Martínez Juan Daniel, Veses Alberto, Callén María Soledad, López José Manuel, García Tomás, Murillo Ramón
Instituto de Carboquímica (ICB-CSIC), Miguel Luesma Castán 4, 50018 Zaragoza, Spain.
Energy Fuels. 2023 Feb 6;37(4):2886-2896. doi: 10.1021/acs.energyfuels.2c03850. eCollection 2023 Feb 16.
Tire pyrolysis oil (TPO) is one of the most interesting products derived from the pyrolysis of end-of-life tires. Among others, it contains valuable chemicals, such as benzene, toluene, ethylbenzene, and xylene (BTEX), as well as limonene. In order to recover these chemicals, a pilot-scale distillation plant has been designed, erected, and operated using TPO derived from an industrial-scale pyrolysis plant. The distillation facility consists of a packed column (20 kg/h) and is within the fifth technological readiness level. This work describes for the first time the fractioning of the TPO in a continuous operational mode under industrially relevant conditions. For this purpose, different reboiler temperatures (250-290 °C) and reflux ratios (up to 2.4) were preliminarily assessed on the yields and properties of the resulting products: light fraction (LF) and heavy fraction (HF). Thus, the distillation plant is capable of producing 27.0-36.7 and 63.3-73.0 wt % of LF and HF, respectively. The highest BTEX concentration in the LF (55.2 wt %) was found using a reboiler temperature of 250 °C and a reflux ratio of 2.4. Contrarily, the highest limonene concentration (4.9 wt %) in the LF was obtained at 290 °C in the reboiler without reflux. In this sense, the lower the reboiler temperature, the higher the BTEX, and the lower the limonene concentration in the LF. The main results herein obtained serve to gain key insights to operate packed distillation columns using complex and promising hydrocarbons as TPO in order to recover valuable products. In addition, this work provides significant information for optimizing the recovery efficiencies of both BTEX and limonene, as well as their potential applications including that for the resulting HF.
轮胎热解油（TPO）是从废旧轮胎热解中获得的最具吸引力的产品之一。其中，它含有苯、甲苯、乙苯和二甲苯（BTEX）等有价值的化学品以及柠檬烯。为了回收这些化学品，设计、搭建并运行了一座中试规模的蒸馏装置，该装置使用来自工业规模热解装置的TPO。该蒸馏设施由一个填料塔（20千克/小时）组成，处于技术就绪水平的第五级。这项工作首次描述了在工业相关条件下以连续运行模式对TPO进行分馏的情况。为此，初步评估了不同的再沸器温度（250 - 290℃）和回流比（高达2.4）对所得产品（轻馏分（LF）和重馏分（HF））产率和性质的影响。因此，该蒸馏装置能够分别生产27.0 - 36.7重量%的LF和63.3 - 73.0重量%的HF。在再沸器温度为250℃且回流比为2.4的情况下，LF中BTEX的最高浓度为55.2重量%。相反，在再沸器温度为290℃且无回流的情况下，LF中柠檬烯的最高浓度为4.9重量%。从这个意义上说，再沸器温度越低，LF中BTEX的浓度越高，柠檬烯的浓度越低。本文获得的主要结果有助于深入了解如何使用复杂且有前景的碳氢化合物TPO来操作填料蒸馏塔，以回收有价值的产品。此外，这项工作为优化BTEX和柠檬烯的回收效率及其潜在应用（包括所得HF的应用）提供了重要信息。
