Insights into effects of ZrO2 crystal phase on syngas-to-olefin conversion over ZnO/ZrO2 and SAPO-34 composite catalysts

doi:10.1016/S1872-2067(21)63908-6

Abstract

Abstract:

The utilization of metal oxide-zeolite catalysts in the syngas-to-olefin reaction is a promising strategy for producing C₂-C₄ olefins from non-petroleum resources. However, the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous. Herein, typical metal oxides (ZnO/ZrO₂) with different crystal phases (monoclinic (m-ZrO₂) and tetragonal (t-ZrO₂)) were employed for syngas conversion. The (ZnO/m-ZrO₂+SAPO-34) composite catalyst exhibited 80.5% selectivity for C₂-C₄ olefins at a CO conversion of 27.9%, where the results are superior to those (CO conversion of 16.4% and C₂-C₄ olefin selectivity of 76.1%) obtained over (ZnO/t-ZrO₂+SAPO-34). The distinct differences are ascribed to the larger number of hydroxyl groups, Lewis acid sites, and oxygen defects in ZnO/m-ZrO₂compared to ZnO/t-ZrO₂. These features result in the formation of more formate and methoxy intermediate species on the ZnO/m-ZrO₂ oxides during syngas conversion, followed by the formation of more light olefins over SAPO-34. The present findings provide useful information for the design of highly efficient ZrO₂-based catalysts for syngas conversion.

Key words: Syngas-to-olefins, Crystal phase, ZnO/ZrO₂, SAPO-34, Composite catalyst

Zhaopeng Liu, Youming Ni, Zhongpan Hu, Yi Fu, Xudong Fang, Qike Jiang, Zhiyang Chen, Wenliang Zhu, Zhongmin Liu. Insights into effects of ZrO₂ crystal phase on syngas-to-olefin conversion over ZnO/ZrO₂ and SAPO-34 composite catalysts[J]. Chinese Journal of Catalysis, 2022, 43(3): 877-884.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63908-6

https://www.cjcatal.com/EN/Y2022/V43/I3/877

Figures/Tables 5

Table 1 Catalytic STO conversion over various composite catalysts.

Composite catalyst	CO conversion (%)	CO₂ selectivity (%)	Hydrocarbon distribution (%)
Composite catalyst	CO conversion (%)	CO₂ selectivity (%)	CH₄	C₂-C₄⁼	C₂-C₄^o	C₅₊
t-ZrO₂+SAPO-34	0.5	undetected	9.1	76.6	12.2	2.1
m-ZrO₂+SAPO-34	3.6	42.2	2.3	82.3	12.6	2.7
ZnO/t-ZrO₂+SAPO-34	14.6	44.2	2.4	79.4	16.4	1.8
ZnO/m-ZrO₂+SAPO-34	22.4	44.8	1.7	84.5	11.5	2.2

Fig. 1. Catalytic STO conversion over (ZnO/ZrO2+SAPO-34) composite catalysts. (a) Effect of reaction pressure (648 K, 2500 mL g-1 h-1, H2/CO molar ratio = 2/1); (b) effect of reaction temperature (1.5 MPa, 2500 mL g-1 h-1), H2/CO molar ratio = 2/1); stability of STO reactions over (ZnO/m-ZrO2+SAPO-34) (c) and (ZnO/t-ZrO2+SAPO-34) (d), (648 K, 1.5 MPa, 2500 mL g-1 h-1, H2/CO molar ratio = 2/1).

Fig. 2. Structural characterization. (a) XRD patterns; (b,c) HRTEM images of ZnO/m-ZrO2 and ZnO/t-ZrO2 catalysts; (d,e) elemental mapping of ZnO/m-ZrO2 and ZnO/t-ZrO2 catalysts.

Fig. 3. FT-IR and XPS data. (a) FTIR spectra of ZnO/ZrO2 catalysts; (b) O 1s XPS profiles of ZnO/ZrO2 catalysts; (c) FTIR spectra of ZnO/ZrO2 catalysts after pyridine adsorption and evacuation at 423 K; (d) DRIFTS profiles after CO adsorption at 643 K.

Fig. 4. In situ DRIFT spectra for syngas conversion over various catalysts. Reaction conditions: 648 K, 0.1 MPa, syngas refers to the mixed gas of CO/H2/Ar = 31.7/63.3/5.

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Insights into effects of ZrO₂ crystal phase on syngas-to-olefin conversion over ZnO/ZrO₂ and SAPO-34 composite catalysts

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