Utilisation of coal tar naphthalene oil fractions for the synthesis of value-added chemicals: alternative paths to mono- and di-methylnaphthalenes.

This study investigates the utilisation of coal tar naphthalene oil fraction (CTNOF), an economical by-product derived from the iron-steel industry, for the production of valuable chemicals, with a particular focus on methylnaphthalenes (MNs) and dimethylnaphthalenes (DMNs). Of specific interest is 2,6-dimethylnaphthalene (2,6-DMN), a pivotal component in the manufacture of polyethylene naphthalate (PEN). The intricate and costly nature of 2,6-DMN production currently poses challenges to the commercial viability of PEN. This study provides the potential heterogeneous reaction pathways for the synthesis of MNs and DMNs via methylation, disproportionation, and isomerisation of CTNOF. The utilisation of CTNOF was investigated in a laboratory-scale fixed bed reactor operating at atmospheric pressure using a mixture of CTNOF: methanol having 1:5 mass ratio over HBeta zeolite catalyst at a temperature of 400 °C and weight hourly space velocity of 2 h−1. The results reveal the successful methylation of CTNOF over the HBeta zeolite catalyst, initially achieving high naphthalene conversion, particularly into 2-MN. This highlights the potential of CTNOF as an alternative feedstock for the production of value-added chemicals. While naphthalene conversion initially reaches 99 wt% within 0.5 h of operation, it gradually decreases to approximately 10 wt% over extended run times. Notably, coke deposition significantly deactivates the HBeta zeolite catalyst during CTNOF methylation, impacting naphthalene conversion. A substantial proportion of naphthalene compounds convert to methylnaphthalenes early in the reaction, predominantly 2-MN, increasing from 14 wt% (in CTNOF feedstock) to 87 wt%. Among DMNs, selectivity for 2,6-DMN, 2,7-DMN, 1,3-DMN, and 1,7-DMN increases, while other DMN isomers exhibit a sharp decrease in selectivity. The distribution of 2,6-triad DMNs rises from 38 wt% in feedstocks to 52–55 wt% with extended reaction times, attributed to MN conversion to DMNs and potential isomerisation from other DMNs. This study underscores the feasibility of using CTNOF for the direct synthesis of valuable chemicals, specifically 2,6-DMN and 2-MN, through methylation over HBeta zeolite catalysts. However, it emphasises the critical role of residence time in coke deposition and the need for optimisation, particularly regarding this parameter, to ensure the efficiency of this catalytic process. [ABSTRACT FROM AUTHOR]