Preparation and Characterization of Sulfated Zirconia-HY Zeolite Catalyst Supported with Pt Metal for Light Naphtha Isomerization

Sura K. Al-Taweel; Haider A. Al-Jendeel; Ban A. Al-Tabbakh

doi:10.52716/jprs.v16i1.1039

Authors

Sura K. Al-Taweel Department of Chemical Engineering, College of Engineering, University of Baghdad, Baghdad, Iraq.
Haider A. Al-Jendeel Department of Chemical Engineering, College of Engineering, University of Baghdad, Baghdad, Iraq.
Ban A. Al-Tabbakh Petroleum Research and Development Center, Ministry of Oil, Baghdad, Iraq.

DOI:

https://doi.org/10.52716/jprs.v16i1.1039

Keywords:

ZrO2 nanotube, sulfated Zirconia, Multi wall carbon nanotube, Acid treatment, Isomerization, Light naphtha, Pt metal

Abstract

Platinum (Pt) supported on sulfated zirconia (SZ) and HY-zeolite as a solid acid catalyst was synthesized successfully for isomerization reaction using precipitation and impregnation method. The physicochemical properties of the catalyst were characterized using various techniques including X-ray diffraction (XRD), Fourier transformation infra-red spectroscopy (FTIR), BET Surface area and pore volume, and Field Emission Scanning Electron Microscopy (FESEM). The prepared composite catalyst Pt/SZ-HY consisted of high Bronsted acidic sites and Lewis acidic sites. The addition of multi-walled carbon nanotubes (MWCNTs) to SZ increased the surface area and pore volume, resulting in smaller crystal sizes and a narrower particle size distribution. However, sulfated zirconia without MWCNTs proved more suitable for the isomerization reaction due to its high functional group density. The Pt/SZ-HY composite catalyst exhibited high Bronsted and Lewis acidic sites, with a 1:1 weight ratio of mesoporous SZ and HY zeolite. The catalytic performance of the Pt/SZ-HY composite was evaluated in the isomerization of light Iraqi naphtha, yielding a maximum conversion of 70.76 mol% at 160°C, 15 bar, and 1 hr-1 LHSV.

References

R. S. Hamied, Z. M. Shakor, A. H. Sadeiq, A. A. A. Razak, and A. T. Khadim, “Kinetic Modeling of Light Naphtha Hydroisomerization in an Industrial Universal Oil Products Penex TM Unit”, Energy Engineering, vol. 120, no. 6, pp. 1371-1386, 2023. https://doi.org/10.32604/ee.2023.028441.

S. A. Al, N. Haider, and A. Al Jendeel, “Hydroisomerization of n ‑ hexane over Pt / TiO 2 catalysts”, Chemical Papers, vol. 78, pp. 9069–9076, 2024. https://doi.org/10.1007/s11696-024-03727-5.

A. T. Jarullah, A. M. Ahmed, H. M. Hussein, A. N. Ahmed, and H. J. Mohammed, “Evaluation of Synthesized Pt/HY-H-Mordenite Composite Catalyst for Isomerization of Light Naphtha”, Tikrit J. Eng. Sci., vol. 30, no. 1, pp. 94–103, 2023. https://doi.org/10.25130/tjes.30.1.9.

Z. Ghaderi, M. H. Peyrovi, and N. Parsafard, “Catalytic study of the n-heptane isomerization over hybrid catalysts”, 3ed International Conference on the: New Technologies in the Oil, Gas & Petrochemical Industries, December, 2021.

Y. H. Khalaf, B. Y. Sherhan Al-Zaidi, and Z. M. Shakour, “Experimental and Kinetic Study of the Effect of using Zr-and Pt-loaded Metals on Y-zeolite-based Catalyst to Improve the Products of n-heptane Hydroisomerization Reactions”, Orbital: The Electronic Journal of Chemistry, vol. 14, no. 3, pp. 153–167, 2022. http://dx.doi.org/10.17807/orbital.v14i3.17429.

A. N. Ahmed, A. T. Jarulah, B. A. A. Altabakh, A. M. Ahmed, and H. J. Mohammed, “Preparation and Characterization of Metal Carbide Zeolite Composite Catalyst”, Journal of Petroleum Research and Studies, vol. 13, no. 4, pp. 115–130, 2023. https://doi.org/10.52716/jprs.v13i4.737.

D. B. A. A. Al-Tabbakh and M. M. Dawood, “Synthesis and Characterization of Sulfated Zirconia Catalyst for Light Naphtha Isomerization Process”, Journal of Petroleum Research and Studies, vol. 12, no. 1(Suppl.), pp. 186–198, 2022. https://doi.org/10.52716/jprs.v12i1(Suppl.).630.

Y. Shao, Y. Li, K. Sun, Z. Zhang, H. Tian, G. Gao, Q. Li, Q. Liu, Q. Liu, and X. Hu, “Sulfated Zirconia with Different Crystal Phases for the Production of Ethyl Levulinate and 5-Hydroxymethylfurfural”, Energy Technology, vol. 8, no. 3 p. 1900951, 2020. https://doi.org/10.1002/ente.201900951.

J. Liu, Z. Zhao, C. Xu, and J. Liu, “Structure , synthesis , and catalytic properties of nanosize cerium-zirconium-based solid solutions in environmental catalysis”, Chinese J. Catal., vol. 40, no. 10, pp. 1438–1487, 2019. https://doi.org/10.1016/S1872-2067(19)63400-5.

S. J. Sekewael, R. A. Pratika, L. Hauli, A. K. Amin, M. Utami, and K. Wijaya, “Recent Progress on Sulfated Nanozirconia as a Solid Acid Catalyst in the Hydrocracking Reaction”, Catalysts, vol. 12, no. 2, p. 191, 2022. https://doi.org/10.3390/catal12020191.

A. Kumar, Priyanka, J. Mangalam, V. Yadav, and T. Goswami, “Synthesis of sulfated zirconia catalyst using sol–gel technique for alkane isomerization”, Reaction Kinetics, Mechanisms and Catalysis, vol. 135, pp. 1929–1944, 2022. https://doi.org/10.1007/s11144-022-02254-2.

M. D. Smolikov, V. A. Shkurenok, D. I. Kir’yanov, and A. S. Belyi, “Active surface formation of tungstated zirconia catalysts for n-heptane isomerization”, Catalysis Today, vol. 329, June 2018, pp. 63–70, 2019. https://doi.org/10.1016/j.cattod.2019.01.036.

S. A. S. Kamel, W. T. Mohammed, and H. Aljendeel, “Synthesis and Characterization of Ni-WO3/Sulfated Zirconia Nano catalyst for Isomerization of N-Hexane and Iraqi Light Naphtha”, Iraqi J. Chem. Pet. Eng., vol. 22, no. 4, pp. 1–10, 2021. https://doi.org/10.31699/IJCPE.2021.4.1.

Z. Ma, X. Meng, N. Liu, and L. Shi, “Pd-Ni doped sulfated zirconia: Study of hydrogen spillover and isomerization of N-hexane”, Mol. Catal., vol. 449, November 2017, pp. 114–121, 2018. https://doi.org/10.1016/j.mcat.2018.02.003.

A. M. Ahmed, A. T. Jarullah, H. M. Hussein, and A. N. Ahmed, “Mordenite-Type Zeolite from Iraq Sand: Synthesis and Characterization”, Journal of Petroleum Research and Studies, vol. 13, no. 3, pp. 126-142, Sep. 2023. https://doi.org/10.52716/jprs.v13i3.709.

N. S. A. Zeki, Y. M. Jaeed, and M. N. Abass, “( JPR & S ) The Effect of Surfactant on Zeolite Preparation from Iraqi Kaolin”, Journal of Petroleum Research and Studies, vol. 8, no. 4, pp. 71–86, 2021. https://doi.org/10.52716/jprs.v8i4.263.

K. Yang, H. Li, S. Zhao, S. Lai, W. Lai, Y. Lian, and W. Fang, “Improvement of Activity and Stability of CuGa Promoted Sulfated Zirconia Catalyst for n-Butane Isomerization”, Industrial & Engineering Chemistry Research, vol. 57, no. 11, pp. 3855–3865, 2018. https://doi.org/10.1021/acs.iecr.7b04590.

P. Wang, W. Zhang, Q. Zhang, Z. Xu, C. Yang, and C. Li, “Comparative study of n -butane isomerization over SO42− / Al2O3 -ZrO2 and HZSM-5 zeolites at low reaction temperatures”, Applied Catalysis A: General, vol. 550, pp. 98–104, 2018. https://doi.org/10.1016/j.apcata.2017.11.006.

N. Liu, Z. Ma, S. Wang, L. Shi, X. Hu, and X. Meng, “Palladium-doped sulfated zirconia: Deactivation behavior in isomerization of n-hexane”, Fuel, vol. 262, p. 116566, 2020. https://doi.org/10.1016/j.fuel.2019.116566.

M. Malekkiani, A. Heshmati, J. Magham, F. Ravari, and M. Dadmehr, “One Pot Synthesis of Ternary MWCNTs/ZnO/Chitosan Nanocomposite for Enhanced Photocatalytic Degradation of Organic Dyes and Antibacterial Activity”, Research Square, 2021. https://doi.org/10.21203/rs.3.rs-882501/v1.

J. Wang, X. Duan, and L. Gong, “Interfacial and Filler Size Effects on Mechanical/ Thermal/ Electrical Properties of CNTs-Reinforced Nanocomposites”, Polymers, vol. 16, no. 6, p. 808, 2024. https://doi.org/10.3390/polym16060808.

R. Rajwanti and D. Tyagi, “Nano sulfated zirconia over silica for highly effective nano sulfated zirconia”, International Journal of Health Sciences, vol. 6, no. S3, pp. 8492–8500, May 2022. https://doi.org/10.53730/ijhs.v6nS3.8007.

S. K. Al-Taweel, H. A. Al-jendeel, and B. A. Al-tabbakh, “Synthesis of sulfated zirconia-HY zeolite catalysts doped by platinum metal for hydroisomerization reaction”, Journal of Ecological Engineering, vol. 26, no. 3, pp. 147–158, 2025. https://doi.org/10.12911/22998993/199586.

Y. Khalaf, B. Sherhan, and Z. Shakour, “Hydroisomerization of n-Heptane in a Fixed-Bed Reactor Using a Synthesized Bimetallic Type-HY Zeolite Catalyst”, Engineering and Technology Journal, vol. 40, no. 9, pp. 1–13, 2022. https://doi.org/10.30684/etj.2022.132491.1124.

N. M. Al-Mhanna, “Simulation of high pressure separator used in crude oil processing”, Processes, vol. 6, no. 11, p. 219, 2018. https://doi.org/10.3390/pr6110219.

N. Johnson, U. C. Sunday, and N. H. Andrew, “Harnessing the Power of Pressurized Separation : Revolutionizing Crude Oil Processing and Storage for Optimal Performance”, Research Square, 2024. https://doi.org/10.21203/rs.3.rs-4169880/v1.

D. Huang, W. Feng, L. Zhang, B. Yue, and H. He, “Insight into the Acidity and Catalytic Performance on Butane Isomerization of Thermal Stable Sulfated Monoclinic Zirconia”, Processes, vol. 10, no. 12, 2022. https://doi.org/10.3390/pr10122693.

D. S. El-Desouki, A. H. Ibrahim, S. M. Abdelazim, N. A. K. Aboul-Gheit, and D. R. Abdel-Hafizar, “The optimum conditions for methanol conversion to dimethyl ether over modified sulfated zirconia catalysts prepared by different methods”, Journal of Fuel Chemistry and Technology, vol. 49, no. 1, pp. 63–71, 2021. https://doi.org/10.1016/S1872-5813(21)60009-9.

Y. Cui, X. Dong, Z. Jiang, Y. Suo, W. Zhang, and Y. Wang, “RSC Advances Study on the preparation and n -heptane”, RSC advances, vol. 14, pp. 4105–4115, 2024. https://doi.org/10.1039/D3RA08454J.

A. K. Hussein, B. A. Al-Tabbakh, and A. T. Jarullah, “Oxidative Desulfurization of Kerosene in Batch Reactor using Magnetite Mesoporous Silica Composite Zeolite Catalyst”, Journal of Petroleum Research and Studies, vol. 14, no. 3, pp. 75-88, Sep. 2024. https://doi.org/10.52716/jprs.v14i3.804.

Y. Gao, R. Gao, G. Zhang, Y. Zheng, and J. Zhao, “Oxidative desulfurization of model fuel in the presence of molecular oxygen over polyoxometalate based catalysts supported on carbon nanotubes”, Fuel, vol. 224, pp. 261–270, July 2018. https://doi.org/10.1016/j.fuel.2018.03.034.

Z. Ghaderi, M. H. Peyrovi, and N. Parsafard, “Effects of Zr, Al, and mordenite on Pt-MCM-48 catalyst in n-heptane isomerization: preparation, characterization and catalytic performance”, Journal of Porous Materials, vol. 30, no. 5, pp. 1789–1795, 2023. https://doi.org/10.1007/s10934-023-01463-x.

P. Zhu, S. Meier, S. Saravanamurugan, and A. Riisager, “Modification of commercial Y zeolites by alkaline-treatment for improved performance in the isomerization of glucose to fructose”, Molecular Catalysis, vol. 510, p. 111686, June 2021. https://doi.org/10.1016/j.mcat.2021.111686.

A. Rachmat, R. Dwifahmi, N. Yuliasari, A. Mara, and D. Desnelli, “Preparation of Ga2O3-modified sulfated zirconia mesopore and its application on cellobiose hydrolysis”, Journal of Metals, Materials and Minerals, vol. 33, no. 3, pp. 12–14, 2023. https://doi.org/10.55713/jmmm.v33i3.1702.

L. Patrylak, O. Pertko, Y. Voloshyna, A. Yakovenko, V. Povazhnyi, O. Melnychuk, and K. Zlochevskyi, “Linear hexane isomerization over bimetallic zeolite catalysts”, Chem. Chem. Technol., vol. 15, no. 3, pp. 330–335, 2021. https://doi.org/10.23939/chcht15.03.330.

L. Shaolong, L. Yuchen, C. Qiang, G. Fanchuan, W. Yixuan, W. Jingyu, Z. Ye, G. Ruiyu, and G. Jiaru, “Preparation of Pt/ CNT Catalyst with High Dispersion Structure via Plasma Jet”, Diamond and Related Materials, p. 110674, 2024, https://doi.org/10.1016/j.diamond.2023.110674.

H. M. Hussain and A. A.K. Mohammed, “Experimental Study of Iraqi Light Naphtha Isomerization over Ni-Pt/H-Mordenite”, Iraqi J. Chem. Pet. Eng., vol. 20, no. 4, pp. 61–66, 2019. https://doi.org/10.31699/IJCPE.2019.4.10.