Supercritical water gasification of glycerol: Intermediates and kinetics

• Quantitative kinetics model for gases production of glycerol SCWG was developed.
• Reaction rates for formation/consumption of H2, CO, CH4 and CO2 were analyzed.
• Temperature for completely SCWG of glycerol was estimated by kinetics model.
• Sensitive analysis of WGSR rate constant was done based on the kinetics model.

In this paper, the liquid products from supercritical water gasification (SCWG) of glycerol were analyzed and some intermediates were identified. A simplified reaction pathway for gases production from SCWG of glycerol was proposed. The first quantitative kinetics model for describing the gaseous products (H2, CO, CH4 and CO2) of SCWG of glycerol was developed. The model comprises seven reactions to describe the typical reactions in SCWG, and the reaction rate constant of each reaction was obtained by using the nonlinear least-square fitting method. The reaction rate analysis showed that the main sources of hydrogen yield were glycerol pyrolysis and steam reforming of intermediates, while the hydrogen yield from water–gas shift reaction (WGSR) was very small. The temperature estimated by the kinetics model for completely SCWG of glycerol solution was given. In addition, the sensitivity analysis of rate constant of WGSR was done based on the model.

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