Low-Temperature Catalytic Decomposition of Hydrogen Sulfide into Hydrogen and Diatomic Gaseous Sulfur
Статья (Full article),
Kinetics and Catalysis
, E-ISSN: 1608-3210
||diatomic sulfur, hydrogen production, hydrogen sulfide decomposition, hydrogen sulfide utilization, reaction thermodynamics, sulfide and metal catalysts, sulfur bacteria, three-phase process, triplet and singlet sulfur
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
A new catalytic reaction of hydrogen sulfide decomposition is discovered, the reaction occurs on metal
catalysts in gas phase according to equation 2H2S - 2H2 + S2(gas) to produce hydrogen and gaseous diatomic sulfur, conversion of hydrogen sulfide at room temperature is close to 15 %. The thermodynamic driving force of the reaction is the formation of the chemical sulfur–sulfur bond between two hydrogen sulfide molecules adsorbed on two adjacent metal atoms in the key surface intermediate and elimination of hydrogen into gas phase. ‘‘Fingerprints’’ of diatomic sulfur adsorbed on the solid surfaces and dissolved in different solvents are studied. In closed vessels in adsorbed or dissolved states, this molecule is stable for a long period of time (weeks). A possible electronic structure of diatomic gaseous sulfur in the singlet state is considered. According to The thermodynamics of three pathways of the hydrogen sulfide decomposition reaction is considered. In the thermal process, the gas-phase dissociation of hydrogen sulfide yields hydrogen and diatomic singlet sulfur. Over sulfide catalysts, the reaction proceeds via the formation of disulfane (H2S2) as the key surface intermediate. This intermediate then decomposes to release hydrogen into the gas phase, and adsorbed singlet sulfur recombines into cyclooctasulfur. Over metal catalysts, H2S decomposes via dissociation into surface atoms followed by the formation of gaseous hydrogen and gaseous triplet disulfur. The last two pathways are thermodynamically forbidden in the gas phase and can take place at room temperature only on the surface of a catalyst. An alternative mechanism is suggested for hydrogen sulfide assimilation in the chemosynthesis process involving sulfur bacteria. To shift the hydrogen sulfide decomposition equilibrium toward the target product (hydrogen), it is suggested that the reaction should be conducted at room temperature as a three-phase process over a solid catalyst under a layer of a solvent that can dissolve hydrogen sulfide and sulfur. In this case, it is possible to attain an H2S conversion close to 100%. Therefore, hydrogen sulfide can be considered as an inexhaustible source of hydrogen, a valuable chemical and an environmentally friendly energetic product.