FeNi/gamma-Al2O3 was prepared by thermally decomposing iron pentacarbonyl and nickel tetracarbonyl onto gamma-Al2O3. Geting bituminous coal (GBC) was subjected to noncatalytic hydroconversion (NCHC) and catalytic hydroconversion (CHC) in the presence of FeNi/gamma-Al2O3 and sulfur at 300 degrees C for 3 h. The reaction mixtures from both NCHC and CHC were fractionated to extracts 1-5 (E-1-E-5) by sequential extraction. The molecular compositions of E-1-E-5 were characterized with a Fourier transform infrared spectrometer, gas chromatography/mass spectrometer (GC/MS), and atmospheric solid analysis probe/time of flight-mass spectrometer (ASAP/TOF-MS). The results show that the yields of E-1-E-5 from CHC of GBC are obviously higher than those from NCHC According to GC/MS analysis, the group components in E-1 from the CHC are dominated by alkanes, arenes, and arenols in remarkable higher yields than those from NCHC, and most of the arenes and arenols are alkyl-substituted ones. The addition of active hydrogen atoms catalytically generated over FeNi-S/gamma-Al2O3 to the ipso-position of condensed aromatic rings (CARs) in GBC could play a crucial role in cleaving-CH2 and-O- linkages connected to the CARs and thereby enhanced the yields of alkylarenes and alkylarenols through CHC Meanwhile, the partial hydrogenation of some CARs during CHC could promote the radical hydrogen transfer along with thermal rupture of some relatively strong bonds to produce soluble molecules. According to ASAP/TOF-MS analysis, the soluble species from both NCHC and CHC have molecular mass distributions ranging from 100 to 500 u. A series of polar and/or involatile organic species. (C) 2015 Elsevier B.V. All rights reserved.