Mechanism insight into the conversion between COS and thiophene during CO2 gasification of carbon-based fuels.

Thiophene is the organic sulfur with good thermal stability in carbon-based fuel, clarifying the conversion mechanism between thiophene and COS is beneficial for achieving in-situ sulfur fixation during CO2 gasification of carbon-based fuels, but the mechanism has rarely been reported. Therefore, calculations based on density functional theory were performed and 16 reaction paths were proposed in this research, clarifying the decomposition mechanism of thiophene and re-fixation mechanism of COS. The attachment of CO2 will lead to the destruction of the thiophene ring and the generation of COS, and CO2 adsorption is the rate-determined step, while the carbon atom that adjacent sulfur atom is the reaction active site. However, the energy barriers of CO2 addition reactions are lower than those of CO2 adsorption reactions, and the energy barrier of reactions occurring on the aliphatics are lower than that occurring on the aromatics. The combination of CO2 and thiophene will thermodynamically lead to the generation of COS and CO. Moreover, gaseous sulfur generated from thiophene decomposition will be converted mutually, while H2S will not be converted into COS. Furthermore, COS will be captured by char, forming solid organic sulfur. The re-fixation of COS will occur on aliphatic chains from the decomposition of aromatics.

Sulfur release behavior and sulfur fixation mechanism during biomass microwave co-pyrolysis of Ascophyllum and rice straw.

Co-pyrolysis with low-sulfur biomass is expected to improve the yield and quality of bio-fuels, without the usage of calcium-based desulfurizer. Sulfur transformation during microwave fluidized-bed co-pyrolysis between terrestrial and marine biomass (Ascophyllum, AS; Rice straw, RS) was investigated. Sulfur release was promoted during biomass co-pyrolysis, but it was inhibited during pyrolysis between AS and low-sulfur char. Thermal cracking of biomass was promoted during co-pyrolysis between biomass, accelerating the combination of H atoms and -SH radicals. Introduction of low-sulfur bio-char (CA) inhibited the generation of bio-char and the release of sulfur. Released sulfur was captured by -OH/C = C functional groups on bio-char through dehydration reactions/addition reactions, forming mercaptan in bio-char. Furthermore, introduction of microwave and bio-char promoted the cyclization and aromatization reaction, converting mercaptan to thiophene and improving the thermal stability of solid sulfur, and thus increasing in-situ sulfur fixation rate.

Mechanism Insight into the Conversion between H2S and Thiophene during Coal Pyrolysis: A Theoretical Study.

Clean coal technology is the important thrust to the achievement of "carbon neutralization"; clearing the transformation mechanism of thiophene, the dominant organic sulfur species in coal, is conducive to promoting the development of sulfur removal technology. DFT calculations were performed, and 28 reaction paths were proposed in this research, clarifying the decomposition mechanism of thiophene and the fixation mechanism of H2S. Thiophene is pyrolyzed mainly through the hydrogen-transfer reaction, which occurs at above 2000 K rather than 800 K. The hydrogen transfer between the C-C bond rather than the C-S bond causes the ring opening. Hydrogen promotes the decomposition of thiophene, which happens at 800 K, with a molar ratio of hydrogen to thiophene of 5. Therefore, thiophene is decomposed at 800 K mainly through the hydrogenation reaction that occurs at para carbons and the C-S bond, the H2S elimination reaction, and the generation of ethane. Furthermore, H2S can be converted into thiophene through the addition reaction with unsaturated hydrocarbon, or the dehydration reaction with hydroxyl or carboxyl groups. The combination between H2S and the aliphatic compound occurs at 800 K, which is mainly influenced by the species of the functional group rather than the composition and morphology of the carbon chain. Meanwhile, the conversion of aromatic compounds tends to the generation of aryl mercaptan rather than thiophene at around 800 K.