Bifunctional CaCO3/HY Catalyst in the Simultaneous Cracking-Deoxygenation of Palm Oil to Diesel-Range Hydrocarbons

Rosyad Adrian Febriansyar, Teguh Riyanto, I. Istadi, Didi D. Anggoro, Bunjerd Jongsomjit


Palm oil is a promising raw material for biofuel production using the simultaneous catalytic mechanism of the bifunctional cracking-deoxygenation reactions. Through the cracking-deoxygenation process, the chains of palmitic acid and oleic acid in the palm oil were converted to diesel-range hydrocarbons. The combination effects of CaCO3 and HY zeolite enhanced the bifunctional catalytic cracking-deoxygenation of palm oil into biofuel, because of the increasing acid and basic sites in the catalysts due to the synergistic roles of CaCO3 and HY. The introduction of CaCO3 on HY zeolite generated both a strong acid and strong basic sites simultaneously on the designed catalyst, which supports the bifunctional mechanisms of hybrid cracking-deoxygenation, respectively. The CaCO3 impregnated on the HY catalyst has a synergistic and bifunctional effect on the catalyst supporting cracking-deoxygenation reaction mechanisms as mentioned previously. The deoxygenation reaction required the bifunctional strong acid and strong basic sites on the CaCO3/HY catalyst through decarboxylation, decarbonylation, and hydrodeoxygenation reaction mechanisms. Meanwhile, the cracking reaction pathway was supported by the strong acid sites generated on the CaCO3/HY catalyst. In other words, the high acidity strength promotes diesel selectivity, whereas the high strength of basicity leads to the deoxygenation reaction.


Bifunctional; Biofuel; Calcium carbonate; Cracking; Deoxygenation; Palm oil

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Al-Othman, Z. A. (2012). A Review: Fundamental aspects of silicate mesoporous materials. Materials, 5(12), 2874–2902.

Anggoro, D. D., Buchori, L., Silaen, G. C. and Utami, R. N. (2017). Preparation, characterization, and activation of Co-Mo/Y zeolite catalyst for coal tar conversion to liquid fuel. Bulletin of Chemical Reaction Engineering and Catalysis, 12(2), 219.

Asikin-Mijan, N., Lee, H. V., Juan, J. C., Noorsaadah, A. R. and Taufiq-Yap, Y. H. (2017). Catalytic deoxygenation of triglycerides to green diesel over modified CaO-based catalysts. RSC Advances, 7(73), 46445–46460.

Asikin-Mijan, N., Lee, H. V., Juan, J. C., Noorsaadah, A. R., Abdulkareem-Alsultan, G., Arumugam, M. and Taufiq-Yap, Y. H. (2016). Waste clamshell-derived CaO supported Co and W catalysts for renewable fuels production via cracking-deoxygenation of triolein. Journal of Analytical and Applied Pyrolysis, 120, 110–120.

Asikin-Mijan, N., Rosman, N. A., AbdulKareem-Alsultan, G., Mastuli, M. S., Lee, H. V., Nabihah-Fauzi, N., Lokman, I. M., Alharthi, F. A., Alghamdi, A. A., Aisyahi, A. A. and Taufiq-Yap, Y. H. (2020). Production of renewable diesel from jatropha curcas oil via pyrolytic-deoxygenation over various multi-wall carbon nanotube-based catalysts. Process Safety and Environmental Protection, 142, 336–349.

Bhatia, S., Mohamed, A. R. and Shah, N. A. A. (2009). Composites as cracking catalysts in the production of biofuel from palm oil: Deactivation studies. Chemical Engineering Journal, 155 (1–2), 347–354.

Bonenfant, D., Kharoune, M., Niquette, P., Mimeault, M. and Hausler, R. (2008). Advances in principal factors influencing carbon dioxide adsorption on zeolites. Science and Technology of Advanced Materials, 9(1), 13007.

Charisiou, N. D., Siakavelas, G., Tzounis, L., Sebastian, V., Monzon, A., Baker, M. A., Hinder, S. J., Polychronopoulou, K., Yentekakis, I. V. and Goula, M. A. (2018). An in depth investigation of deactivation through carbon formation during the biogas dry reforming reaction for Ni supported on modified with {CeO}2 and La2O3 zirconia catalysts. International Journal of Hydrogen Energy, 43(41), 18955–18976.

Cheng, H., Zhang, J., Chen, Y., Zhang, W., Ji, R., Song, Y., Li, W., Bian, Y., Jiang, X., Xue, J. and Han, J. (2022). Hierarchical porous biochars with controlled pore structures derived from co-pyrolysis of potassium/calcium carbonate with cotton straw for efficient sorption of diethyl phthalate from aqueous solution. Bioresource Technology, 346, 126604.

Cheng, S., Wei, L., Julson, J., Muthukumarappan, K. and Kharel, P. R. (2017). Upgrading pyrolysis bio-oil to hydrocarbon enriched biofuel over bifunctional Fe-Ni/HZSM-5 catalyst in supercritical methanol. Fuel Processing Technology, 167, 117–126.

Choo, M.-Y., Oi, L. E., Ling, T. C., Ng, E.-P., Lin, Y.-C., Centi, G. and Juan, J. C. (2020). Deoxygenation of triolein to green diesel in the H2-free condition: Effect of transition metal oxide supported on zeolite Y. Journal of Analytical and Applied Pyrolysis, 147, 104797.

Corma, A. and Orchillés, A. V. (2000). Current views on the mechanism of catalytic cracking. Microporous and Mesoporous Materials, 35–36, 21–30.

Dias, J. A. C. and Assaf, J. M. (2003). Influence of calcium content in Ni/CaO/γ-Al2O3 catalysts for CO2-reforming of methane. Catalysis Today, 85(1), 59–68.

Doyle, A. M., Albayati, T. M., Abbas, A. S. and Alismaeel, Z. T. (2016). Biodiesel production by esterification of oleic acid over zeolite y prepared from kaolin. Renew Energy, 97, 19–23.

Elias, S., Rabiu, A. M., Okeleye, B. I., Okudoh, V. and Oyekola, O. (2020). Bifunctional heterogeneous catalyst for biodiesel production from waste vegetable oil. Applied Sciences, 10(9), 3153.

Ezeh, C. I., Yang, X., He, J., Snape, C. and Cheng, X. M. (2018). Correlating ultrasonic impulse and addition of ZnO promoter with CO2 conversion and methanol selectivity of CuO/ZrO2 catalysts. Ultrasonics Sonochemistry, 42, 48–56.

Fathi, S., Sohrabi, M. and Falamaki, C. (2014). Improvement of HZSM-5 performance by alkaline treatments: Comparative catalytic study in the MTG reactions. Fuel, 116, 529–537.

Gallei, E. and Stumpf, G. (1976). Infrared Spectroscopic studies of the adsorption of carbon dioxide and the coadsorption of carbon dioxide and water on CaY- and NiY-Zeolites. Journal of Colloid and Interface Science, 55(2), 415–420.

Golubev, I. S., Dik, P. P., Kazakov, M. O., Pereyma, V. Yu., Klimov, O. V., Smirnova, M. Yu., Prosvirin, I. P., Gerasimov, E. Yu., Kondrashev, D. O., Golovachev, V. A., Vedernikov, O. S., Kleimenov, A. V. and Noskov, A. S. (2021). The effect of Si/Al ratio of zeolite Y in NiW catalyst for second stage hydrocracking. Catalysis Today, 378, 65–74.

Gosselink, R. W., Hollak, S. A. W., Chang, S.-W., van Haveren, J., de Jong, K. P., Bitter, J. H. and van Es, D. S. (2013). Reaction pathways for the deoxygenation of vegetable oils and related model compounds. ChemSusChem, 6(9), 1576–1594.

Hancsók, J., Magyar, S., and Holló, A. (2007). Importance of isoparaffins in the crude oil refining industry. Chemical Engineering Transactions, 11, 41–46.

Hartanto, D., Sin Yuan, L., Mutia Sari, S., Sugiarso, D., Kris Murwarni, I., Ersam, T., Prasetyoko, D. and Nur, H. (2016). The use of the combination of ftir, pyridine adsorption, 27Al and 29Si MAS NMR to determine the brönsted and lewis acidic sites. Jurnal Teknologi, 78(6), 223–228.

Hermida, L., Abdullah, A. Z. and Mohamed, A. R. (2015). Deoxygenation of fatty acid to produce diesel-like hydrocarbons: A review of process conditions, reaction kinetics and mechanism. Renewable and Sustainable Energy Reviews, 42, 1223–1233.

Huang, Y. C., Fowkes, F. M., Lloyd, T. B. and Sanders, N. D. (1991). Adsorption of calcium ions from calcium chloride solutions onto calcium carbonate particles. Langmuir, 7(8), 1742–1748.

Huang, Z., Zhang, J., Li, P., Xu, L., Zhang, X., Yuan, Y. and Xu, L. (2017). Tert-butylation of naphthalene by tertiary butanol over HY zeolite and cerium-modified HY catalysts. Catalysis Science & Technology, 7(20), 4700–4709.

Istadi, I., Riyanto, T., Buchori, L., Anggoro, D. D., Gilbert, G., Meiranti, K. A., and Khofiyanida, E. (2020a). Enhancing brønsted and lewis acid sites of the utilized spent rfcc catalyst waste for the continuous cracking process of palm oil to biofuels. Industrial and Engineering Chemistry Research, 59(20), 9459–9468.

Istadi, I., Riyanto, T., Buchori, L., Anggoro, D. D., Pakpahan, A. W. S. and Pakpahan, A. J. (2021a). Biofuels production from catalytic cracking of palm oil using modified HY zeolite catalysts over a continuous fixed bed catalytic reactor. International Journal of Renewable Energy Development, 10(1), 149–156.

Istadi, I., Riyanto, T., Buchori, L., Anggoro, D. D., Saputra, R. A., Muhamad, T. G. (2020b). Effect of temperature on plasma-assisted catalytic cracking of palm oil into biofuels. International Journal of Renewable Energy Development, 9(1), 107–112.

Istadi, I., Riyanto, T., Khofiyanida, E., Buchori, L., Anggoro, D. D., Sumantri, I., Putro, B. H. S. and Firnanda, A. S. (2021b). Low-oxygenated biofuels production from palm oil through hydrocracking process using the enhanced spent RFCC catalysts. Bioresource Technology Reports, 14, 100677.

Jun, Y., Lee, S., Lee, K. and Choi, M. (2017). Effects of secondary mesoporosity and zeolite crystallinity on catalyst deactivation of ZSM-5 in Propanal conversion. Microporous and Mesoporous Materials, 245, 16–23.

Khan, S., Kay Lup, A. N., Qureshi, K. M., Abnisa, F., Wan Daud, W. M. A. and Patah, M. F. A. A (2019). Review on deoxygenation of triglycerides for jet fuel range hydrocarbons. Journal of Analytical and Applied Pyrolysis, 140, 1–24.

Kianfar, E., Salimi, M., Pirouzfar, V. and Koohestani, B. (2018). Synthesis and modification of zeolite ZSM-5 catalyst with solutions of calcium carbonate (CaCO3) and sodium carbonate (Na2CO3) for methanol to gasoline conversion. International Journal of Chemical Reactor Engineering, 16(7), 1-7.

Kubička, D., Horáček, J., Setnička, M., Bulánek, R., Zukal, A. and Kubičková, I. (2014). Effect of support-active phase interactions on the catalyst activity and selectivity in deoxygenation of triglycerides. Applied Catalysis B: Environmental, 145, 101–107.

Kwon, K. C., Mayfield, H., Marolla, T., Nichols, B., and Mashburn, M. (2011). Catalytic deoxygenation of liquid biomass for hydrocarbon fuels. Renew Energy, 36(3), 907–915.

Lawan, I., Garba, Z. N., Zhou, W., Zhang, M. and Yuan, Z. (2020). Synergies between the Microwave Reactor and CaO/zeolite catalyst in waste lard biodiesel production. Renew Energy, 145, 2550–2560.

Li, S.-C., Lin, Y.-C. and Li, Y.-P. (2021). Understanding the catalytic activity of microporous and mesoporous zeolites in cracking by experiments and simulations. Catalysts, 11(9), 1114.

Li, T., Cheng, J., Huang, R., Yang, W., Zhou, J. and Cen, K. (2016). Hydrocracking of palm oil to jet biofuel over different zeolites. International Journal of Hydrogen Energy, 41(47), 21883–21887.

Liu, L. and Corma, A. (2018). Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chemical Reviews, 118(10), 4981–5079.

Meng, B., Ren, S., Zhang, X., Chen, K., Wei, W., Guo, Q. and Shen, B. (2022). Enhancement of the strong brønsted acidity and mesoporosity: Zr4+ promoted framework modification of zeolite Y. Microporous and Mesoporous Materials, 335, 111849.

Munnik, P., de Jongh, P. E. and de Jong, K. P. (2015). Recent developments in the synthesis of supported catalysts. Chemical Reviews, 115(14), 6687–6718.

Oenema, J., Hofmann, J. P., Hensen, E. J. M., Zečević, J. and Jong, K. P. (2020). Assessment of the location of Pt nanoparticles in Pt/Zeolite Y/Γ‐Al2O3 composite catalysts. ChemCatChem, 12(2), 615–622.

Ooi, X. Y., Gao, W., Ong, H. C., Lee, H. V., Juan, J. C., Chen, W. H. and Lee, K. T. (2019). Overview on catalytic deoxygenation for biofuel synthesis using metal oxide supported catalysts. Renewable and Sustainable Energy Reviews, 112, 834–852.

Oyebanji, J. A., Okekunle, P. O. and Fayomi, O. S. I. (2020). Synthesis and characterization of zeolite-Y using ficus exasperata leaf: A preliminary study. Case Studies in Chemical and Environmental Engineering, 2, 100063.

Papageridis, K. N., Charisiou, N. D., Douvartzides, S., Sebastian, V., Hinder, S. J., Baker, M. A., AlKhoori, S., Polychronopoulou, K. and Goula, M. A. (2020). Promoting effect of CaO-MgO mixed oxide on Ni/γ-Al2O3 catalyst for selective catalytic deoxygenation of palm oil. Renew Energy, 162, 1793–1810.

Peng, X., Cheng, K., Kang, J., Gu, B., Yu, X., Zhang, Q. and Wang, Y. (2015). Impact of hydrogenolysis on the selectivity of the fischer-tropsch synthesis: Diesel fuel production over mesoporous zeolite-Y-supported cobalt nanoparticles. Angewandte Chemie, 127(15), 4636–4639.

Phung, T. K., Casazza, A. A., Aliakbarian, B., Finocchio, E., Perego, P. and Busca, G. (2013). Catalytic conversion of ethyl acetate and acetic acid on alumina as models of vegetable oils conversion to biofuels. Chemical Engineering Journal, 215–216, 838–848.

Puriwat, J., Chaitree, W., Suriye, K., Dokjampa, S., Praserthdam, P. and Panpranot, J. (2010). Elucidation of the basicity dependence of 1-butene isomerization on MgO/Mg(OH)2 catalysts. Catalysis Communication, 12(2), 80–85.

Putluru, S. S. R., Jensen, A. D., Riisager, A. and Fehrmann, R. (2011). Alkali resistant fe-zeolite catalysts for SCR of NO with NH3 in flue gases. Topics in Catalysis, 54 (16–18), 1286–1292.

Ramesh, A., Tamizhdurai, P. and Shanthi, K. (2019). Catalytic hydrodeoxygenation of jojoba oil to the green-fuel application on NI-MoS/Mesoporous Zirconia-Silica Catalysts. Renew Energy, 138, 161–173.

Riyanto, T., Istadi, I., Buchori, L., Anggoro, D. D., and Dani Nandiyanto, A. B. (2020). Plasma-assisted catalytic cracking as an advanced process for vegetable oils conversion to biofuels: A mini review. Industrial and Engineering Chemistry Research, 59(40), 17632–17652.

Riyanto, T., Istadi, I., Jongsomjit, B., Anggoro, D. D., Pratama, A. A. and al Faris, M. A. (2021). Improved brønsted to lewis (B/L) ratio of Co- and Mo-impregnated ZSM-5 catalysts for palm oil conversion to hydrocarbon-rich biofuels. Catalysts, 11(11), 1286.

Santillan-Jimenez, E. and Crocker, M. (2012). Catalytic deoxygenation of fatty acids and their derivatives to hydrocarbon fuels via decarboxylation/decarbonylation. Journal of Chemical Technology and Biotechnology, 87(8), 1041–1050.

Sartipi, S., Makkee, M., Kapteijn, F. and Gascon, J. (2014). Catalysis engineering of bifunctional solids for the one-step synthesis of liquid fuels from syngas: A Review. Catalysis Science & Technology, 4(4), 893–907.

Seifi, H. and Sadrameli, S. M. (2016). Improvement of renewable transportation fuel properties by deoxygenation process using thermal and catalytic cracking of triglycerides and their methyl esters. Applied Thermal Engineering, 100, 1102–1110.

Shakirova, L. Kh., Pluzhnikova, M. F. and Tsybulevskii, A. M. (1980). Mechanism of catalytic cracking of hydrocarbons on zeolites. Petroleum Chemistry U.S.S.R., 20(1), 45–54.

Srihanun, N., Dujjanutat, P., Muanruksa, P. and Kaewkannetra, P. (2020). Biofuels of green diesel–kerosene–gasoline production from palm oil: Effect of palladium cooperated with second metal on hydrocracking reaction. Catalysts, 10(2), 241.

Suárez, N., Pérez-Pariente, J., Márquez-Álvarez, C., Grande Casas, M., Mayoral, A. and Moreno, A. (2019). Preparation of mesoporous beta zeolite by fluoride treatment in liquid phase. textural, acid and catalytic properties. Microporous and Mesoporous Materials, 284, 296–303.

Sugiyama, S., Sakuwa, Y., Ogino, T., Sakamoto, N., Shimoda, N., Katoh, M. and Kimura, N. (2019). Gas-phase epoxidation of propylene to propylene oxide on a supported catalyst modified with various dopants. Catalysts, 9, 638.

Suprun, W., Lutecki, M., Haber, T. and Papp, H. (2009). Acidic catalysts for the dehydration of glycerol: Activity and deactivation. Journal of Molecular Catalysis A: Chemical, 309 (1–2), 71–78.

Tsai, W.-T. (2013). Microstructural characterization of calcite-based powder materials prepared by planetary ball milling. Materials, 6(8), 3361–3372.

Twaiq, F. A. A., Mohamad, A. R. and Bhatia, S. (2004). Performance of composite catalysts in palm oil cracking for the production of liquid fuels and chemicals. Fuel Processing Technology, 85(11), 1283–1300.

Wang, H., Lin, H., Zheng, Y., Ng, S., Brown, H., and Xia, Y. (2019). Kaolin-based catalyst as a triglyceride FCC upgrading catalyst with high deoxygenation, mild cracking, and low dehydrogenation performances. Catalysis Today, 319, 164–171.

Wang, X., Fang, Q., Wang, J., Gui, K. and Thomas, H. R. (2020). Effect of CaCO3 on catalytic activity of Fe–Ce/Ti catalysts for NH3-SCR reaction. RSC Advances, 10(73), 44876–44883.

Wei, T., Wang, M., Wei, W., Sun, Y. and Zhong, B. (2003). Effect of base strength and basicity on catalytic behavior of solid bases for synthesis of dimethyl carbonate from propylene carbonate and methanol. Fuel Processing Technology, 83(1–3), 175–182.

Xu, Z.-X., Liu, P., Xu, G.-S., Liu, Q., He, Z.-X., and Wang, Q. (2017). Bio-fuel oil characteristic from catalytic cracking of hydrogenated palm oil. Energy, 133, 666–675.

Yi, L., Liu, H., Xiao, K., Wang, G., Zhang, Q., Hu, H. and Yao, H. (2019). In Situ upgrading of bio-oil via CaO catalyst derived from organic precursors. Proceedings of the Combustion Institute, 37(3), 3119–3126.

Yigezu, Z. D. and Muthukumar, K. (2014). Catalytic cracking of vegetable oil with metal oxides for biofuel production. Energy Conversion and Management, 84, 326–333.

Zhao, W., Huang, J., Ni, K., Zhang, X., Lai, Z., Cai, Y. and Li, X. (2018). Research on non-thermal plasma assisted HZSM-5 online catalytic upgrading bio-oil. Journal of the Energy Institute, 91(4), 595–604.

Zhao, X., Wei, L., Cheng, S. and Julson, J. (2015). Optimization of catalytic cracking process for upgrading camelina oil to hydrocarbon biofuel. Industrial Crops and Products, 77, 516–526.

Zhao, X., Wei, L., Julson, J., Gu, Z. and Cao, Y. (2015). Catalytic cracking of inedible camelina oils to hydrocarbon fuels over bifunctional Zn/ZSM-5 catalysts. Korean Journal of Chemical Engineering, 32(8), 1528–1541.

Zheng, Y., Guo, Y., Wang, J., Luo, L. and Zhu, T. (2021). Ca doping effect on the competition of NH3–SCR and NH3 oxidation reactions over vanadium-based catalysts. The Journal of Physical Chemistry C, 125(11), 6128–6136.



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