Synthesis and Characterization ZSM-5 Based on Kaolin as a Catalyst for Catalytic Cracking of Heavy Distillate

This article describes the study of synthesis of ZSM-5 Zeolite based on kaolin as catalysts for catalytic cracking of heavy distillate. There are five types of formulas A, B, C, D, and E synthesized with varying the molar ratios of SiO₂/Al₂O₃, SiO₂/Na₂O, and H₂O/SiO₂ and characterized by chemical compound, microstructure and catalytic performance. Three methods conducted the catalytic cracking of heavy distillate such as without catalyst, Ni-Mo commercial catalyst, and bifunctional catalyst ZSM-5 from Formula E, which was impregnated with transition metals (Ni, Mo) to be Ni-Mo/HZSM-5. The catalytical performance test result shows that, under operational conditions (~350 ^°C, 1 MPa), middle distillate hydrocarbon is obtained by the catalytic cracking of heavy distillate using Ni-Mo commercial catalyst and Ni-Mo/HZSM-5 Formula E catalyst. When a Ni-Mo/HZSM-5 Formula E catalyst and Ni-Mo Commercial Catalyst were used in the cracking process, a light hydrocarbon fraction (C₃ - C₅) was formed.

Catalytic Cracking; Formulation; Heavy Distillate; Zeolite

Due to the scarcity and depletion of traditional light petroleum resources, low-quality heavy oils and or residues obtained by processing heavy crudes are considered a suitable alternate source for transportation fuels, energy, and petrochemicals to meet the needs of rapidly growing populations and civilizations. Furthermore, numerous statistical studies have revealed that heavy crude reservoirs are significantly larger than conventional oil reservoirs, necessitating deep upgrading of heavy crude for refining and petrochemicals (Corma et al., 2017).

       The abundance of heavy crude oil reserves and the high demand for light olefins, particularly propylene, have created new opportunities to develop advanced catalyst and process technologies that efficiently convert asphaltene-enriched crudes to high-value chemicals. Indeed, many petrochemicals are produced as by-products of crude oil refining, as the primary goal of a crude oil refinery is to create transportation fuel (Alotaibi et al., 2018). 
    Catalytic cracking of hydrocarbons is important for industrial manufacturing because it has higher cracking conversion efficiency, higher light alkene selectivity, and less carbon deposition than thermal cracking (Sadrameli, 2016). ZSM-5 zeolite is the most commonly used catalyst for hydrocarbon catalytic cracking due to its acidity, unique pore structure, and high thermal and hydrothermal stability (Xue et al., 2017; Ahmed et al., 2017).

       Zeolites are advanced chemical materials that are used in a variety of petrochemical applications. There has been a surge in research interest in improving and enhancing the effectiveness of ZSM-5 as a catalyst in recent years. There has been a lot of interest in finding less expensive, more environmentally friendly alternative starting materials for the synthesis of ZSM-5 (Agustina et al., 2020; Reddy et al., 2020). Because it contains the necessary constituents for an aluminosilicate zeolite material, kaolin has been extensively researched as a zeolite precursor; its ubiquitous nature and utility in zeolite synthesis are well known as a low-cost method of obtaining catalysts (Hartati et al., 2020; Nugraha et al., 2021).

    The kaolin precursor influences physicochemical properties like morphology, porosity, and acidity, and optimal synthesis conditions are required for ZSM-5 synthesis from specific kaolin. However, studies of kaolin from different areas are critical because its varies depending on its geological occurrence. Chemical compositions of materials influence their properties, and variations in the structure and design of kaolin can thus influence its subsequent chemical reactivity (Pan et al., 2017; Krisnandi et al., 2019). The kaolin-based ZSM-5 catalyst showed good activity and selectivity to valuable fuel range hydrocarbons (Nugraha et al., 2021). Furthermore, significant efforts have been made to improve the catalytic activity of ZSM-5 catalysts by loading Ni and Mo on the supports. The shape of the XRD diffraction pattern of the ZSM-5 catalyst will be affected by the impregnation process of Ni and Mo metals at a specific concentration (Kedia & Zaidi, 2014; Ramasubramanian, et al. 2018).

       The previous studies have reported the determination of physical-chemical characteristics of “Badau Belitung kaolin” and their dehydroxylation effect during metakaolinization and metakaolinization on the specific surface area (Ulfiati et al., 2020a; Ulfiati et al., 2020b). The current study aims to observe the physicochemical properties and catalytical performance of ZSM-5 catalyst based on kaolin produced. The catalyst is expected to be used in heavy distillate catalytic cracking. This study used a heavy distillate fraction of crude oil with a boiling point of more than350 ^°C as feedstock.

    The synthesis of bifunctional Ni-Mo/HZSM-5 for catalytic cracking of petroleum heavy fractions was carried out using “Badau Belitung kaolin” as raw material. There are five formulas: A, B, C, D, and E, with varying SiO₂/Al₂O₃, SiO₂/Na₂O, and H₂O/SiO₂ molar ratios. The surface area and pore volume of the catalysts Formula A, C and D increased significantly after Ni and Mo metals impregnation. The surface area and pore volume of the catalysts of formulas B and E remained relatively stable. This is due to a structural change from crystalline to amorphous. The result of performance test of the catalyst on the catalytic cracking process, where it does not use a catalyst, the yields did not produce a light hydrocarbon fraction (C₃-C₅), whereas when using a bifunctional catalyst Ni-Mo/HZSM-5 Formula E, it is seen that there is a fair amount of hydrocarbon fraction (C₃-C₅), as well as for the cracking process using Ni-Mo Commercial Catalyst. As a result, it is possible to conclude that the catalyst synthesized with Formula E has a fairly good cracking ability. When compared to the Ni-Mo commercial catalyst, the catalyst's performance test results showed roughly similar results in the catalytic cracking process of the heavy distillate fraction.

        The research was funded by a Research Grant from Penelitian Disertasi Doktor Kementerian Riset dan Teknologi/Badan Riset dan Inovasi Nasional Tahun Anggaran 2021 Nomor: NKB-328/UN2.RST/HKP.05.00/2021. The authors would also like to acknowledge the technical assistance provided by the Universitas Indonesia Advanced Materials Laboratory and the PPPTMGB "LEMIGAS" Catalyst Laboratory.

Agustina, T.E., Melwita, E., Bahrin, D., Gayatri, R., Purwaningtyas, I.F., 2020. Synthesis of Nano-Photocatalyst ZnO-Natural Zeolite to Degrade Procion Red. International Journal of Technology, Volume 11(3), pp. 472–481

Ahmed, M.H., Muraza, O., Jamil, A.K., Shafei, E.N., Yamani, Z.H., Choi, K.H., 2017. Steam Catalytic Cracking of n-dodecane over Ni and Ni/Co Bimetallic Catalyst Supported on Hierarchical BEA Zeolite. Energy & Fuels, Volume 31(5), pp. 5482–5490

Kedia, A.O. and Zaidi, H.A., 2014. Conversion of Methanol to Hydrocarbons over Ni-ZSM-5 Conversion of Methanol to Hydrocarbons Over Ni-ZSM-5 Catalyst. International Journal Advanced Research Science Engineering, Volume 3(1), pp. 350–356

Alotaibi, F.M., Gonz´alez-Cort´es, S., Alotibi, M.F., Xiao, T., Al-Megren, H., Yang, G., Edwards, P.P., 2018. Enhancing the production of light olefins from heavy crude oils: Turning challenges into opportunities. Catalysis, Volume 317, pp. 86–98

Ayodele O.B., Abdullah A.Z., 2019. Exploring Kaolinite as Dry Methane Reforming Catalyst Support: Influences of Chemical Activation, Organic Ligand Functionalization and Calcination Temperature. Applied Catalysis A, General, Volume 576, pp. 20–31

Corma, A., Corresa, E., Mathieu, Y., Sauvanaud, L., Al-Bogami, S., Al Ghrami M.S., Bourane, A., 2017. Crude Oil to Chemicals: Light Olefins from Crude Oil. Catalysis Science & Technology, Volume 7(1), pp. 12–46

Gholami, Z., Gholami, F., Tišler, Z., Tomas, M., Vakili, M., 2021. A Review on Production of Light Olefins via Fluid Catalytic Cracking. Energies, Volume 14(4), pp. 1089

Ramasubramanian, V., Ramsurn, H. and Price, G.L., 2019. “Methane dehydro- aromatization – A study on hydrogen use for catalyst reduction, role of molybdenum, the nature of catalyst support and significance of Bronsted acid sites.  Journal of Energy Chemistry, Volume 34, pp. 20–32

Hartati, Trisunaryanti, W., Mukti, R.R., Kartika, I.A., Firda, P.B.D., Sumbogo, S.D., Prasetyoko, D., Bahruji, H., 2020. Highly Selective Hierarchical ZSM-5 from Kaolin for Catalytic Cracking of Calophyllum Inophyllum Oil to Biofuel. Journal of the Energy Institute, Volume 93(6), pp. 2238–2246

Hidayat, A., Mukti, N.I.F., Handoko, B., Sutrisno, B., 2018. Biodiesel Production from Rice Bran Oil over Modified Natural Zeolite Catalyst. International Journal of Technology, Volume 9(2), pp. 400–411

Krisnandi, Y.K., Saragi, I.R., Sihombing, R., Ekananda, R., Sari, I.P., Griffith, B.E., Hanna, J.V., 2019. Article: Synthesis and Characterization of Crystalline NaY-Zeolite from Belitung Kaolin as Catalyst for n-Hexadecane Cracking. Crystals, Volume 9(8), pp. 404

Kubliha, M., Trnovcová, V., Ondruška, J., Štub?a, I., Bošák, O., Kaljuvee, T., 2017. Comparison of Dehydration in Kaolin and Illite Using DC Conductivity Measurements. Applied Clay Science, Volume 149, pp. 8–12

Maliwan S., Koji M., Kaito O., Misaki O., Yuichiro H., Norikazu N., Sira S., 2019. Bifunctional ZSM-5/hydrotalcite Composite for Enhanced Production of 5-Hydroxymethylfurfural from Glucose. New Journal of Chemistry, Volume 43, pp. 9483–9490

Nugraha, R.E., Prasetyoko, D., Mijan, N.A., Bahruji, H., Suprapto, S., Taufiq-Yap, Y.H., Jalil, A.A., 2021. The Effect of Structure Directing Agents on Micro/Mesopore Structures of Aluminosilicates from Indonesian Kaolin as Deoxygenation Catalysts. Microporous and Mesoporous Materials, Volume 315, pp. 110917

Pan, F., Lu, X., Yan Y., Wang, T., 2017. Synthesis of Nano/Micro Scale ZSM-5 from Kaolin and Its Catalytic Performance. Kinetics and Catalysis, Volume 58(5), pp. 541–548

Reddy, J.K., Lad, S., Mantri, K., Das, J., Raman, G., Jasra, R.V., 2020. Zeolite?based Catalysts for the Removal of Trace Olefins from Aromatic Streams. Applied Petrochemical Research, Volume 10, pp. 107–114

Sadrameli, S.M., 2016. Thermal/Catalytic Cracking of Liquid Hydrocarbons for The Production of Olefins: A State-of-The Art-Review II: Catalytic Cracking Review. Fuel, Volume 173, pp. 285–297

Machmudah, S., Ceaser, M.R., Alwajdy, M.F., Winardi, S., Kanda, H. and Goto, M., 2019. Hydrothermal and Solvothermal Synthesis of Cerium-Zirconium Oxides for Catalyst Applications. International Journal of Technology, Volume 10(3), pp. 582-592

Ulfiati, R., Dhaneswara, D., Fatriansyah, J.F., Harjanto, S., 2020a. The Effect of Calcination Temperature on Metakaolin Characteristic Synthesized from Badau Belitung Kaolin. Key Engineering Materials, Volume 841, pp. 312–316

Ulfiati, R., Rozaq, F.M., Dhaneswara, D., Harjanto, S., 2020b. Characterization of Calcined Badau Belitung Kaolin as Potential Raw Materials of Zeolite. Int. AIP Conference Proceedings, Volume 2232(1), pp. 040011

Xue, T., Liu, H., Zhang, Y., Wu, H., Wu, P., He, M., 2017. Synthesis of ZSM-5 with Hierarchical Porosity: In-Situ Conversion of The Mesoporous Silica-Alumina Species to Hierarchical Zeolite. Microporous and Mesoporous Materials, Volume 242, pp. 190–199

Yan, B., Li, W., Tao, J., Xu, N., Li, X., Chen, G., 2017. Hydrogen Production by Aqueous Phase Reforming of Phenol over Ni / ZSM-5 Catalysts. Int. J. Hydrogen Energy, Volume 42(10), pp. 6674 – 6682

Zhou X., Liu Y., Meng X., Shen B., Xiao F., 2013. Synthesis and Catalytic Cracking Performance of Fe/Ti ZSM-5 Zeolite from Attapulgite Mineral. Chin J Catal, Volume 34(8), pp. 1504–1512