The effects of CO2 on organic groups in bituminous coal and high-rank coal via Fourier transform infrared spectroscopy

Abstract

The interactions between supercritical CO2 and coal and their effects on changes in the coal pore structure and organic groups play a critical role in the CO2 geological storage-enhanced coalbed methane recovery. To investigate the effects of supercritical CO2 on organic groups in coals of different ranks and its mechanisms under different temperature and pressure conditions, CO2 sequestration processes in bituminous coals and high-rank coals were replicated using a high-pressure reactor. Four coal samples of different ranks were exposed to supercritical CO2 and water under three temperatures and pressures for 240 h. Fourier transform infrared spectroscopy was used to provide semiquantitative ratios and Fourier transform infrared spectra of coal samples before and after the supercritical CO2–H2O treatment. The results show that interactions between supercritical CO2 and coal were controlled by the coal macromolecular structure, and semianthracite is the inflection point of interaction characteristics for coal samples of different ranks. Bituminous coal, including high- and low-volatility bituminous coal, has a low degree of condensation of its aromatic structure, and its aromatic nuclei can facilitate addition reactions. Swellings primarily break cross-links between aromatic nuclei in the same aromatic layer. These characteristics favor the polymerization addition of aliphatic side chains of aromatic nuclei, causing an increase in the degree of condensation of the aromatic structures in bituminous coal. High-rank coals including semianthracite and anthracite have a high degree of condensation of their aromatic structures, and the aromatic nuclei favor substitution reactions. Swellings primarily break cross-links connecting different aromatic layers, and bond dissociation reactions and sulfuration reactions are more significant for high-rank coal. These characteristics cause a decrease in the degree of condensation of the aromatic structure in high-rank coal. Temperature and pressure have a great impact on interactions between supercritical CO2 and coal and are controlled by the reaction types of the organic groups. With the increase in experimental temperature and pressure, the changes in the organic group content can be classified as the descending type, the rising type, the lower opening parabola type, and the upper opening parabola type. 45.0°C and 10 MPa is the inflection point of the changes in the organic group content. Descending- and rising-type changes favor addition, bond dissociation, and sulfuration reactions, which are endothermic. The reaction rate of supercritical CO2 and the organic groups increases, and the effects caused by temperature and pressure decrease as the temperature and pressure increase. Lower opening parabola- and upper opening parabola-type changes favor substitution, oxidation, and addition polymerization reactions, which are exothermic. These changes were significantly affected by a variety of reactions and were suppressed by high temperature and pressure. When the temperature is ≤45.0°C and the pressure is ≤10 MPa, supercritical CO2 has remarkable effects on alkyl and hydroxy groups and has a stronger effect on bituminous coal. When the temperature is >45.0°C and the pressure is >10 MPa, supercritical CO2 has remarkable effects on oxygen- and sulfur-containing groups and has a greater effect on high-rank coals.