Efficient carbon integration of CO2 in propane aromatization over acidic zeolites

doi:10.1016/S1872-2067(25)64680-8

Abstract

Abstract:

Direct converting carbon dioxide (CO₂) and propane (C₃H₈) into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO₂ emission and adequately utilize C₃H₈ in shale gas. Owing to their thermodynamic resistance, converting CO₂ and C₃H₈ respectively remains difficult. Here, we achieve 60.2% aromatics selectivity and 48.8% propane conversion over H-ZSM-5-25 via a zeolite-catalyzing the coupling of CO₂ and C₃H₈. Operando dual-beam FTIR spectroscopy combined with ¹³C-labeled CO₂ tracing experiments revealed that CO₂ is directly involved in the generation of aromatics, with its carbon atoms selectively embedded into the aromatic ring, bypassing the reverse water-gas shift pathway. Accordingly, a cooperative aromatization mechanism is proposed. Thereinto, lactones, produced from CO₂ and olefins, are proven to be the key intermediate. This work not only provides an opportunity for simultaneous conversion of CO₂ and C₃H₈, but also expends coupling strategy designing of CO₂ and alkanes over acidic zeolites.

Key words: CO₂ utilization, Propane aromatization, Coupling effect, Acidic zeolites, Lactone

Cheng Li, Xudong Fang, Bin Li, Siyang Yan, Zhiyang Chen, Leilei Yang, Shaowen Hao, Hongchao Liu, Jiaxu Liu, Wenliang Zhu. Efficient carbon integration of CO₂ in propane aromatization over acidic zeolites[J]. Chinese Journal of Catalysis, 2025, 72: 314-322.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64680-8

https://www.cjcatal.com/EN/Y2025/V72/I5/314

Figures/Tables 5

Fig. 1. CO2-C3H8 co-conversion to aromatics over acidic zeolites with varied framework structures. (a) Schematic illustration of the co-conversion strategy. (b) Catalytic performances of different zeolitic topologies in propane aromatization, with and without CO2 co-feeding. (c) Propane conversion and product distribution over H-ZSM-5 at 0.1 MPa under various gas atmospheres. (d) Aromatic selectivity profiles over H-ZSM-5 at 3.0 MPa under different reaction environments. Reaction conditions: (b,d) 723 K, 20 kPa C3H8, (2570 kPa CO2, 410 kPa Ar solid) or (2980 kPa Ar dash), 1000 mL/gcat/h; (c) 723 K, 0.72 kPa C3H8, (86.85 kPa CO2, 13.43 kPa Ar) or (100.28 kPa Ar), 1000 mL/gcat/h. Note that olefins represent C2=-C4=, alkanes represent C1-C40 (apart from C3H8), and others represent C5+ hydrocarbon excluding aromatics.

Fig. 2. Catalytic behavior of H-ZSM-5 catalysts with varying SiO2/Al2O3 ratios on the co-conversion of CO2 and C3H8. (a) Selectivity distribution of main products. (b) Correlation between aluminum content in H-ZSM-5 and the selectivity toward aromatics, alkanes, and olefins. Reaction conditions: (a) 723 K, 20 kPa C3H8, (2570 kPa CO2, 410 kPa Ar) or (2980 kPa Ar), 1000 mL/gcat/h; (b) 723 K, 20 kPa C3H8, 2570 kPa CO2, 410 kPa Ar, 1000 mL/gcat/h; Note that olefins represent C2=-C4=, alkanes represent C1-C40 (apart from C3H8), and others represent C5+ hydrocarbon excluding aromatics.

Fig. 3. Impact of reaction parameters on the co-conversion of CO2 and C3H8 over H-ZSM-5-25. (a) Variation in propane conversion and product distribution with total reaction pressure. (b) Dependence of C3H8 conversion and product selectivity on reaction temperature. (c) Effect of CO2 partial pressure on selectivity trends and converted CO2/ C3H8 ratios. (d) Product profile and propane conversion as a function of contact time. Reaction conditions: (a) 723 K, C3H8:CO2 = 1:120, 1000 mL/gcat/h; (b) 20 kPa C3H8, 2570 kPa CO2, 410 kPa Ar, 1000 mL/gcat/h; (c) 723 K, 20 kPa C3H8, 0-2570 kPa CO2, 1000 mL/gcat/h, Ar as balance gas; (d) 723 K, 20 kPa C3H8, 2570 kPa CO2, 410 kPa Ar. Note that olefins represent C2=-C4=, alkanes represent C1-C40 (apart from C3H8), and others represent C5+ hydrocarbon excluding aromatics.

Fig. 4. Mechanistic investigation of the CO2-C3H8 co-conversion over H-ZSM-5-25. (a) Correlation between contact time and light hydrocarbon formation. (b) Effect of contact time on residual surface species and aromatic selectivity. (c) Operando dual-beam FTIR spectra of propane conversion under different gas atmospheres. (d) 13C isotope distribution in aromatic products. (e) 13C liquid-state NMR spectra of products derived from the coupling reaction between 13CO2 and C3H8. Reaction conditions: (a,b) 723 K, 20 kPa C3H8, 2570 kPa CO2, 410 kPa Ar; (c) 423-723 K, 1.0 MPa, C3H8:CO2 = 1:99 (up), C3H8 : Ar = 1:99 (down), 40000 mL/gcat/h; (d,e) 723 K, 1.5 kPa C3H8, 500 kPa CO2, 798.5 kPa Ar, 1300 mL/gcat/h.

Fig. 5. Schematic illustration of the CO2-C3H8 coupling aromatization over H-ZSM-5.

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Efficient carbon integration of CO₂ in propane aromatization over acidic zeolites

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