4.7 Article

Polyoxometalate catalyzed oxidative desulfurization of diesel range distillates from waste tire pyrolysis oil

Journal

JOURNAL OF CLEANER PRODUCTION
Volume 389, Issue -, Pages -

Publisher

ELSEVIER SCI LTD
DOI: 10.1016/j.jclepro.2023.136038

Keywords

Distillation; Oxidative desulfurization; Mild conditions; Polyoxometalate; Tire pyrolysis oil

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The study focuses on the sulfur removal from tire pyrolysis oil (TPO) by distillation and oxidation desulfurization process (ODS). A fraction of TPO with boiling point range of 190-350 °C, designated as TPO190-350 °C, was obtained by distillation. The sulfides in TPO190-350 °C were mainly benzothiophene derivatives. A POM-based catalyst was used in the ODS process to remove sulfur compounds from the oil, and it showed excellent catalytic performance and recyclability. The desulfurization efficiency of TPO190-350 °C was achieved up to 91.28%, reducing the initial sulfur contents from 11033 ppm to 961 ppm.
The properties of tire pyrolysis oil are similar to diesel oil, but the high sulfur content in the pyrolysis oil limits its use in diesel engines. In this work, taking the boiling point range of traditional diesel oil as the cutting temperature, a fraction in the temperature range of 190-350 degrees C was obtained by distillation of tire pyrolysis oil (TPO190-350 degrees C). The sulfides in TPO190-350 degrees C are mainly benzothiophene derivatives. And a simple and effective POM-based catalyst ([C16H33N(CH3)3]3PW4O24) has been used in the oxidation desulfurization process for the removal of sulfur compounds from the oil. The catalyst played the role of transferring reactive oxygen species atoms on H2O2 to sulfur compounds. The benzothiophene, dibenzothiophene, and 4,6-dimethyl-dibenzothiophene (500 ppm S) in model oil could be converted to the corresponding sulfone within 1 h at 40 degrees C. Even if the sulfur content was increased to 2000 ppm, the catalyst exhibited well catalytic performance under the same conditions. The catalyst could be recycled and reused with no loss of desulfurization efficiency. Distillation could effectively reduce the presence of olefins in the oil leading to reduce oxidation performance during the oxidation desulfurization process (ODS). In the subsequent desulfurization experiments of TPO190-350 degrees C, a high desulfurization efficiency (91.28%) was achieved for TPO190-350 degrees C, with initial sulfur contents of 11033 ppm declining to 961 ppm.

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