Catalytic hydroconversion of extraction residue from Shengli lignite over Fe–S/ZSM-5

• Fe–S/ZSM-5 shows high activity for CHC of Shenli lignite extraction residue (ER).
• Some CH2 and O in the ER could be connected to condensed aromatic rings (CARs).
• Much higher yield of soluble portion was obtained from CHC than from NCHC of the ER.
• Radical hydrogen transfer to the CARs could be a crucial step for CHC of the ER.

A highly dispersive Fe/ZSM-5 as the precursor of Fe–S/ZSM-5 was prepared by decomposing Fe(CO)5 onto ZSM-5 zeolite at 250 °C. Shengli lignite (SL) was isolated to extractable portion (EP) and extraction residue (ER) by exhaustive extraction with isometric carbon disulfide/acetone mixed solvent (IMCDSAMS) under ultrasonic irradiation. The EP and ER were analyzed with a direct analysis in real time ionization source coupled to ion trap mass spectrometer. Both of them and SL were analyzed with a Fourier transform infrared spectrometer. The ER was subjected to non-catalytic hydroconversion (NCHC) and catalytic hydroconversion (CHC) over Fe–S/ZSM-5, which was formed by in situ reaction of Fe/ZSM-5 with sulfur added, in cyclohexane under pressurized hydrogen at 300 °C. The reaction mixtures were sequentially extracted with petroleum ether, carbon disulfide, methanol, acetone, and IMCDSAMS to afford extracts 1–5 (E1–E5), which were analyzed with a gas chromatography/mass spectrometer (GC/MS). As model reactions, the CHCs of di(1-naphthyl)methane (DNM) and diphenylmethane (DPM) over Fe–S/ZSM-5 were also conducted in cyclohexane at 300 °C. The results show that more than 50% of organic matter in the ER was converted to a soluble portion by the CHC, whereas the yield of soluble portion from the NCHC is only 10.52%. GC/MS-detectable species only appear in the E1, which mainly consists of alkanes, arenes, and arenols either from the NCHC or from the CHC. DNM was selectively hydrocracked to naphthalene and 1-methylnaphthalene over Fe–S/ZSM-5, while DPM hydrocracking did not proceed, indicating that Fe–S/ZSM-5 catalyzed the formation of radical hydrogen from molecular hydrogen and subsequent radical hydrogen transfer (RHT) to the ipso-position of naphthalene ring in DNM. Some CH2 and O in the ER could be connected to condensed aromatic rings (CARs). Analogously, RHT to the ipso-position of CARs in the ER resulted in the release of arenes and phenols from the ER.