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<p>This study presents the conversion of syngas (synthesis gas, CO + H<sub>2</sub>) into isobutylene with monoclinic zirconia (<i>m-</i>ZrO<sub>2</sub>), mixed monoclinic/tetragonal zirconia (<i>m</i>/<i>t</i>-ZrO<sub>2</sub>), tetragonal zirconia (<i>t-</i>ZrO<sub>2</sub>) and Ce/La-doped zirconia samples. The physical and chemical properties of the catalyst samples were characterised with nitrogen physisorption, NH<sub>3</sub> and CO<sub>2</sub> temperature-programmed desorption (TPD) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Sample material crystal structures were analysed with powder X-ray diffraction (PXRD) analysis. The pure monoclinic ZrO<sub>2</sub> sample showed the best catalytic performance with 66% CO conversion and 44&#xa0;mol-% C/hydrocarbons isobutylene selectivity at reaction conditions of 450&#xa0;°C, 45&#xa0;bar, GHSV = 2000&#xa0;h<sup>−1</sup>, and CO: H<sub>2</sub> = 1:1. While pure monoclinic ZrO<sub>2</sub> was a highly efficient catalyst for the isosynthesis reaction, pure tetragonal ZrO<sub>2</sub> produced only a minor amount of isobutylene (~ 1&#xa0;mol-%C/hydrocarbons). Interestingly, Ce/La-doped zirconia had a&#xa0;cubic/tetragonal crystal structure, while showing selectivity and activity comparable to <i>m</i>-ZrO<sub>2</sub> (CO conversion 64% and isobutylene selectivity of 40&#xa0;mol-% C/hydrocarbons). Although samples with a purely <i>t</i>-ZrO₂ crystal phase significantly reduced the desired isobutylene selectivity, catalysts with relatively high Ce/La loadings (17% and 5% of the total catalyst mass) in the cubic/tetragonal crystal structure achieved high isobutylene activity and selectivity, owing to the dopant-induced high base-to-acid site ratio and enhanced synthesis gas adsorption capacity. According to the results from density functional theory (DFT) calculations, the poor selectivity of the <i>t-</i>ZrO<sub>2</sub> phase towards isobutylene was due to the promoted intermediate methanation on the coordinatively saturated sites of <i>t-</i>ZrO<sub>2</sub>. Compared to the <i>t</i>-ZrO<sub>2</sub> sample, <i>m</i>-ZrO<sub>2</sub> showed high isobutylene selectivity and activity related to high base to acid site ratio, high synthesis gas adsorption capacity, and kinetically favourable crystal structure to form C<sub>2+</sub> hydrocarbons from C<sub>1</sub> intermediates. These results are important factors in the future work to prepare intrinsically active and isobutylene selective catalysts for the isosynthesis reaction.</p>

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Production of Isobutylene from Syngas – Isosynthesis Over Zirconia-Based Catalysts

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年9月18日

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  • Niko Heikkinen,
  • Laura Keskiväli,
  • Krista Kuutti,
  • Rasmus Ikonen,
  • Bhumi A. Baraiya,
  • Ville Korpelin,
  • Manu Lahtinen,
  • Jaana Kanervo,
  • Mikko J. Heikkilä,
  • Xinwei Ye,
  • Bert M. Weckhuysen,
  • Karoliina Honkala,
  • Juha Lehtonen,
  • Matti Reinikainen

摘要

This study presents the conversion of syngas (synthesis gas, CO + H2) into isobutylene with monoclinic zirconia (m-ZrO2), mixed monoclinic/tetragonal zirconia (m/t-ZrO2), tetragonal zirconia (t-ZrO2) and Ce/La-doped zirconia samples. The physical and chemical properties of the catalyst samples were characterised with nitrogen physisorption, NH3 and CO2 temperature-programmed desorption (TPD) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Sample material crystal structures were analysed with powder X-ray diffraction (PXRD) analysis. The pure monoclinic ZrO2 sample showed the best catalytic performance with 66% CO conversion and 44 mol-% C/hydrocarbons isobutylene selectivity at reaction conditions of 450 °C, 45 bar, GHSV = 2000 h−1, and CO: H2 = 1:1. While pure monoclinic ZrO2 was a highly efficient catalyst for the isosynthesis reaction, pure tetragonal ZrO2 produced only a minor amount of isobutylene (~ 1 mol-%C/hydrocarbons). Interestingly, Ce/La-doped zirconia had a cubic/tetragonal crystal structure, while showing selectivity and activity comparable to m-ZrO2 (CO conversion 64% and isobutylene selectivity of 40 mol-% C/hydrocarbons). Although samples with a purely t-ZrO₂ crystal phase significantly reduced the desired isobutylene selectivity, catalysts with relatively high Ce/La loadings (17% and 5% of the total catalyst mass) in the cubic/tetragonal crystal structure achieved high isobutylene activity and selectivity, owing to the dopant-induced high base-to-acid site ratio and enhanced synthesis gas adsorption capacity. According to the results from density functional theory (DFT) calculations, the poor selectivity of the t-ZrO2 phase towards isobutylene was due to the promoted intermediate methanation on the coordinatively saturated sites of t-ZrO2. Compared to the t-ZrO2 sample, m-ZrO2 showed high isobutylene selectivity and activity related to high base to acid site ratio, high synthesis gas adsorption capacity, and kinetically favourable crystal structure to form C2+ hydrocarbons from C1 intermediates. These results are important factors in the future work to prepare intrinsically active and isobutylene selective catalysts for the isosynthesis reaction.