Abstract
To tune the product selectivity by controlling the complicated reaction path is a big challenge in Fischer–Tropsch synthesis. Here, we report an integrated catalytic process for the direct conversion of syngas (CO/H2) into different types of liquid fuels without subsequent hydrorefining post-treatments of Fischer–Tropsch waxes. Outstanding selectivities for gasoline, jet fuel and diesel fuel as high as 74, 72 and 58% are achieved, respectively, by only using mesoporous Y-type zeolites in combination with cobalt nanoparticles. The types of liquid fuels can be readily tuned by controlling the porosity and acid properties of the zeolites. We further build a new product-distribution model for the bifunctional catalysts, which do not obey the traditional Anderson–Schulz–Flory (ASF) distribution. The present work offers a simple and effective method for the direct synthesis of different types of liquid fuels.
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Data availability
The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.
References
Khodakov, A. Y., Chu, W. & Fongarland, P. Advances in the development of novel cobalt Fischer–Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels. Chem. Rev. 107, 1692–1744 (2007).
Huber, G. W., Iborra, S. & Corma, A. Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. Chem. Rev. 106, 4044–4098 (2006).
Higman, C. & Tam., S. Advances in coal gasification, hydrogenation, and gas treating for the production of chemicals and fuels. Chem. Rev. 114, 1673–1708 (2014).
Navarro, V., Van Spronsen, M. A. & Frenken, J. W. M. In situ observation of self-assembled hydrocarbon Fischer–Tropsch products on a cobalt catalyst. Nat. Chem. 8, 929–934 (2016).
Gao, P. et al. Direct conversion of CO2 into liquid fuels with high selectivity over a bifunctional catalyst. Nat. Chem. 9, 1019–1024 (2017).
Dry, M. E. The Fischer–Tropsch process: 1950–2000. Catal. Today 71, 227–241 (2002).
de Klerk, A. Fischer–Tropsch Refining (Wiley, Weinheim, 2011).
Maitlis, P. M. & de Klerk, A. Greener Fischer–Tropsch Processes for Fuels and Feedstocks (Wiley, Weinheim, 2013).
Flory, P. J. et al. Molecular size distribution in linear condensation polymers. J. Am. Chem. Soc. 58, 1877–1885 (1936).
Friedel, R. A. & Anderson, R. B. Composition of synthetic liquid fuels. I. Product distribution and analysis of C5–C8 paraffin isomers from cobalt catalyst. J. Am. Chem. Soc. 72, 1212–1215 (1950).
Sartipi, S. et al. Hierarchical H-ZSM-5-supported cobalt for the direct synthesis of gasoline-range hydrocarbons from syngas: advantages, limitations, and mechanistic insight. J. Catal. 305, 179–190 (2013).
Sartipi, S., Makkee, M., Kapteijn, F. & Gascon, J. Catalysis engineering of bifunctional solids for the one-step synthesis of liquid fuels from syngas: a review. Catal. Sci. Technol. 4, 893–907 (2014).
Kang, J. et al. Mesoporous zeolite-supported ruthenium nanoparticles as highly selective Fischer–Tropsch catalysts for the production of C5–C11 isoparaffins. Angew. Chem. Int. Ed. 50, 5200–5203 (2011).
Bao, J., He, J., Zhang, Y., Yoneyama, Y. & Tsubaki, N. A core/shell catalyst produces a spatially confined effect and shape selectivity in a consecutive reaction. Angew. Chem. Int. Ed. 47, 353–356 (2008).
Yamane, N. et al. Building premium secondary reaction field with a miniaturized capsule catalyst to realize efficient synthesis of a liquid fuel directly from syngas. Catal. Sci. Technol. 7, 1996–2000 (2017).
Kang, J. et al. Ruthenium nanoparticles supported on carbon nanotubes as efficient catalysts for selective conversion of synthesis gas to diesel fuel. Angew. Chem. Int. Ed. 48, 2565–2568 (2009).
Peng, X. et al. Impact of hydrogenolysis on Fischer–Tropsch synthesis selectivity: diesel fuel production over mesoporous zeolite Y-supported cobalt nanoparticles. Angew. Chem. Int. Ed. 54, 4553–4556 (2015).
Sartipi, S. et al. Insights into the catalytic performance of mesoporous H-ZSM-5-supported cobalt in Fischer–Tropsch synthesis. ChemCatChem 6, 142–151 (2014).
Sartipi, S. et al. Towards liquid fuels from biosyngas: effect of zeolite structure in hierarchical-zeolite-supported cobalt catalysts. ChemSusChem 6, 1646–1650 (2013).
Zhang, Q., Kang, J. & Wang, Y. Development of novel catalysts for Fischer–Tropsch synthesis: tuning the product selectivity. ChemCatChem 2, 1030–1058 (2010).
Cheng, K. et al. Mesoporous beta zeolite-supported ruthenium nanoparticles for selective conversion of synthesis gas to C5–C11 isoparaffins. ACS Catal. 2, 441–449 (2012).
de Jong, K. P. et al. Zeolite Y crystals with trimodal porosity as ideal hydrocracking catalysts. Angew. Chem. Int. Ed. 49, 10074–10078 (2010).
Vervloet, D. et al. Fischer–Tropsch reaction–diffusion in a cobalt catalyst particle: aspects of activity and selectivity for a variable chain growth probability. Catal. Sci. Technol. 2, 1221–1233 (2012).
Weitkamp, J. Catalytic hydrocracking—mechanisms and versatility of the process. ChemCatChem 4, 292–306 (2012).
Scherzer, J. & Gruia, A. J. Hydrocracking Science and Technology (Marcel Dekker, New York, 1996).
de Klerk, A. Environmentally friendly refining: Fischer–Tropsch versus crude oil. Green Chem. 9, 560–565 (2007).
Leckel, D. Diesel production from Fischer–Tropsch: the past, the present, and new concepts. Energy Fuels 23, 2342–2358 (2009).
Wu, T. et al. Physical and chemical properties of GTL–diesel fuel blends and their effects on performance and emissions of a multicylinder DI compression ignition engine. Energy Fuels 21, 1908–1914 (2007).
Abu-Jrai, A. et al. Effect of gas-to-liquid diesel fuels on combustion characteristics, engine emissions, and exhaust gas fuel reforming. Comparative study. Energy Fuels 20, 2377–2384 (2006).
Maxwell, I. E. Zeolite catalysis in hydroprocessing technology. Catal. Today 1, 385–413 (1987).
Bouchy, C. et al. Fischer–Tropsch waxes upgrading via hydrocracking and selective hydroisomerization. Oil Gas Sci. Technol. 64, 91–112 (2009).
Calemma, V. et al. Middle distillates from hydrocracking of FT waxes: composition, characteristics and emission properties. Catal. Today 149, 40–46 (2010).
Katada, N., Igi, H., Kim, J. H. & Niwa., M. Determination of the acidic properties of zeolite by theoretical analysis of temperature-programmed desorption of ammonia based on adsorption equilibrium. J. Phys. Chem. B 101, 5969–5977 (1997).
Woolery, G. L. et al. On the nature of framework Brønsted and Lewis acid sites in ZSM-5. Zeolites 19, 288–296 (1997).
Garralón, G., Cormat, A. & Formés, V. Evidence for the presence of superacid nonframework hydroxyl groups in dealuminated HY zeolites. Zeolites 9, 84–86 (1989).
Cerqueira, H. S., Caeiro, G., Costa, L. & Ramôa Ribeiro, F. Deactivation of FCC catalysts. J. Mol. Catal. A 292, 1–13 (2008).
Sousa-Aguiara, E. F., Trigueiro, F. E. & Zotin, F. M. Z. The role of rare earth elements in zeolites and cracking catalysts. Catal. Today 218, 115–122 (2013).
Duan, L. et al. Adsorption, co-adsorption, and reactions of sulfur compounds, aromatics, olefins over Ce-exchanged Y zeolite. J. Phys. Chem. C 116, 25748–25756 (2012).
Xue, M. et al. Preparation of cerium-loaded Y-zeolites for removal of organic sulfur compounds from hydrodesulfurizated gasoline and diesel oil. J. Colloid Interface Sci. 298, 535–542 (2006).
Borg, Ø.et al. Effect of biomass-derived synthesis gas impurity elements on cobalt Fischer–Tropsch catalyst performance including in situ sulphur and nitrogen addition. J. Catal. 279, 163–173 (2011)..
Lillebø, A. H. et al. The effect of alkali and alkaline earth elements on cobalt based Fischer–Tropsch catalysts. Catal. Today 215, 60–66 (2013).
Buttefey, S. et al. A simple model for predicting the Na+ distribution in anhydrous NaY and NaX zeolites. J. Phys. Chem. B 105, 9569–9575 (2001).
Sexton, B. A. et al. An XPS and TPR study of the reduction of promoted cobalt-kieselguhr Fischer–Tropsch catalysts. J. Catal. 97, 390–406 (1986).
Ernst, B. et al. Study on a cobalt silica catalyst during reduction and Fischer–Tropsch reaction: in situ EXAFS compared to XPS and XRD. Catal. Today 39, 329–341 (1998).
Moodley, D. J. et al. Carbon deposition as a deactivation mechanism of cobalt-based Fischer–Tropsch synthesis catalysts under realistic conditions. Appl. Catal. A 354, 102–110 (2009).
Ferrari, A. C. & Robertson, J. Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 61, 14095–14107 (2000).
Pimenta, M. A. et al. Studying disorder in graphite-based systems by Raman spectroscopy. Phys. Chem. Chem. Phys. 9, 1276–1291 (2007).
Galvis, H. M. T. et al. Supported iron nanoparticles as catalysts for sustainable production of lower olefins. Science 335, 835–838 (2012).
Verboekend, D., Vilé, G. & Ramírez, J. P. Hierarchical Y and USY zeolites designed by post-synthetic strategies. Adv. Funct. Mater. 22, 916–928 (2012).
Eggenhuisen, T. M. et al. Fundamentals of melt infiltration for the preparation of supported metal catalysts. The case of Co/SiO2 for Fischer–Tropsch synthesis. J. Am. Chem. Soc. 132, 18318–18325 (2010).
Acknowledgements
This work was supported by the New Energy and Industrial Technology Development Organization of Japan, Japan Science and Technology Agency (MIRAI-JPMJMI17E2) and Natural Science Foundation of China (21433008, 91545203 and 21528302). We acknowledge J. Kang (Xiamen University, China), M. Tan (Institute of Coal Chemistry, Chinese Academy of Sciences, China), and A. Hashimoto, T. Hara and Y. Hara (National Institute for Materials Science, Japan) for performing supplementary reaction tests and characterization in the later stages of this work.
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J.L., Y.H., L.T. and P.Z. performed most of the experiments and analysed the experimental data. A.O. performed the TEM characterization. X.P., Y.W. and N.T. designed the study, analysed the data and wrote the manuscript. H.A. and G.Y. contributed to the experimental design. N.T. supervised the whole project. All authors discussed the results and commented on the manuscript at all stages.
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Supplementary Information
Supplementary Tables 1–13; Supplementary Figures 1–17; Supplementary Note; Supplementary Equations; Supplementary References
Supplementary Data Set 1
Matrix for the Gasoline distribution model
Supplementary Data Set 2
Matrix for the Jet fuel distribution model
Supplementary Data Set 3
Matrix for the Diesel distribution model
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Li, J., He, Y., Tan, L. et al. Integrated tuneable synthesis of liquid fuels via Fischer–Tropsch technology. Nat Catal 1, 787–793 (2018). https://doi.org/10.1038/s41929-018-0144-z
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DOI: https://doi.org/10.1038/s41929-018-0144-z