Tuning cobalt carbide wettability environment for Fischer-Tropsch to olefins with high carbon efficiency

doi:10.1016/S1872-2067(23)64410-9

Abstract

Abstract:

Fischer-Tropsch synthesis to olefins (FTO) with high carbon efficiency is an important but challenging research target. Current routes for direct syngas conversion to olefins suffer from high CO₂ selectivity and low olefin yields due to the inevitable water-gas shift (WGS) reaction. Herein, we report that product selectivity can be controlled by tuning the wettability of the environment around the active center through simple physical mixing of cobalt carbide (Co₂C) with a hydrophobic SiO₂ component. The suppressed WGS reactivity results in a greatly improved catalytic performance of Co₂C, significantly decreased CO₂ selectivity (from 47.8% to 16.8%), and increased olefin selectivity (by ~65%) and activity (by 30%). The local hydrophobic environment favors the rapid diffusion of water away from the Co₂C active center, thus remarkably enhancing the linear adsorption of CO and suppressing the production of CO₂ via WGS. This work provides a simple yet effective strategy to modulate the product selectivity and improve the carbon efficiency of the FTO process.

Key words: Fischer-Tropsch to olefins, Syngas conversion, Cobalt carbide, Hydrophobic, Low CO₂ selectivity

Peigong Liu, Tiejun Lin, Lei Guo, Xiaozhe Liu, Kun Gong, Taizhen Yao, Yunlei An, Liangshu Zhong. Tuning cobalt carbide wettability environment for Fischer-Tropsch to olefins with high carbon efficiency[J]. Chinese Journal of Catalysis, 2023, 48: 150-163.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64410-9

https://www.cjcatal.com/EN/Y2023/V48/I5/150

Figures/Tables 12

Fig. 1. Catalytic performance of various catalysts. (a) CO conversion and product selectivity of CMA and CMASc composite oxides with different mixing ratios. (b) Comparison of the catalytic activity and CO2 formation rate calculated based on the total molar CO consumption. (c) Space-time yield of olefins and olefin formation rate. (d) Stability test over the CMASc-1/1 catalyst. Reaction conditions: H2/CO = 0.5, 260 °C, 10 bar, 4000 mL·g-1·h-1.

Fig. 2. CO hydrogenation performance over composite catalysts with different proximity. (a) CO conversion and product selectivity (including CO2) over varied catalysts. (b) Granule mixing of 40-60 mesh CMA and 40-60 mesh hydrophobic SiO2. (c) Powder mixture of CMA and hydrophobic SiO2. (d) Core-shell structured CMA@SiO2-c. ROH denotes oxygenates. Reaction conditions: H2/CO = 0.5, 260 °C, 10 bar, 4000 mL·g-1·h-1.

Fig. 3. (a) FTIR spectra of SiO2. Water droplet contact angle of SiO2 (b) and SiO2-c (c). (d) TG-DTG curves of hydrophobic SiO2-c.

Fig. 4. FTIR spectra of various fresh (a) and reduced (b) samples. Water droplet contact angles of fresh (c) and reduced (d) CMASc-1/1 composite catalysts.

Fig. 5. XRD patterns of various fresh (a), reduced (b), and spent (c) catalysts. (d) H2-TPR profile of various catalysts.

Fig. 6. (HR)TEM images of various spent catalysts. (a) CMA; (b) CMASc-1/1; (c) CMASc-1/5.

Fig. 7. CO/H2O-TPSR-MS of spent CMA and CMASc-1/1 samples.

Fig. 8. CO/H2-TPSR-MS of the spent CMA and CMASc-1/1 samples. (a) Signal of H2O (m/z = 18). (b) Signal of CO2 (m/z = 44).

Fig. 9. WGS probe reaction over the working CMA (a) and CMASc-1/1 (b) samples.

Fig. 10. DRIFTS spectra of CO adsorption. Spent CMA (a) and CMASc-1/1 (b) in the absence of H2O. Spent CMA (c) and CMASc-1/1 (d) in the presence of H2O.

Fig. 11. Effect of H2O partial pressure on CO conversion and CO2 selectivity over working CMA and CMASc-1/1 (a) and its partial enlarged detail (b).

Fig. 12. Transient response curves obtained from propene hydrogenation pulse experiments without (a,c) and with (b,d) the water vapor over the spent CMA and CMASc-1/1 catalyst. R: peak area ratio of C3H6/C3H8.

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