W, Wu X, Cheng B, Tao T, Min X, Mi R, et al. Synthesis and Applications of SAPO‐34 Molecular Sieves. Chem Eur J. 2022; 28(11): e202102787. https://doi.org/10.1002/chem.202102787.

Alismaeel ZT, Abbas AS, Albayati TM, Doyle AM. Biodiesel from batch and continuous oleic acid esterification using zeolite catalysts. Fuel. 2018; 234: 170-6. https://doi.org/10.1016/j.fuel.2018.07.025.

Shakir F, Hussein HQ, Abdulwahhab ZT. Influence of Nanosilica on Solvent Deasphalting for Upgrading Iraqi Heavy Crude Oil. Baghdad Sci J. 2023; 20(1): 0144-56. https://doi.org/10.21123/bsj.2022.6895.

Al-Daffay RKH, Al-Hamdani AAS. Synthesis, Characterization, and Thermal Analysis of a New Acidicazo Ligand's Metal Complexes. Baghdad Sci J. 2023; 20(1): 0121-33. http://dx.doi.org/10.21123/bsj.2022.6709.

Al-Jubouri SM. The static aging effect on the seedless synthesis of different ranges FAU-type zeolite Y at various factors. J Chem Pet Eng. 2019; 20(4): 7-13. https://doi.org/10.31699/IJCPE.2019.4.2.

Ma Y-K, Alomar TS, AlMasoud N, El-Bahy ZM, Chia S, Daou TJ, et al. Effects of Synthesis Variables on SAPO-34 Crystallization Templated Using Pyridinium Supramolecule and Its Catalytic Activity in Microwave Esterification Synthesis of Propyl Levulinate. Catalysts. 2023; 13(4): 680. https://doi.org/10.3390/catal13040680.

Meng F, Liang X, Wang L, Yang G, Huang X, Li Z. Rational design of SAPO-34 zeolite in bifunctional catalysts for syngas conversion into light olefins. Ind Eng Chem Res. 2022; 61(31): 11397-406. https://doi.org/10.1021/acs.iecr.2c01111.

Álvaro-Muñoz T, Sastre E, Márquez-Álvarez C. Microwave-assisted synthesis of plate-like SAPO-34 nanocrystals with increased catalyst lifetime in the methanol-to-olefin reaction. Catal Sci Technol. 2014; 4(12): 4330-9. https://doi.org/10.1039/C4CY00775A.

Shalmani FM, Halladj R, Askari S. Effect of contributing factors on microwave-assisted hydrothermal synthesis of nanosized SAPO-34 molecular sieves. Powder Technol. 2012; 221: 395-402. https://doi.org/10.1016/j.powtec.2012.01.036.

Yao J, Rong Y, Gao Z, Tang X, Zha F, Tian H, et al. Metal–organic framework-assisted synthesis of Zr-modified SAPO-34 zeolites with hierarchical porous structure for the catalytic transformation of methanol to olefins. Catal Sci Technol. 2022; 12(3): 894-905. https://doi.org/10.1039/D1CY01838H.

Xiang X, Yang M, Gao B, Qiao Y, Tian P, Xu S, et al. Direct Cu 2+ ion-exchanged into as-synthesized SAPO-34 and its catalytic application in the selective catalytic reduction of NO with NH 3. RSC Adv. 2016; 6(15): 12544-52. https://doi.org/10.1039/C5RA22868A.

Mirza K, Ghadiri M, Haghighi M, Afghan A. Hydrothermal synthesize of modified Fe, Ag and K-SAPO-34 nanostructured catalysts used in methanol conversion to light olefins. Microporous Mesoporous Mat. 2018; 260: 155-65. https://doi.org/10.1016/j.micromeso.2017.10.045.

Eslami AA, Haghighi M, Sadeghpour P. Short time microwave/seed-assisted synthesis and physicochemical characterization of nanostructured MnAPSO-34 catalyst used in methanol conversion to light olefins. Powder Technol. 2017; 310: 187-200. https://doi.org/10.1016/j.powtec.2017.01.017.

Yang M, Fan D, Wei Y, Tian P, Liu Z. Recent progress in methanol‐to‐olefins (MTO) catalysts. Adv Mater. 2019; 31(50): 1902181. https://doi.org/10.1002/adma.201902181.

Majeed JT, Majeed NS, editors. Fast Synthesis and Characterization of Nano-SSZ-13 Zeolite by Hydrothermal Method. 2022 Muthanna International Conference on Engineering Science and Technology (MICEST); 2022: IEEE. https://doi.org/10.1109/MICEST54286.2022.9790195.

Wang C, Wang J, Wang J, Shen M. Promotional effect of ion-exchanged K on the low-temperature hydrothermal stability of Cu/SAPO-34 and its synergic application with Fe/Beta catalysts. Front Environ Sci Eng. 2021; 15: 1-13. https://doi.org/10.1007/s11783-020-1322-1.

Aljendeel H, Hussein HQ. Advanced Study of Promoted Pt/SAPO-11 Catalyst for Hydroisomerization of the n-Decane Model and Lube Oil. J Chem Pet Eng. 2021; 22(2): 17-26. https://doi.org/10.31699/IJCPE.2021.2.3.

Al-Jubouri SM, Al-Jendeel HA, Rashid SA, Al-Batty S. Antibiotics adsorption from contaminated water by composites of ZSM-5 zeolite nanocrystals coated carbon. J Water Process Eng. 2022; 47: 102745. https://doi.org/10.1016/j.jwpe.2022.102745.

Liu H, Kianfar E. Investigation the synthesis of nano-SAPO-34 catalyst prepared by different templates for MTO process. Catal Lett. 2021; 151: 787-802. https://doi.org/10.1007/s10562-020-03333-6.

Wang Q, Wang X, Liu Y, Zhang L, Ma X, Zheng J, et al. Controlled synthesis of hierarchically porous SAPO-34 zeolites with tailored crystal size and morphology. Chem Phys Lett. 2022; 794: 139513. https://doi.org/10.1016/j.cplett.2022.139513.

Akhgar S, Towfighi J, Hamidzadeh M. MTO performance over seed-assisted SAPO-34 zeolites synthesized by reducing template consumption. J Mater Res Technol. 2020; 9(6): 12126-36. https://doi.org/10.1016/j.jmrt.2020.08.067.

Yang L, Wang C, Zhang L, Dai W, Chu Y, Xu J, et al. Stabilizing the framework of SAPO-34 zeolite toward long-term methanol-to-olefins conversion. Nat Commun. 2021; 12(1): 4661. https://doi.org/10.1038/s41467-021-24403-2.

Downloads

Issue

Section

article

How to Cite

1.
Direct K+ and Ag+ Ion-exchanged into SAPO-34 Prepared via Microwave Irradiation and Its Performance in MTO. Baghdad Sci.J [Internet]. [cited 2024 Jun. 14];21(12). Available from: https://bsj.uobaghdad.edu.iq/index.php/BSJ/article/view/9017