||The Production of Hydro-processed Renewable Diesel (HRD) through non-sulfide catalyst
||Department of Aeronautics & Astronautics
Hydro-processed Renewable Diesel(HRD)
Because the traditional commercial catalyst NiMoS2/γ-Al2O3 contained sulfur, lead to the product and the environment are polluted by sulfur. In addition, precious metal catalysts such as Pd/C are too expensive. Therefore, in this study, the production of non-sulfide catalysts is mainly developed and palm oil is converted into hydro-processed renewable diesel (HRD). First, the catalysts with different supports (γ-Al2O3 and SAPO-11) and metals (Ni and Mo) are compared in experiments. Through different temperature, pressure, H2-to-oil ratio and weight hourly space velocity (WHSV), using GC-MS/FID and GC-TCD to explore the composition of liquid and gas products. Analyze the conversion rate, selectivity and yield, and study the best experimental conditions for this catalyst. After the catalyst is deactivated, it is regenerated by calcining. Use XRD, TGA, FTIR and Nitrogen adsorption/desorption isotherm to analyze the characteristics of fresh, deactivated and regenerated catalysts. Finally, test the fuel characteristics of HRD (including: cetane number, autoignition temperature, flash point, and smoke point).
EXTENDED ABSTRACT III
2.1 原料 6
2.2 催化劑製作 7
2.3 實驗設備 7
2.4 實驗步驟 9
2.5 催化劑特性檢測儀器 10
2.5.1 X-射線粉末繞射光譜(Powder X-Ray Diffraction; PXRD) 10
2.5.2熱重分析儀 (Thermal Gravimetric Analysis；TGA) 10
2.5.3氮氣等溫吸附/脫附測量(N2 Adsorption/Desorption Isotherm) 10
2.5.4穿透式電子顯微鏡 (Transmission Electron Microscopy；TEM) 10
2.5.5傅立葉轉換红外光谱 (Fourier-transform infrared spectroscopy；FTIR) 10
2.6 產物分析 11
2.7 計算方法 12
2.8 燃油特性測試方法 13
3.1 催化劑中金屬與載體對產物組成的影響 14
3.2 操作參數對產物組成的影響 17
3.3 催化劑特性分析 22
3.3.1 X光繞射分析(XRD) 22
3.3.2 結構特性分析(BET) 23
3.3.3 熱重分析(TGA) 24
3.3.4 傅立葉轉換红外光谱分析(FTIR) 25
3.4 催化劑耐久與再生實驗 26
3.5 燃油性質分析 33
 X. Li, X. Luo, Y. Jin, J. Li, H. Zhang, A. Zhang, and J. Xie, "Heterogeneous sulfur-free hydrodeoxygenation catalysts for selectively upgrading the renewable bio-oils to second generation biofuels," Renewable and Sustainable Energy Reviews, vol. 82, pp. 3762-3797, 2018.
 M. Patel and A. Kumar, "Production of renewable diesel through the hydroprocessing of lignocellulosic biomass-derived bio-oil: A review," Renewable and Sustainable Energy Reviews, vol. 58, pp. 1293-1307, 2016.
 S. Bezergianni and A. Dimitriadis, "Comparison between different types of renewable diesel," Renewable and Sustainable Energy Reviews, vol. 21, pp. 110-116, 2013.
 G. Knothe, "Biodiesel and renewable diesel: a comparison," Progress in energy and combustion science, vol. 36, pp. 364-373, 2010.
 D. Singh, K. Subramanian, and S. Singal, "Emissions and fuel consumption characteristics of a heavy duty diesel engine fueled with hydroprocessed renewable diesel and biodiesel," Applied Energy, vol. 155, pp. 440-446, 2015.
 D. Singh, K. Subramanian, R. Bal, S. Singh, and R. Badola, "Combustion and emission characteristics of a light duty diesel engine fueled with hydro-processed renewable diesel," Energy, vol. 154, pp. 498-507, 2018.
 H.-J. Liu, R.-H. Chen, and W.-C. Wang, "The non-regulated emissions from a turbo-charged diesel engine under steady-state operation with hydro-processed renewable diesel (HRD)," Fuel, vol. 263, p. 116762, 2020.
 A. Srifa, K. Faungnawakij, V. Itthibenchapong, and S. Assabumrungrat, "Roles of monometallic catalysts in hydrodeoxygenation of palm oil to green diesel," Chemical Engineering Journal, vol. 278, pp. 249-258, 2015.
 A. Srifa, K. Faungnawakij, V. Itthibenchapong, N. Viriya-Empikul, T. Charinpanitkul, and S. Assabumrungrat, "Production of bio-hydrogenated diesel by catalytic hydrotreating of palm oil over NiMoS2/γ-Al2O3 catalyst," Bioresource technology, vol. 158, pp. 81-90, 2014.
 A. Vonortas and N. Papayannakos, "Comparative analysis of biodiesel versus green diesel," Wiley Interdisciplinary Reviews: Energy and Environment, vol. 3, pp. 3-23, 2014.
 K.-H. Hsu, W.-C. Wang, and Y.-C. Liu, "Experimental studies and techno-economic analysis of hydro-processed renewable diesel production in Taiwan," Energy, vol. 164, pp. 99-111, 2018.
 X. Man, C. Cheung, Z. Ning, L. Wei, and Z. Huang, "Influence of engine load and speed on regulated and unregulated emissions of a diesel engine fueled with diesel fuel blended with waste cooking oil biodiesel," Fuel, vol. 180, pp. 41-49, 2016.
 Y. Di, C. Cheung, and Z. Huang, "Experimental investigation on regulated and unregulated emissions of a diesel engine fueled with ultra-low sulfur diesel fuel blended with biodiesel from waste cooking oil," Science of the total environment, vol. 407, pp. 835-846, 2009.
 D. Ogunkoya, W. L. Roberts, T. Fang, and N. Thapaliya, "Investigation of the effects of renewable diesel fuels on engine performance, combustion, and emissions," Fuel, vol. 140, pp. 541-554, 2015.
 S. Chen, G. Zhou, and C. Miao, "Green and renewable bio-diesel produce from oil hydrodeoxygenation: Strategies for catalyst development and mechanism," Renewable and Sustainable Energy Reviews, vol. 101, pp. 568-589, 2019.
 M. Hajjari, M. Tabatabaei, M. Aghbashlo, and H. Ghanavati, "A review on the prospects of sustainable biodiesel production: A global scenario with an emphasis on waste-oil biodiesel utilization," Renewable and Sustainable Energy Reviews, vol. 72, pp. 445-464, 2017.
 T. N. Kalnes, K. P. Koers, T. Marker, and D. R. Shonnard, "A technoeconomic and environmental life cycle comparison of green diesel to biodiesel and syndiesel," Environmental Progress & Sustainable Energy: An Official Publication of the American Institute of Chemical Engineers, vol. 28, pp. 111-120, 2009.
 R. Sotelo-Boyás, F. Trejo-Zárraga, and F. Hernández-Loyo, "Hydroconversion of triglycerides into green liquid fuels," Hydrogenation, vol. 338, p. 338, 2012.
 R. Zarchin, M. Rabaev, R. Vidruk-Nehemya, M. V. Landau, and M. Herskowitz, "Hydroprocessing of soybean oil on nickel-phosphide supported catalysts," Fuel, vol. 139, pp. 684-691, 2015.
 B. Veriansyah, J. Y. Han, S. K. Kim, S.-A. Hong, Y. J. Kim, J. S. Lim, Y.-W. Shu, S.-G. Oh, and J. Kim, "Production of renewable diesel by hydroprocessing of soybean oil: Effect of catalysts," Fuel, vol. 94, pp. 578-585, 2012.
 Y. Sugami, E. Minami, and S. Saka, "Renewable diesel production from rapeseed oil with hydrothermal hydrogenation and subsequent decarboxylation," Fuel, vol. 166, pp. 376-381, 2016.
 W. Pérez, J. Marín, J. del Río, J. Peña, and L. Rios, "Upgrading of palm oil renewable diesel through hydroisomerization and formulation of an optimal blend," Fuel, vol. 209, pp. 442-448, 2017.
 J. Chen and Q. Xu, "Hydrodeoxygenation of biodiesel-related fatty acid methyl esters to diesel-range alkanes over zeolite-supported ruthenium catalysts," Catalysis Science & Technology, vol. 6, pp. 7239-7251, 2016.
 R. Tiwari, B. S. Rana, R. Kumar, D. Verma, R. Kumar, R. K. Joshi, M. O. Garg, and A. K. Sinha, "Hydrotreating and hydrocracking catalysts for processing of waste soya-oil and refinery-oil mixtures," Catalysis Communications, vol. 12, pp. 559-562, 2011.
 K. Jeništová, I. Hachemi, P. Mäki-Arvela, N. Kumar, M. Peurla, L. Čapek, J. Wärnå, and D. Y. Murzin, "Hydrodeoxygenation of stearic acid and tall oil fatty acids over Ni-alumina catalysts: Influence of reaction parameters and kinetic modelling," Chemical Engineering Journal, vol. 316, pp. 401-409, 2017.
 M. Ameen, M. T. Azizan, S. Yusup, A. Ramli, and M. Yasir, "Catalytic hydrodeoxygenation of triglycerides: An approach to clean diesel fuel production," Renewable and Sustainable Energy Reviews, vol. 80, pp. 1072-1088, 2017.
 N. Arun, J. Maley, N. Chen, R. Sammynaiken, Y. Hu, and A. K. Dalai, "NiMo nitride supported on γ-Al2O3 for hydrodeoxygenation of oleic acid: Novel characterization and activity study," Catalysis Today, vol. 291, pp. 153-159, 2017.
 I. Hachemi, N. Kumar, P. Mäki-Arvela, J. Roine, M. Peurla, J. Hemming, J. Salonen, and D. Y. Murzin, "Sulfur-free Ni catalyst for production of green diesel by hydrodeoxygenation," Journal of Catalysis, vol. 347, pp. 205-221, 2017.
 S. Zheng, M. Kates, M. Dubé, and D. McLean, "Acid-catalyzed production of biodiesel from waste frying oil," Biomass and bioenergy, vol. 30, pp. 267-272, 2006.
 H. Chen, Q. Wang, X. Zhang, and L. Wang, "Effect of support on the NiMo phase and its catalytic hydrodeoxygenation of triglycerides," Fuel, vol. 159, pp. 430-435, 2015.
 M. Ameen, M. T. Azizan, A. Ramli, S. Yusup, and B. Abdullah, "The effect of metal loading over Ni/γ-Al2O3 and Mo/γ-Al2O3 catalysts on reaction routes of hydrodeoxygenation of rubber seed oil for green diesel production," Catalysis Today, 2019.
 E. Kordouli, L. Sygellou, C. Kordulis, K. Bourikas, and A. Lycourghiotis, "Probing the synergistic ratio of the NiMo/γ-Al2O3 reduced catalysts for the transformation of natural triglycerides into green diesel," Applied Catalysis B: Environmental, vol. 209, pp. 12-22, 2017.
 H. Wang, G. Li, K. Rogers, H. Lin, Y. Zheng, and S. Ng, "Hydrotreating of waste cooking oil over supported CoMoS catalyst–Catalyst deactivation mechanism study," Molecular Catalysis, vol. 443, pp. 228-240, 2017.
 P. Šimáček, D. Kubička, G. Šebor, and M. Pospíšil, "Hydroprocessed rapeseed oil as a source of hydrocarbon-based biodiesel," Fuel, vol. 88, pp. 456-460, 2009.
 S. K. Kim, S. Brand, H.-s. Lee, Y. Kim, and J. Kim, "Production of renewable diesel by hydrotreatment of soybean oil: Effect of reaction parameters," Chemical Engineering Journal, vol. 228, pp. 114-123, 2013.
 E. Kordouli, B. Pawelec, K. Bourikas, C. Kordulis, J. L. G. Fierro, and A. Lycourghiotis, "Mo promoted Ni-Al2O3 co-precipitated catalysts for green diesel production," Applied Catalysis B: Environmental, vol. 229, pp. 139-154, 2018.
 D. Méndez-Mateos, V. L. Barrio, J. M. Requies, and J. F. Cambra, "A study of deactivation by H 2 S and regeneration of a Ni catalyst supported on Al 2 O 3, during methanation of CO 2. Effect of the promoters Co, Cr, Fe and Mo," RSC Advances, vol. 10, pp. 16551-16564, 2020.
 K. Kohli, R. Prajapati, S. K. Maity, M. Sau, and B. K. Sharma, "Accelerated pre-coking of NiMo/γ-Al2O3 catalyst: Effect on the hydroprocessing activity of vacuum residue," Fuel, vol. 235, pp. 437-447, 2019.
 M. Ameen, M. T. Azizan, S. Yusup, A. Ramli, M. Shahbaz, A. Aqsha, H. Kaur, and C. K. Wai, "Parametric Studies on Hydrodeoxygenation of Rubber Seed Oil for Diesel Range Hydrocarbon Production," Energy & Fuels, vol. 34, pp. 4603-4617, 2020.
 W.-C. Wang and C.-H. Hsieh, "Hydro-processing of biomass-derived oil into straight-chain alkanes," Chemical Engineering Research and Design, vol. 153, pp. 63-74, 2020.
 B. Behnejad, M. Abdouss, and A. Tavasoli, "NI-MO SUPPORTED NANOPOROUS GRAPHENE AS A NOVEL CATALYST FOR HDS AND HDN OF HEAVY NAPHTHA," Brazilian Journal of Chemical Engineering, vol. 36, pp. 265-273, 2019.
 M. Grilc, B. Likozar, and J. Levec, "Hydrotreatment of solvolytically liquefied lignocellulosic biomass over NiMo/Al2O3 catalyst: Reaction mechanism, hydrodeoxygenation kinetics and mass transfer model based on FTIR," Biomass and Bioenergy, vol. 63, pp. 300-312, 2014.
 I. Bortel, J. Vávra, and M. Takáts, "Effect of HVO fuel mixtures on emissions and performance of a passenger car size diesel engine," Renewable Energy, vol. 140, pp. 680-691, 2019.