Effect of TiO2 on Acidity and Dispersion of H3PW12O40 in Bifunctional Cu-ZnO(Al)-H3PW12O40/TiO2 Catalysts for Direct Dimethyl Ether Synthesis

Catalysts Pub Date : 2024-07-08 DOI:10.3390/catal14070435
Elena Millán Ordóñez, Noelia Mota Toledo, Bertrand Revel, Olivier Lafon, R. N. Navarro Yerga
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Abstract

The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H3PW12O40, HPW) supported on TiO2 combined with a Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. In this work, different types of TiO2 were used as a support to study the effect of changes in the structure of the TiO2 support on the acidity and dispersion of HPW. Various TiO2 supports with different structural and surface characteristics have been studied and the results indicate that: (i) the crystallinity and crystallite size of the primary particles of the HPW units depend on the TiO2 support; (ii) the pore size distribution of the TiO2 support affects the surface segregation of the heteropolyacids; and (iii) changes in the supported HPW acid catalysts do not significantly alter the crystal structure of the CuO and ZnO phases after contact with CZA in bifunctional catalysts. The activity results indicate that the variation in the intrinsic activity of the Cu-ZnOx centers in the bifunctional catalysts for direct DME synthesis is minimal due to the limited alteration of the crystal structure of the centers.
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TiO2 对直接合成二甲醚的双功能 Cu-ZnO(Al)-H3PW12O40/TiO2 催化剂中 H3PW12O40 的酸度和分散性的影响
研究了基于磷钨酸(H3PW12O40,HPW)的双功能混合催化剂与 Cu-ZnO(Al)催化剂在以合成气为原料直接合成二甲醚(DME)过程中的性能。在这项工作中,使用了不同类型的 TiO2 作为载体,以研究 TiO2 载体结构的变化对 HPW 酸性和分散性的影响。研究了具有不同结构和表面特征的各种二氧化钛载体,结果表明(i) 高纯水单元初级粒子的结晶度和晶粒大小取决于 TiO2 载体;(ii) TiO2 载体的孔径分布会影响杂多酸的表面离析;(iii) 在双功能催化剂中,支持的高纯水酸性催化剂与 CZA 接触后,CuO 和 ZnO 相的晶体结构变化不大。活性结果表明,由于双功能催化剂中 Cu-ZnOx 中心的晶体结构变化有限,因此直接合成二甲醚的 Cu-ZnOx 中心的内在活性变化极小。
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