Understanding the reaction-induced restructuring of CoOx species in silicalite-1 to control selectivity in non-oxidative dehydrogenation of propane

doi:10.1016/S1872-2067(25)64724-3

Abstract

Abstract:

Non-oxidative dehydrogenation of propane (PDH) is an important route for large-scale on purpose propene production. Although cobalt-based catalysts are promising alternatives to currently used platinum- or chromium oxide-based catalysts, their further developments are hindered by the uncertainties related to the kind of the active sites involved in the desired and side reactions. To contribute to closing such a gap, we systematically investigate the role of oxidized CoO_x and metallic Co⁰ species in the PDH reaction over catalysts based in Silicalite-1 with supported CoO_x species differing in their redox properties. C₃H₈ pulse experiments with sub-millisecond and second resolution at pulse sizes of about 13 and 2200 nmol, respectively, combined with in-depth catalyst characterization and PDH tests at different propane conversions enabled us to understand how the reaction-induced reduction of CoO_x affects product selectivity. Propane readily reacts with CoO_x to yield propene, carbon oxides and water. The formed Co⁰ species show high activity to coking and cracking reactions. However, if the size of such species is below 2 nm, these undesired reactions are significantly hindered due to the coverage of the active sites by carbon-containing species. The remaining uncovered surface Co⁰ sites selectively dehydrogenate propane to propene. The best-performing catalyst showed higher activity than a commercial-like K-CrO_x/Al₂O₃ and operated durable in a series of 10 dehydrogenation/regeneration cycles under industrial relevant conditions. The space time yield of propene formation of 0.97 kg·h^-1·kg_cat^-1 was achieved at 550 °C, 52% equilibrium propane conversion and 95% propene selectivity.

Key words: Propane, Dehydrogenation, Propene, Cobalt, Mechanism

Qiyang Zhang, Vita A. Kondratenko, Xiangnong Ding, Jana Weiss, Stephan Bartling, Elizaveta Fedorova, Dan Zhao, Dmitry E. Doronkin, Dongxu Wang, Christoph Kubis, Evgenii V. Kondratenko. Understanding the reaction-induced restructuring of CoO_x species in silicalite-1 to control selectivity in non-oxidative dehydrogenation of propane[J]. Chinese Journal of Catalysis, 2025, 74: 108-119.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64724-3

https://www.cjcatal.com/EN/Y2025/V74/I7/108

Figures/Tables 10

Fig. 1. HAADF-STEM images of as-prepared 0.6Co/S-1 (a), 1Co/S-1 (b), 3Co/S-1 (c), and 5Co/S-1 (d).

Fig. 2. UV-vis spectra (a) and Co K-edge XANES (b) of the fresh catalysts and reference samples (Co3O4 and Co foil). The corresponding k2-weighted Fourier transform spectra are shown in (c).

Fig. 3. (a) H2-TPR profiles of xCo/S-1. (b) Quasi in situ XPS spectra of 1Co/S-1 after treatment at 550 °C with 20 vol% O2/Ar or 40 vol% H2/Ar. (c) In situ UV-vis spectra of 1Co/S-1 after treatment at 550 °C with 40 vol% H2/Ar.

Fig. 4. (a) The rate of propene formation over xCo/S-1. Temperature-resolved m/z values of 42 (C3H6) (b), 16 (CH4) (c) and 18 (H2O) (d) collected during temperature-programmed surface reaction of C3H8 with xCo/S-1 between 300 and 600 °C. (e) Arrhenius plots of the propene formation rate over xCo/S-1 as well as the respective apparent activation energy (Ea). (f) Ea versus the size of CoOx NP determined by HAADF-STEM (Fig. 1).

Fig. 5. The selectivity-conversion relationships for propene (a), C1-C2 hydrocarbons (b) and coke (c) formed over 0.6Co/S-1, 1Co/S-1 and 3Co/S-1. Proposed reaction pathways for propane dehydrogenation over 0.6Co/S-1 and 1Co/S-1 (d) as well as 3Co/S-1 (e). Reaction conditions: T = 550 °C, C3H8:N2 = 2:3, WHSV(C3H8) = 2.4-14.1 h-1.

Fig. 6. The normalized transient responses recorded upon pulsing a C3H8:Ar = 1:1 mixture at 550 °C over oxidized 1Co/S-1 (a) and 5Co/S-1 (d). C3H6 (b,e) and H2 (c,f) response recorded at 550 °C after pulsing (1mL) of a C3H8/Ar = 1:19 mixture over oxidized 1Co/S-1 (b,c) and 5Co/S-1 (e,f). Before the C3H8 pulses, the catalysts were exposed to a flow of O2/Ar = 1:4 (10 mL·min-1) at 550 °C for 30 min and then flushed with Ar for 20 min.

Fig. 7. The normalized transient responses recorded upon pulsing of a C3H8:Ar = 1:1 mixture at 550 °C over reduced 1Co/S-1 (a) and 5Co/S-1 (d). C3H6 (b,e) and H2 (c,f) response recorded at 550 °C after pulsing (1mL) of an C3H8/Ar = 1:19 mixture over reduced 1Co/S-1 (b,c) and 5Co/S-1 (e,f). Before the C3H8 pulses, the catalysts were exposed to a flow of H2/Ar=1:4 (10 mL/min) at 550°C for 30 min and then flushed with Ar for 20 min.

Fig. 8. (a) Operando UV-vis spectra of 1Co/S-1 during the C3H8 pulses (1mL pulse size) at 550 °C using a feed with 5 vol% C3H8 in Ar. (b) Operando Raman spectra of 1Co/S-1 collected during exposure to a feed with 40 vol% C3H8 in N2 at 550 °C.

Fig. 9. (a) Time-on-stream profiles of propane conversion and propene selectivity over tested samples. (b) Space time yield of propene formation (STY(C3H6)) determined over 1Co/S-1 and previously reported Co-based catalysts (Table S4) versus X(C3H8)exp/X(C3H8)eq. Reaction conditions: T = 550 °C, catalyst amount = 100 mg, WHSV(C3H8) = 4.7 h-1, C3H8:N2 = 2:3.

Fig. 10. Propane conversion and propene selectivity over 1Co/S-1 in 10 PDH/ regeneration cycles. Reaction conditions: T = 550 °C, catalyst amount = 100 mg, WHSV(C3H8) = 4.7 h-1, C3H8:N2 = 2:3. Each cycle consisted of a PDH stage lasted for 120 min and a regeneration stage lasted for 30 min.

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