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One-step conversion of crude oil to light olefins using a multi-zone reactor

Abstract

With the demand for gasoline and diesel expected to decline in the near future, crude-to-chemicals technologies have the potential to become the most important processes in the petrochemical industry. This trend has triggered intense research to maximize the production of light olefins and aromatics at the expense of fuels, which calls for disruptive processes able to transform crude oil to chemicals in an efficient and environmentally friendly way. Here we propose a catalytic reactor concept consisting of a multi-zone fluidized bed that is able to perform several refining steps in a single reactor vessel. This configuration allows for in situ catalyst stripping and regeneration, while the incorporation of silicon carbide in the catalyst confers it with improved physical, mechanical and heat-transport properties. As a result, this reactor–catalyst combination has shown stable conversion of untreated Arabian Light crude into light olefins with yields per pass of over 30 wt% with a minimum production of dry gas.

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Fig. 1: Catalytic performance of the MZFB reactor.
Fig. 2: Coke quantification by TGA of the spent catalyst.
Fig. 3: Identification of the post-reacted zeolite-trapped species.
Fig. 4: Catalytic performance of ACM-101 in the cracking of AL crude.
Fig. 5: Analysis of liquid products.

Data availability

All data presented in this study are included in this published manuscript and its Supplementary Information or are available from the corresponding author upon reasonable request.

References

  1. 1.

    Murphree, E. V., Brown, C. L., Fischer, H. G. M., Gohr, E. J. & Sweeney, W. J. Fluid catalyst process. Catalytic cracking of petroleum. Ind. Eng. Chem. 35, 768–773 (1943).

    CAS  Article  Google Scholar 

  2. 2.

    Wilson, J. W. Fluid Catalytic Cracking Technology and Operations (PennWell Books, 1997).

  3. 3.

    World Oil Outlook 2040 (Organization of the Petroleum Exporting Countries, 2019).

  4. 4.

    Corma, A. et al. Direct crude oil cracking for producing chemicals: thermal cracking modeling. Fuel 211, 726–736 (2018).

    CAS  Article  Google Scholar 

  5. 5.

    Corma, A. et al. Crude oil to chemicals: light olefins from crude oil. Catal. Sci. Technol. 7, 12–46 (2017).

    CAS  Article  Google Scholar 

  6. 6.

    Amghizar, I., Vandewalle, L. A., Van Geem, K. M. & Marin, G. B. New trends in olefin production. Engineering 3, 171–178 (2017).

    CAS  Article  Google Scholar 

  7. 7.

    Geerts, M. et al. Crude to olefins: effect of feedstock composition on coke formation in a bench-scale steam cracking furnace. Ind. Eng. Chem. Res. 59, 2849–2859 (2020).

    CAS  Article  Google Scholar 

  8. 8.

    Alotaibi, F. M. et al. Enhancing the production of light olefins from heavy crude oils: turning challenges into opportunities. Catal. Today 317, 86–98 (2018).

    CAS  Article  Google Scholar 

  9. 9.

    Vogt, E. T. C. & Weckhuysen, B. M. Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis. Chem. Soc. Rev. 44, 7342–7370 (2015).

    CAS  Article  Google Scholar 

  10. 10.

    Knight, J. & Mehlberg, R. Maximize propylene from your FCC unit. Hydrocarb. Process. 90, 91–95 (2011).

    CAS  Google Scholar 

  11. 11.

    Soni, D. S. & Castagnos, L. F. System and method for selective component cracking to maximize production of light olefins. Eur. patent EP1713884 (2005).

  12. 12.

    Pittman, R. M. & Upson, L. L. FCC process with improved yield of light olefins. US patent US6538169 (2000).

  13. 13.

    Chaohe, Y., Xiaobo, C., Jinhong, Z., Chunyi, L. & Honghong, S. Advances of two-stage riser catalytic cracking of heavy oil for maximizing propylene yield (TMP) process. Appl. Petrochem. Res. 4, 435–439 (2014).

    CAS  Article  Google Scholar 

  14. 14.

    Steinhofer, A. Make petrochemicals from crude oil. Hydrocarb. Process. Pet. Refiner 44, 134–142 (1965).

    CAS  Google Scholar 

  15. 15.

    Asinger, F. Mono-Olefins: Chemistry and Technology (Elsevier Science, 2013).

  16. 16.

    朱根权, 李正, 谢朝钢, 鲁维民 (Petroleum hydrocarbon catalytic conversion method for high output of ethylene, propylene and light aromatic hydrocarbons). Chinese patent CN102443423A (2010).

  17. 17.

    Tullo, A. H. Why the future of oil is in chemicals, not fuels. Chem. Eng. News 97 (2019).

  18. 18.

    Gascon, J., Tellez, C., Herguido, J., Jakobsen, H. A. & Menéndez, M. Modeling of fluidized bed reactors with two reaction zones. AIChE J. 52, 3911–3923 (2006).

    CAS  Article  Google Scholar 

  19. 19.

    Hupp, S. S. & Swift, H. E. Oxidative coupling of toluene to stilbene. Ind. Eng. Chem. Prod. Res. Dev. 18, 117–122 (1979).

    CAS  Article  Google Scholar 

  20. 20.

    Soler, J., Nieto, J. M. L., Herguido, J., Menéndez, M. & Santamaría, J. Oxidative dehydrogenation of n-butane in a two-zone fluidized-bed reactor. Ind. Eng. Chem. Res. 38, 90–97 (1999).

    CAS  Article  Google Scholar 

  21. 21.

    Rubio, O., Herguido, J. & Menéndez, A. Two-zone fluidized bed reactor for simultaneous reaction and catalyst reoxidation: influence of reactor size. Appl. Catal. A 272, 321–327 (2004).

    CAS  Article  Google Scholar 

  22. 22.

    Gascon, J., Tellez, C., Herguido, J. & Menéndez, A. A two-zone fluidized bed reactor for catalytic propane dehydrogenation. Chem. Eng. J. 106, 91–96 (2005).

    CAS  Article  Google Scholar 

  23. 23.

    Julian, I., Herguido, J. & Menéndez, M. Particle mixing in a two-section two-zone fluidized bed reactor. Experimental technique and counter-current back-mixing model validation. Ind. Eng. Chem. Res. 52, 13587–13596 (2013).

    CAS  Article  Google Scholar 

  24. 24.

    Speight, J. G. & Özüm, B. Petroleum Refining Processes (Marcel Dekker, 2002).

  25. 25.

    Parthasarathi, R. S. & Alabduljabbar, S. S. HS-FCC high-severity fluidized catalytic cracking: a newcomer to the FCC family. Appl. Petrochem. Res. 4, 441–444 (2014).

    CAS  Article  Google Scholar 

  26. 26.

    den Hollander, M. A., Wissink, M., Makkee, M. & Moulijn, J. A. Gasoline conversion: reactivity towards cracking with equilibrated FCC and ZSM-5 catalysts. Appl. Catal. A 223, 85–102 (2002).

    CAS  Article  Google Scholar 

  27. 27.

    Zhang, J., Shan, H., Chen, X., Li, C. & Yang, C. In situ upgrading of light fluid catalytic cracking naphtha for minimum loss. Ind. Eng. Chem. Res. 52, 6366–6376 (2013).

    CAS  Article  Google Scholar 

  28. 28.

    Siddiqui, M. A. B., Aitani, A. M., Saeed, M. R., Al-Yassir, N. & Al-Khattaf, S. Enhancing propylene production from catalytic cracking of Arabian Light VGO over novel zeolites as FCC catalyst additives. Fuel 90, 459–466 (2011).

    CAS  Article  Google Scholar 

  29. 29.

    Chen, S. & Manos, G. Study of coke and coke precursors during catalytic cracking of n-hexane and 1-hexene over ultrastable Y zeolite. Catal. Lett. 96, 195–200 (2004).

    CAS  Article  Google Scholar 

  30. 30.

    den Hollander, M. A., Makkee, M. & Moulijn, J. A. Coke formation in fluid catalytic cracking studied with the microriser. Catal. Today 46, 27–35 (1998).

    Article  Google Scholar 

  31. 31.

    Otterstedt, J. E., Gevert, S. B., Jäås, S. G. & Menon, P. G. Fluid catalytic cracking of heavy (residual) oil fractions: a review. Appl. Catal. 22, 159–179 (1986).

    CAS  Article  Google Scholar 

  32. 32.

    Absi-Halabi, M., Stanislaus, A. & Trimm, D. L. Coke formation on catalysts during the hydroprocessing of heavy oils. Appl. Catal. 72, 193–215 (1991).

    CAS  Article  Google Scholar 

  33. 33.

    Ramirez, A. et al. Effect of zeolite topology and reactor configuration on the direct conversion of CO2 to light olefins and aromatics. ACS Catal. 9, 6320–6334 (2019).

    CAS  Article  Google Scholar 

  34. 34.

    Chowdhury, A. D. et al. Electrophilic aromatic substitution over zeolites generates Wheland-type reaction intermediates. Nat. Catal. 1, 23–31 (2018).

    CAS  Article  Google Scholar 

  35. 35.

    Qi, G. et al. Behaviors of coke deposition on SAPO-34 catalyst during methanol conversion to light olefins. Fuel Process. Technol. 88, 437–441 (2007).

    CAS  Article  Google Scholar 

  36. 36.

    Zhao, X. B. et al. Achieving a superlong lifetime in the zeolite-catalyzed MTO reaction under high pressure: synergistic effect of hydrogen and water. ACS Catal. 9, 3017–3025 (2019).

    CAS  Article  Google Scholar 

  37. 37.

    Corma, A., Marie, O. & Ortega, F. J. Interaction of water with the surface of a zeolite catalyst during catalytic cracking: a spectroscopy and kinetic study. J. Catal. 222, 338–347 (2004).

    CAS  Article  Google Scholar 

  38. 38.

    Shoinkhorova, T. et al. Shaping of ZSM-5-based catalysts via spray drying: effect on methanol-to-olefins performance. ACS Appl. Mater. Interfaces 11, 44133–44143 (2019).

    CAS  Article  Google Scholar 

  39. 39.

    Ghrib, Y. et al. Synthesis of cocrystallized USY/ZSM-5 zeolites from kaolin and its use as fluid catalytic cracking catalysts. Catal. Sci. Technol. 8, 716–725 (2018).

    CAS  Article  Google Scholar 

  40. 40.

    Haas, A., Finger, K.-E. & Alkemade, U. Application of the energy gradient selectivity concept to fluid catalytic cracking catalysts. Appl. Catal. A 115, 103–120 (1994).

    CAS  Article  Google Scholar 

  41. 41.

    Adewuyia, Y. G., Klocke, D. J. & Buchanan, J. S. Effects of high-level additions of ZSM-5 to a fluid catalytic cracking (FCC) RE-USY catalyst. Appl. Catal. A 131, 121–133 (1995).

    Article  Google Scholar 

  42. 42.

    Rahimi, N. & Karimzadeh, R. Catalytic cracking of hydrocarbons over modified ZSM-5 zeolites to produce light olefins: a review. Appl. Catal. A 398, 1–17 (2011).

    CAS  Article  Google Scholar 

  43. 43.

    Corma, A. et al. Methylcyclohexane and methylcyclohexene cracking over zeolite Y catalysts. Appl. Catal. 67, 307–324 (1990).

    Article  Google Scholar 

Download references

Acknowledgements

We acknowledge Saudi Aramco for financial support. Y. Saih, S. Telalovic and L. E. Gevers are gratefully acknowledged for technical support and S. Ramirez Cherbuy for the artwork design.

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Authors

Contributions

J.G. conceived, designed and supervised the project together with M.A. and A.R.-G. All catalytic assessment experiments and data interpretation were carried out by M.A. and A.R.-G. Synthesis and characterization of the ACM-101 catalyst formulation was the responsibility of T.S. and A.D. The ssNMR analysis and data interpretation was performed by A.D.C. and E.A.-H. Thermogravimetric analysis was performed by J.V., M.A., A.R.-G. and I.H. SIMDIS analysis of liquid products was performed by J.V., A.R.-G. and M.A. FT-ICR MS and GC-MS analyses were performed by I.H. and W.Z. CFD simulations were performed by S.R.K. and supervised by P.C. All kinetics simulations for AL/oxygen auto-ignition were the responsibility of S.M.S. Participation in the discussion of results and industrial applicability was contributed by A.B.S., O.S.A., I.M.-O. and W.X. The manuscript was drafted by M.A., A.R.-G. and J.G. with input from all the authors.

Corresponding author

Correspondence to Jorge Gascon.

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Competing interests

Two patent applications (WO2020109885(A1) and provisional application number PCT/IB2020/057120) have been filed by the authors covering different aspects of this work.

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Peer review information Nature Catalysis thanks Guang Cao, Kevin M. Van Geem and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary methods, discussion, Figs. 1–14, Tables 1–6 and refs. 1–35.

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Alabdullah, M., Rodriguez-Gomez, A., Shoinkhorova, T. et al. One-step conversion of crude oil to light olefins using a multi-zone reactor. Nat Catal 4, 233–241 (2021). https://doi.org/10.1038/s41929-021-00580-7

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