Hydrogen production from hydrogen sulfide of Black sea in the process of low temperature catalytic decomposition of H₂S

The review is devoted to a very urgent problem of utilization of toxic hydrogen sulfide of the Black Sea for the production of hydrogen – a generally recognized environmentally friendly energy carrier of the future and a valuable chemical reagent. The possibilities of the recently discovered method of low-temperature catalytic decomposition of hydrogen sulfide (LTCDHS) for the production of hydrogen and elemental sulfur with the H2S conversion close to 100% are considered. Since this process is carried out at room temperature without the supply of thermal energy from the outside, the main attention is paid to the thermodynamic aspect of the implementation of this chemical transformation. The mechanism of the LTCDHS reaction on sulfide and metal catalysts is considered in the framework of the non-equilibrium thermodynamics of the irreversible processes for open systems, since this process is carried out at the expense of the internal chemical energy of the substrate molecules – hydrogen sulfide. On sulfide catalysts, the irreversible process of H2S decomposition proceeds through the stage of formation of disulfane, H2S2, as a key intermediate, and the reaction products are hydrogen and solid sulfur. The reaction proceeds through a series of successive exothermic stages of dissociation of hydrogen sulfide molecules, in which the entropy of the system decreases due to its scattering (dissipation) into the environment in the form of bound energy TΔS. The remaining part of the free en-ergy is accumulated on the surface of the catalyst and is used for the energy-consuming stage of decomposition of the adsorbed key intermediate. Similarly, a metal catalyst ensures the capture and accumulation of energy from the exothermic processes of adsorption and dissociation of the initial hydrogen sulfide molecules into the atomic adsorbed state of hydrogen and sulfur. The stored energy is used for the chemical transformation of the adsorbed intermediates into the final products of the reaction: molecular hydrogen and diatomic triplet sulfur, followed by their desorption into the gas phase. When hydrogen sulfide is decomposed on metal catalysts at room temperature, along with hydro-gen, a previously unknown diatomic gaseous sulfur is obtained in the ground triplet state, the existence of which is predicted by quantum chemistry. Some properties of triplet sulfur and white globular hexagonal sulfur obtained from its saturated aqueous solutions, which is a previously unknown allotrope of solid sulfur, are considered. The concept of the crucial role of catalysts in the process of LTCDHS is formulated. Depending on the type of catalysts (sulfide or metal), the LTCDHS reaction proceeds via two different routes due to the use of the internal energy of the substrate molecules – hydrogen sulfide. It is concluded that the proposed LTCDHS method is the most acceptable (from the point of view of energy, ecology and economics) technology for the utilization of hydrogen sulfide in the Black Sea to obtain the target product – hydrogen, and a valuable chemical commodity product – elemental sulfur. However, the developed method of LTCDHS goes far beyond the considered problem of the Black Sea. This development can be easily adapted to the existing industrial processes of toxic hydrogen sulfide utilization by the Claus method, when instead of high - temperature, metal- and energy-intensive processes of hydrogen sulfide processing, its catalytic low-temperature decomposition processes will come to obtain the target product - hydrogen. Therefore, hydrogen sulfide as a source of hydrogen production by the LTCDHS method can help to solve the problem of hydrogen energy developing in the near future.

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