Ethanol-to-hydrocarbons (ETH) process, is investigated in this work due to the requirement of sustainable production route for light olefins such as ethene and propene. Majority of the mechanism insights of ETH process are principally proposed based on the methanol-to-hydrocarbons (MTH) process, which involves a homologous reaction system. The reaction intermediate species including cyclopentenyl cations and aromatics species, which are denoted as “hydrocarbon pool (HCP)” species in MTH process, were discovered and identified in the ETH process by in situ solid-state ¹³C NMR (ssNMR) experiments, advanced 2D ¹³C–¹³C INADEQUATE (Incredible Natural Abundance DoublE QUAntum Transfer Experiment) ssNMR experiment, ¹²C/¹³C-C₂H₅OH isotope switching experiments complemented by gas chromatography-mass spectroscopy (GC–MS). Especially, in the ETH reaction, ethylcyclopentenyl cations and their deprotonated form were first captured and exhibited relatively higher activity in the formation of ethene and propene. Multi-routes with the participation of these active intermediates were proposed and evaluated by density functional theory calculation (DFT), demonstrating that they can play important roles in the formation of olefins. Ethene formation are mainly formed from ethanol dehydration, whereas propene can be produced via multi-routes with the participation of the captured HCP species. Moreover, the detailed reaction routes may be modulated by the temperature. This work provides direct evidences of the critical function of HCP species in the ETH process and reveals the mechanism of olefin formation.

由于对乙烯和丙烯等轻质烯烃的可持续生产路线的要求，本文研究了乙醇制烃 (ETH) 工艺。ETH过程的大部分机理见解主要是基于甲醇制烃（MTH）过程提出的，该过程涉及同源反应系统。通过原位固态¹³ C NMR (ssNMR) 实验，在 ETH 工艺中发现并鉴定了 MTH 工艺中称为“烃库 (HCP)”的反应中间体物质，包括环戊烯基阳离子和芳烃物质，先进的2D ¹³ C– ¹³ C INADEQUATE（难以置信的自然丰度双量子转移实验）ssNMR 实验，¹²C/ ¹³ C-C ₂ H ₅OH 同位素转换实验辅以气相色谱-质谱 (GC-MS)。特别是在 ETH 反应中，乙基环戊烯基阳离子及其去质子化形式首先被捕获，并在乙烯和丙烯的形成中表现出较高的活性。通过密度泛函理论计算（DFT）提出并评估了这些活性中间体参与的多路线，证明它们可以在烯烃的形成中发挥重要作用。乙烯的形成主要由乙醇脱水形成，而丙烯可以通过多种途径在捕获的 HCP 物种的参与下生产。此外，详细的反应路线可能会受到温度的调节。