Heterogeneous Catalyst based on Nickel Modified into Indonesian Natural Zeolite in Green Diesel Production from Crude Palm Oil

Green diesel is an alternative renewable and environmentally friendly fuel in the transportation sector. This study aimed to modify Indonesian natural zeolite (NZ) with nickel and apply it as a catalyst in green diesel production from crude palm oil (CPO). The materials were prepared with different Ni content of 3, 5, and 10 wt.% and characterized in detail using X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), Fourier Transform infra-red Spectroscopy (FTIR), and Surface Area Analyzer (SAA). Catalytic tests were performed in a batch reactor at a temperature of 375 °C and a pressure of 12 bar for 2 hours. Gas Chromatography-Mass Spectrometry (GC–MS) analysis was used to determine the liquid product. Based on XRD analysis, the crystallinity of materials tends to decrease after being modified with Ni. Concomitantly, the presence of Ni was indicated by new peaks with increasing intensity at 2? = 44°, 55°, and 76°. SEM analysis shows morphological changes in materials with decreasing particle sizes. The presence of Ni is also known by the presence of small spheres scattered in the material and black shades observed in TEM analysis. Based on IUPAC, the resulting isotherm graph is categorized as type I with type IV loop hysteresis and classified as micropore with an average pore size is <2 nm. The highest activity and selectivity on C₁₅ were achieved up to 77.34% and 53.11% when 3% of Ni modified NZ was applied as Catalyst compared to NZ, and other Ni modified NZ.

Crude Palm Oil; Green Diesel; Hydrodeoxygenation; Natural zeolite; Nickel

    Energy consumption is increasing drastically, along with the various increasing sectors of life. The major energy consumption area is the transportation sector that is still limited to non–renewable sources such as fossil fuels and would soon be exhausted. Therefore, exploring new renewable sources and clean energy, e.g., geothermal, solar system, the hydroelectric, wind, and bioenergy from plants and animals, would have great impact (Ameen et al., 2017).
    Biofuel based on vegetable oils, such as palm oil, are a potential alternative energy source because of their abundance, renewability, and easy processing (Ameen et al., 2019; Mardiana et al., 2022). Palm oil comprises a mixture of mono-alkyl esters from a long chain of fatty acids (mostly 17–19 carbon atoms), which can be converted into biodiesel through a catalytic process (Hermida et al., 2015). However, biodiesel is constrained with those by oxygenating products, which might cause damage to the diesel engines. The oxidative nature of biodiesel is determined by the presence of C=O and C=C bonds within the products and toxic emissions of nitrogen oxide (NO_x) (Ajala et al., 2015; Putra et al., 2018). Therefore, further research is required to develop green diesel with free–oxygen and n–paraffin (C_xH_y) components with cetane numbers approaching 100. In addition, diesel–range alkanes are obtained as the final products with high stability and eco–friendly (Alvarez-galvan et al., 2019; Chen et al., 2018; Muharam & Soedarsono, 2020).
    The production of green diesel can be achieved through the hydrodeoxygenation (HDO) reaction that aims to remove oxygen to reduce biodiesel’s oxidative levels (Yuswan et al., 2018; Shafaghat et al., 2018). The HDO reaction requires high temperature and pressure. Therefore, the HDO reaction needs a catalyst that assists in the production of second-generation biodiesel through faster and more effective reactions. However, the development of catalysts for the HDO reaction is constrained by the resistance of the catalyst material to high temperatures and low product selectivity (Lani et al., 2016). Natural zeolite can be a heterogeneous catalyst in the HDO reaction because it contains active acidic sites and robust physicochemical stability (Arun et al., 2015). In addition, natural zeolites exhibit high thermal stability, organic solvents resistance, low–cost, and non–toxicity (Primo & Garcia, 2014). The natural zeolite could be activated through physical and chemical treatments to remove impurities and enhance the amount of pore and zeolite specific surface area (Setiawan & Mahatmanti, 2018). Furthermore, the selectivity of catalytic reactions also can be increased through the loading of metals on the supporting material (Inokawa et al., 2010; Yulizar et al., 2016). As a result, the catalytic performance can be improved by increasing the active site of the Catalyst. The selection of metals for the HDO process is a challenge for current research.
    The noble metal catalysts such as Pd (Yang et al., 2017), Ru (Dwiatmoko et al., 2019), and Pt (Yang et al., 2015) have also been used for HDO catalytic activity at low temperatures, but the high price of these metals is detrimental for the production cost-effectiveness. Thus, considering the low stability and high cost of these precious metal catalysts, it is imperative to develop alternative non–noble metal-based catalyst for HDO (Chen et al., 2018; Hachemi et al., 2017). Transition metals can be used as alternative catalysts such as cobalt (Co), iron (Fe), molybdenum (Mo), and nickel (Ni) (Hongloi et al., 2019). Nickel is an attractive metal due to its high availability, excellent hydrogenation capability, and good stability (Gamliel et al., 2018). Ni has better properties than other transition metals (Cu, Co, and Fe) concerning atomic volume, structure, and atomic radius. The d–electrons and the density level of energy around the lattice plane of Ni are higher than other transition metals, thus affecting catalytic properties (Chen et al., 2018; De et al., 2016).
    Nickel-based heterogeneous catalysts are the most widely shown good performance in deoxygenation reaction (Hongloi et al., 2019). It has been reported that hydrogen molecules could be trapped in the surface defects of nickel (Liu et al., 2013). Moreover, the electronic properties of Ni metal allow similar activity reactions to those of noble metals (Pd or Pt), such as the selective C–C or C–H cleavage for hydrocarbon reaction (De et al., 2016; Hongloi et al., 2019). Kaewmeesri et al. (2015) reported Ni/?–Al₂O₃ catalysts for the methyl palmitate HDO reaction with a conversion of 60% and alkane C₁₀–C₁₂ selectivity of 58%. Research conducted by Ma and Zhao (2015) using nickel–metal nanoparticles embedded in Hierarchica Beta Zeolite (HBEA) zeolite catalyst showed the total yields of n–octadecane (C18) kept stable at 70 wt% after one h. By using palm oil as feedstocks, Susanto et al. (2016) tested NiMo/ZAL (Clinoptilolite type) catalyst for hydrodeoxygenation reaction under hydrogen pressure of 15 bar and temperature of 375°C. The result showed that the renewable diesel yield (C₁₃–C₁₉) produced a conversion of around 80.87% and selectivity of 52.78%.  At the same time, the Ni/SAPO–11 catalyst used to convert palm oil to the hydrodeoxygenation reaction obtained an alkane yield (C₁₅–C₁₈) of around 70% conversion and 80% isomerization selectivity of long alkanes (Liu et al., 2014).
    According to Hongloi et al. (2019), Ni/ZrO₂ could convert palmitic acid to n–alkane as the main composition in green diesel (C₁₅–C₁₈) of 98.33% and n–pentadecane (C₁₅) with selectivity by 76%. Hachemi et al. (2017) also studied sulfur-free Ni supported on H–Y zeolites ?–Al₂O_3, and SiO₂ synthesized by the wet impregnation method. They were tested in hydrodeoxygenation (HDO) of stearic acid. The result showed that C₁₇ was the main product from HDO of stearic acid over Ni/H–Y zeolites, Ni/?–Al₂O₃, and Ni/SiO2 representing 50% of products obtained from HDO. Similar research conducted by Yang et al. (2012) reported the supported Ni2P/SBA–15 catalyst was tested for the HDO of methyl oleate produced n–alkanes in the C₁₅–C₁₈ range which are formed from a feedstock composed mainly of C₁₈ (80%).
     The utilization of NZ modified by Fe in HDO reaction of refined palm oil was firstly investigated by our group (Putra et al., 2018) and showed high conversion up 89% and selectivity of C₁₅–C₁₈ up to 76%. The selection of metal embedded into NZ play a crucial role in the activity and selectivity of Catalyst. So far, modification of NZ with Ni as Catalyst for green diesel production has never been studied. Herein, this study will investigate the effect of Ni with different metal loading (3, 5, and 10 wt.%) modified into NZ in catalyzing green diesel production from crude palm oil. 

    In this study, NZ shows suitability with the simulated pattern of MOR and HEU phases. The presence of Ni metal nanoparticles on NZ as supporting material had no significant influence on the chemical structure of zeolite but changed the morphology and decreased the crystallinity. Variation of Ni–metal loading increase the surface area and pore volume. Catalytic test of Ni/NZ material in converting crude palm oil to C₁₅–C₁₈ as the main composition in green diesel achieved high selectivity up to 53.11%. Decarboxylation and decarbonylation were simulated as the main pathway reactions, which were dominated by the C₁₅ hydrocarbons chain. Finally, Ni/NZ exhibited a synergistic effect in selectivity to green diesel production from crude palm oil, showing its promising catalytic application.

    The authors acknowledge the financial support from the Ministry of Research, Technology, and Higher Education of the Republic of Indonesia through the Student Creativity Program (PKM-PE) 2018. Moreover, WWL would also like to acknowledge L’Oréal–UNESCO for Women in Science for the award in 2014.

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