The effect of heavy aromatic sulfur compounds on sulfur in cracked naphtha

The scope of the present study was to elucidate the effect of heavy sulfur compounds, commonly found in the gas oils, on the percentage of sulfur in gasoline range during the Fluid Catalytic Cracking (FCC) process. Five model sulfur compounds commonly found in the gas oils were studied: benzothiophene, 2-methyl-benzothiophene, 3-decyl-thiophene, dibenzothiophene and 4,6-dimethyl-dibenzothiophene. In order to maintain a realistic hydrocarbon environment each one of the heavy sulfur model compounds were diluted in conventional gas oil. Their cracking behaviour were studied using a steamed deactivated FCC catalyst, while the run tests were performed in an automated Short Contact Time Microactivity Test Unit (SCT-MAT) operated at 560 °C and 12 s run time. The experimental results indicated that the long chain alkyl-thiophene (3-decyl-thiophene) is mainly responsible for the increase of sulfur amount in the gasoline range during cracking, through dealkylation and side cracking reactions for the production of thiophene and shorter chain alkyl-thiophenes, respectively. That sulfur compound was also the most reactive one with respect to desulfurization, since it was highly cracked to H2S and decomposed to S in coke. On contrary, the polycyclic sulfur compounds did not affect the sulfur amount in gasoline, while their reactions were strongly related to their chemical structure. Thus, the main reaction pathway of the alkylated 2-methyl-benzothiophene and 4,6-dibenzothiophene during the FCC process was isomerization, while for benzothiophene and dibenzothiophene alkylation reactions were dominated.