Gas diffusivities of coal are not measured directly but are normally regressed by fitting mathematical diffusion models to fractional sorption data measured in sorption experiments. This paper firstly measured three fractional adsorption curves at various equilibrium pressures with the manometric method. The measured fractional adsorption curves were then modeled with one single-fitting-parameter (SFP) model and three triple-fitting-parameter (TFP) models. The modeling results showed that the TFP models were phenomenologically over-parameterized due to the usage of three fitting parameters, which may be excessive for curve fitting. The phenomenological over-parameterization resulted in multiple pressure-dependences of gas diffusivity for the TFP models. The TFP models should thus be carefully used. On the other hand, the dual-fitting-parameter (DFP) models also have excellent performance in curve fitting and can produce interpretable modeling results. The DFP models can be used as an alternative to the TFP model in the future.

Diffusion kinetics is widely acknowledged to dominate gas flow in coal matrix blocks. Knowledge of this topic is important for ongoing coalbed methane recovery and CO₂-enhanced coalbed methane production. Because laboratory diffusivity measurements are normally conducted on powdered coals, it is unclear how representative the results are for coalbeds. Investigations into the effects of particle size on gas diffusivity can provide insights into the in situ diffusivity of the coal matrix. This paper presents measured CH₄ desorption data in two Chinese anthracites (one brittle, one hard) having different particle sizes, to investigate the effects of particle size on diffusion kinetics. The experimental data were fitted by both the unipore (UP) and bidisperse (BD) models. The BD model agreed better with the measured data than the UP model, especially for the brittle coal. This indicated that the brittle coal was more abundant in macropores than the hard coal. Diffusivity in the hard coal decreased with increasing particle size but varied stochastically within a small value range in the brittle coal as the particle size increased. The diffusivity of the brittle coal, with its higher vitrinite content and lower inertinite content, was greater compared with the hard coal. This was inconsistent with reported data in which vitrinite had a smaller diffusivity than inertinite. This anomalous phenomenon may be caused by the generation of comparatively more macropores during grinding in the brittle coal. These results indicate that the effects of particle size on diffusivity may be coal-dependent, and further, the effects of particle size are influenced by other factors, including coal structure.