• International Journal of Technology (IJTech)
  • Vol 13, No 4 (2022)

Catalytic Conversion of Beef Tallow to Biofuels using MgO Nanoparticles Green Synthesized by Zingiber officinale Roscoe Rhizome Extract

Catalytic Conversion of Beef Tallow to Biofuels using MgO Nanoparticles Green Synthesized by Zingiber officinale Roscoe Rhizome Extract

Title: Catalytic Conversion of Beef Tallow to Biofuels using MgO Nanoparticles Green Synthesized by Zingiber officinale Roscoe Rhizome Extract
Adi Riyadhi, Yoki Yulizar, Bambang Heru Susanto

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Riyadhi, A., Yulizar, Y., Susanto, B.H., 2021. Catalytic Conversion of Beef Tallow to Biofuels using MgO Nanoparticles Green Synthesized by Zingiber officinale Roscoe Rhizome Extract. International Journal of Technology. Volume 13(4), pp. 900-911

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Adi Riyadhi 1. Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 16424, Indonesia 2. Department of Chemistry, Faculty of Science and Technology, Universitas Islam
Yoki Yulizar Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok 16424, Indonesia
Bambang Heru Susanto Department of Chemical Engineering, Faculty of Engineering, Universitas Indonesia, Depok 16424, Indonesia
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Abstract
Catalytic Conversion of Beef Tallow to Biofuels using MgO Nanoparticles Green Synthesized by Zingiber officinale Roscoe Rhizome Extract

MgO nanoparticles (MgONPs) have been successfully synthesized using ZOE (Zingiber officinale Roscoe extract in water) and applied for catalytic conversion of beef tallow to bio gasoline, kerosene and diesel. ZOE was used due to containing the alkaloid as a weak base source to hydrolyze Mg(NO3)2 precursor and form the MgONPs. The synthesized MgONPs was characterized using UV-Vis spectrophotometer, X-ray diffraction (XRD), particle size analyzer (PSA), Brunauer?Emmett?Teller (BET) surface areas, UV–Vis diffuse reflectance spectrophotometry (DRS), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) and transmission electron microscopy (TEM). The catalyst activity was performed to convert beef tallow to biofuel in the stainless-steel reactors at 3000C for 60 min. The conversion results of beef tallow were analyzed using gas chromatography-mass spectrometry (GC-MS). The beef tallow conversion shows that all fatty acids derived from beef tallow are converted to gases and liquids fractions. The conversion using catalyst to feed weight ratio of  4 wt. % produced the liquid fractions containing the dominant of alkanes (62.85%) and cyclic compounds (18.77%). Pentadecane and Heptadecane are the main compounds in liquid products, which indicates a decarboxylation reaction.

Beef tallow; Decarboxylation; MgO Nanoparticles; Zingiber officinale Roscoe

Introduction

    Fatty acids derived from animals and plants can be converted into hydrocarbons through the process of cracking (Nasikin et al., 2009), deoxygenation (Susanto et al., 2016; Muharam & Soedarsono, 2020), decarboxylation (Wu et al., 2016). Using catalysts, and decarbonylation (Dawes et al., 2015) to gasoline, kerosene, and diesel. The MgO catalyst prepared from magnesium oxalate was studied by Khromova et al. (2013) and is useful for decarboxylation of pentanoic acid to dibutyl ketone. MgO catalysts are also useful for the decarboxylation reaction of naphthenic acid from crude oil in petroleum (Zhang et al., 2006). MgO catalysts encourage the decarboxylation of fatty acids into hydrocarbons and CO2 (Natewong et al., 2016; Dickerson & Soria, 2013). Decarboxylation of oleic acid occurs at 300 0C decarboxylation and pyrolysis reactions occur at 350°C while the dominant pyrolysis reaction is it 400°C (Roh et al., 2011). Leong et al. (2016) also reported that the highest yield of the liquid fraction from the crude glycerol pyrolysis result was obtained at a temperature of 400°C. The mechanism of magnesium oxides as a catalyst in the decarboxylation of acids has been studied in works (Perera et al., 2015; Na et al., 2010; Gasanov et al., 2013; Diez et al., 2000). Strong chemisorption of a carboxyl group (?COOH) on the MgO surface leads to a decarboxylation reaction (Perera et al., 2015)Nanocatalysts can be used to increase the yield and performance of biofuel production. Various nanotechnology applications depend on nano-size properties, morphology, and surfaces reactivity (Sekoai et al., 2019). MgO nanoparticle catalysts can be synthesized using plant extracts, and this method continues to be developed due to using environmentally friendly materials. Some plant extracts that have been studied for MgO NPs synthesis include the Neem leaf plant (Moorthy et al., 2015), Rosemary flower (Abdallah et al., 2019), Cajanus cajan leaf (Surya et al., 2021), and Trigonella 
       Rhizome Ginger (Zingiber officinale Roscoe) is an Indonesian spice that is very important in everyday life, especially in health. Ginger is a medicinal plant that contains alkaloids (Riaz et al., 2015). Alkaloids are a group of the weak organic base that is mostly heterocyclic and found in plants. Alkaloids can form salts when reacting with acids. Alkaloids content in dried ginger (Zingiber officinale Roscoe) is 5.86% (w/w) (Raaof et al., 2013). Ginger extract has been widely used as auxiliary material for nanomaterial synthesis. Ginger extract was used to synthesize AgNPs with particle sizes of 10-20 nm (Velmurugan et al., 2014) and AuNps with the size of 5-20 nm  (Yang et al., 2017). Ginger extract has a high alkaloid content and potency for nanoparticle formation of MgO. In forming metal oxide, nanoparticles need a weak base source as an alkaloid in the plant extract for hydrolyzing metal ion to metal hydroxide, finally forming metal oxide nanoparticles after calcination (Yulizar et al., 2018).
     This study aimed to develop an effective and efficient catalyst at low temperatures to produce biogasoline, kerosene, and diesel from beef tallow. MgONPs synthesis used white ginger extract (Zingiber officinale Roscoe) as a weak base and Mg(NO3)2 as a precursor. Catalyst characterization and chemical properties of products are carried out using some chemical instrumentations. MgONPs catalyst activity was conducted on the conversion of beef tallow to biogasoline, kerosene, and diesel productions.

Conclusion

    MgONPs have been successfully synthesized using the green synthesis method from magnesium nitrate precursor and white ginger extract as the weak base source and capping agents. The results of MgONPs characterization show the hexagonal shape and the nano size of 79.25 nm. MgONPs catalytic activity of the beef tallow conversion at low temperatures (300°C) for 60 min showed that a higher catalyst resulted in higher gasses, gasoline, and kerosene products, contrary to diesel products. The liquid fractions consist of gasoline, kerosene, and diesel products. The amount of gasoline, kerosene, and cyclic compounds of liquid fraction resulting from beef tallow conversion using MgONPs catalyst is more than the commercial MgO catalyst. MgONPs catalyst encourages more cracking process than commercial MgO. Higher MgONPs catalysts ratio also indicated higher alkanes and cyclic compound products due to the catalytic deoxygenation and cracking process. The primary compounds of the liquid product are pentadecane and Heptadecane, which indicates that decarboxylation reaction occurs from hexadecanoic acid and octadecanoic acid. Tallow and vegetable oils have similar fatty acid content, so catalyst MgONPs can also convert vegetable oils to biofuel.

Acknowledgement

    The Indonesia Endowment Fund for Education funded this research, Ministry of Finance, Republik Indonesia (LPDP Kementerian Keuangan RI) for the Scholarships and Research Grants (No. S-168/LPDP.3/2017).

Supplementary Material
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R1-CE-4821-20210713211658.docx ---
References

Abdallah, Y., Ogunyemi, S.O., Abdelazez, A., Zhang, M., Hong, X., Ibrahim, E., Hossain, A., Fouad, H., Li, B., Chen, J., 2019. The Green Synthesis of MgO Nano-Flowers Using Rosmarinus officinalis L. (Rosemary) and the Antibacterial Activities against Xanthomonas oryzae pv. oryzae. BioMed Research International, Volume 2019, pp. 1–8

Badar, Nurhanna, Chayed, N.F., Rusdi, R., Kamarudin, N., Kamarulzaman, N., 2012. Band Gap Energies of Magnesium Oxide Nanomaterials Synthesized by the Sol-Gel Method. Advanced Materials Research, Volume 545, pp. 157–160

Dawes, G.J.S., Scott, E.L., Le Nôtre, J., Sanders, J.P.M., Bitter, J.H., 2015. Deoxygenation of Biobased Molecules by Decarboxylation and Decarbonylation - A Review on The Role of Heterogeneous, Homogeneous and Bio-Catalysis. Green Chemistry, Volume 17(6), pp. 3231–3250

Demirbas, A. 2015. Recovery of Gasoline and Diesel Range Hydrocarbons from Waste Vegetable Oils. Petroleum Science and Technology, Volume 33(19), pp. 1703–1711.

Dickerson, T., & Soria, J., 2013. Catalytic Fast Pyrolysis: A review. Energies, Volume 6(1), pp. 514–538

Diez, V.K., Apesteguía, C.R., Di Cosimo, J.I., 2000. Acid-Base Properties and Active Site Requirements for Elimination Reactions on Alkali-Promoted MgO Catalysts. Catalysis Today, Volume 63(1), pp. 53–62

Dragu, A., Kinayyigit, S., García-Suárez, E.J., Florea, M., Stepan, E., Velea, S., Tanase, L., Collière, V., Philippot, K., Granger, P., Parvulescu, V.I., 2015. Deoxygenation of Oleic Acid: Influence of The Synthesis Route of Pd/Mesoporous Carbon Nanocatalysts onto Their Activity and Selectivity. Applied Catalysis A: General, Volume 504, pp. 81–91

Fan, L., Chen, P., Zhang, Y., Liu, S., Liu, Y., Wang, Y., Dai, L., Ruan, R., 2017. Fast Microwave-Assisted Catalytic Co-Pyrolysis of Lignin and Low-Density Polyethylene with HZSM-5 and MgO for Improved Bio-Oil Yield and Quality. Bioresource Technology, Volume 225, pp. 199–205

Gajengi, A.L., Sasaki, T., Bhanage, B.M., 2017. Mechanistic Aspects of Formation of MgO Nanoparticles under Microwave Irradiation and its Catalytic Application. Advanced Powder Technology, Volume 28(4), pp. 1185–1192

Gasanov, A.G., Azizov, A.G., Aliyeva, S.T., Gasanova, G.D., Guseynov, N.S., Khalilova, S.R., Ayyubov, I.G., 2013. Application of Magnesium and Titanium Oxides as Catalysts in Reaction Decarboxylation of Acids. Processes of petrochemistry and oil-refining. Volume 14(55), pp. 169–174

Judith Vijaya, Jayaprakash, N., Kombaiah, K., Kaviyarasu, K., Kennedy, L.J., Ramalingam, R.J., Lohedan, H.A. Al, Mohammed, M.A.V., Maaza, M., 2017. Bioreduction Potentials of Dried Root of Zingiber officinale for A Simple Green Synthesis of Silver Nanoparticles: Antibacterial Studies. Journal of Photochemistry and Photobiology B: Biology, Volume 177, pp. 62–68

Khromova, S.A., Smirnov, A.A., Selishcheva, S.A., Kukushkin, R.G., Dundich, V.O., Trusov, L.I., Yakovlev, V.A., 2013. Magnesium-Containing Catalysts for The Decarboxylation of Bio-Oil. Catalysis in industry, Volume 5(3), pp. 260–268

Leong, S.K., Lam, S.S., Ani, F.N., Ng, J.H., Chong, C.T., 2016. Production of Pyrolyzed Oil from Crude Glycerol using A Microwave Heating Technique. International Journal of Technology, Volume 7(2), pp. 323–331

Luo, Y., Guda, V.K., Hassan, E.B., Steele, P.H., Mitchell, B., Yu, F., 2016. Hydrodeoxygenation of Oxidized Distilled Bio-Oil for The Production of Gasoline Fuel Type. Energy Conversion and Management, Volume 112, pp. 319–327

Maher, K.D., Kirkwood, K.M., Gray, M.R., Bressler, D.C., 2008. Pyrolytic Decarboxylation and Cracking of Stearic Acid. Industrial and Engineering Chemistry Research, Volume 47(15), pp. 5328–5336

Moorthy, S.K., Ashok, C.H., Rao, K.V., Viswanathan, C., 2015. Synthesis and Characterization of MgO Nanoparticles by Neem Leaves Through Green Method. Materials Today: Proceedings, Volume 2(9), pp. 4360–4368

Muharam, Y., Soedarsono, J.A., 2020. Hydrodeoxygenation of Vegetable Oil in a Trickle Bed Reactor for Renewable Diesel Production. International Journal of Technology, Volume 11(7), pp. 1292–1299

Na, J.G., Yi, B.E., Kim, J.N., Yi, K.B., Park, S.Y., Park, J.H., Kim, J.N., Ko, C.H., 2010. Hydrocarbon Production from Decarboxylation of Fatty Acid without Hydrogen. Catalysis Today, Volume 156(1–2), pp. 44–48

Nasikin, M., Susanto, B.H., Hirsaman, M.A., Wijanarko, A., 2009. Biogasoline from Palm Oil by Simultaneous Cracking and Hydrogenation Reaction over Nimo / zeolite Catalyst. World Applied Sciences Journal, Volume 5, pp. 74–79

Natewong, P., Murakami, Y., Tani, H., Asami, K., Natewonga, P., Murakamib, Y., Tanic, H., Asami, K., 2016. Effect of Support Material on MgO-Based Catalyst for Production of New Hydrocarbon Bio-Diesel. American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS), Volume 22(1), pp. 153–165

Noruzi, M., 2015. Biosynthesis of Gold Nanoparticles using Plant Extracts. Bioprocess and Biosystems Engineering, Volume 38(1), pp 1–14

Oh, H.-Y., Park, J.-H., Rhee, Y.-W., Kim, J.-N., 2011. Decarboxylation of Naphthenic Acid using Alkaline Earth Metal Oxide. Journal of Industrial and Engineering Chemistry, Volume 17, pp. 788–793

Perera, D.C., Hewage, J.W., de Silva, N., 2015. Theoretical Study of Catalytic Decomposition of Acetic Acid on MgO Nanosurface. Computational and Theoretical Chemistry, Volume 1064, pp. 1–6

Pugazhendhi, A., Prabhu, R., Muruganantham, K., Shanmuganathan, R., Natarajan, S., 2019. Anticancer, Antimicrobial and Photocatalytic Activities of Green Synthesized Magnesium Oxide Nanoparticles (MgONPs) using Aqueous Extract of Sargassum wightii. Journal of Photochemistry and Photobiology B: Biology, Volume 190, pp. 86–97

Raaof, A., Al-naqqash, Z.A., Jawad, A.M., Muhsan, S.M., 2013. Evaluation of The Activity of Crude Alkaloids Extracts of Zingiber officinale Roscoe., Thymus vulgaris L. and Acacia arabica L. as coagulant agent in lab mice. Biomedicine and Biotechnology, Volume 1(2), pp. 11–16

Riaz, H., Begum, A., Raza, S.A., Khan, Z. M.-U.-D., Yousaf, H., Tariq, A., 2015. Antimicrobial Property and Phytochemical Study of Ginger Found in Local Area of Punjab, Pakistan. International Current Pharmaceutical Journal, Volume 4(7), pp. 405–409

Riyadhi, A., Yulizar, Y., Susanto, B.H., 2020. Catalytic Conversion of Beef Tallow with MgO derived from MgCO3 for Biofuels Production. IOP Conference Series: Materials Science and Engineering

Roh, H.-S., Eum, I.-H., Jeong, D.-W., Yi, B.E., Na, J.-G., 2011. The Effect of Calcination Temperature on The Performance of Ni/MgO–Al2O3 Catalysts for Decarboxylation of Oleic Acid. Catalysis Today, Volume 164(1), pp. 457–460

Santillan-Jimenez, E., Crocker, M., 2012. Catalytic Deoxygenation of Fatty Acids and Their Derivatives to Hydrocarbon Fuels via Decarboxylation/Decarbonylation. Journal of Chemical Technology and Biotechnology, Volume 87(8), pp. 1041–1050

Sekoai, P.T., Naphtaly, C., Ouma, M., Petrus, S., Modisha, P., Engelbrecht, N., Bessarabov, D. G., Ghimire, A., 2019. Application of nanoparticles in biofuels: An overview. Volume 237, pp. 380–397

Suresh, J., Pradheesh, G., Alexramani, V., Sundrarajan, M., Ig, S., 2018. Green Synthesis and Characterization of Hexagonal Shaped MgO Nanoparticles using Insulin Plant (Costus pictus D. Don) Leave Extract and its Antimicrobial as well as Anticancer Activity. Advanced Powder Technology, Volume 29(7), pp. 1685–1694

Surya, R.M., Yulizar, Y., Cahyana, A.H., Apriandanu, D.O.B., 2021. One-pot Cajanus cajan (L.) Millsp. Leaf Extract-mediated Preparation of MgFe2ONanoparticles: Optical, Structural, Morphological And Particle Size Analyses. Solid State Communications, Volume 326, pp. 114170

Susanto, B.H., Prakasa, M.B., Nasikin, M., Sukirno., 2016. Synthesis of Renewable Diesel from Palm Oil and Jatropha Curcas Oil Through Hydrodeoxygenation Using NiMo/ZAL. International Journal of Technology, Volume 7(8), pp. 1404–1411

Velmurugan, P., Anbalagan, K., Manosathyadevan, M., Lee, K.-J., Cho, M., Lee, S.-M., Park, J.-H., Oh, S.-G., Bang, K.-S., Oh, B.-T., 2014. Green Synthesis of Silver and Gold Nanoparticles using Zingiber Officinale Root Extract and Antibacterial Activity of Silver Nanoparticles Against Food Pathogens. Bioprocess Biosyst Eng, Volume 37(10), pp. 1935–1943

Vergheese, M., Vishal, S.K., 2018. Green synthesis of Magnesium Oxide nanoparticles using Trigonella foenum-graecum leaf extract and its antibacterial activity. Volume 7(3), pp. 1193–1200

Wu, J., Shi, J., Fu, J., Leidl, J.A., Hou, Z., Lu, X., 2016. Catalytic Decarboxylation of Fatty Acids to Aviation Fuels over Nickel Supported on Activated Carbon. Nature Publishing Group, Volume 6, pp. 27820

Yang, N., Li, F., Jian, T., Liu, C., Sun, H., Wang, L., Xu, H., 2017. Biogenic Synthesis of Silver Nanoparticles using Ginger (Zingiber Officinale) Extract and Their Antibacterial Properties Against Aquatic Pathogens. Acta Oceanologica Sinica, Volume 36(12), pp. 95–100

Yulizar, Y., Bakri, R., Oky, D., Apriandanu, B., Hidayat, T., 2018. Nano-Structures & Nano-Objects ZnO / CuO Nanocomposite Prepared in One-Pot Green Synthesis using Seed Bark Extract of Theobroma cacao. Nano-Structures & Nano-Objects, Volume 16, pp. 300–305

Zhang, A., Ma, Q., Wang, K., Liu, X., Shuler, P., Tang, Y., 2006. Naphthenic Acid Removal from Crude Oil Through Catalytic Decarboxylation on Magnesium Oxide. Applied Catalysis, Volume 303, pp. 103–109