The formation and release of volatiles during isothermal fast pyrolysis of vinegar residue (VR) were investigated in a micro-fluidized bed using fast process mass spectrometry (FP-MS), gas chromatography (GC), and time-of-flight mass spectrometry (TOF-MS). Rapid heating, online sample introduction, and high-frequency detection enabled time-resolved analysis of signal intensity, conversion, yield, and formation rate for representative condensable compounds (monocyclic aromatics, furans, and aliphatic oxygenates) and non-condensable gases (H₂, C₂H₄, C₂H₆, CH₄, CO, and CO₂). Monocyclic aromatic formation was suppressed at 500 °C and favored at higher temperatures, while furans and aliphatic oxygenates showed the opposite trend. Formation rates increased with temperature over different ranges depending on the compound: 500–1000 °C for benzene and phenol, 500–700 °C for acetone and furfural, and 500–600 °C for glycolaldehyde and furan. Monocyclic aromatics had substantially higher activation energies for formation (Eₐ) than furans and aliphatic oxygenates. For individual condensable compounds, Eₐ was markedly higher during the slow formation stage (S2) than during the fast formation stage (S1). Most non-condensable gases were released during S1. The gases evolved in a distinct sequence below 600 °C, but this sequence was no longer evident above 800 °C. CO₂ and CO predominated at 500 °C, while the yields of CO, CH₄, and C₂H₄ increased substantially at 1000 °C. The sensitivity of gas formation rates to temperature decreased in the order H₂ > C₂H₆ ≈ C₂H₄ > CH₄ > CO > CO₂. In S1, the relative order of Eₐ among five gas species was H₂ > C₂H₄ > C₂H₆ > CH₄ > CO. In S2, the order was H₂ > CO > C₂H₄ > CH₄ > C₂H₆ > CO₂. Volatile formation pathways were proposed based on the conversion of cellulose, hemicellulose, and lignin. These temperature-dependent release profiles and kinetic data provide a basis for the design of VR gasification processes.
 

Biomass gasification, fast pyrolysis, fluidized bed, kinetics, online analysis