Empress Catherine II Saint Petersburg Mining University, Saint Petersburg, Russia

L. A. Yachmenova, Candidate of Engineering Sciences, Assistant of the Department of General and Technical Physics
A. G. Syrkov, Doctor of Engineering Sciences, Professor of the Department of General and Technical Physics, e-mail: Syrkov_AG@pers.spmi.ru
V. R. Kabirov, Post-Graduate of the Department of General and Physical Chemistry, e-mail: vkabirov1@gmail.com

The work is devoted to the development of scientific and technological principles, detailing the physico-chemical mechanism of obtaining dispersed metals (Ni, Cu) from oxide raw materials with a minimum carbon footprint, using non-traditional reducing agents. The ideology of solid-state hydride synthesis (SHS) of metals is the basis for solving these tasks. The special trait of SHS is the realization of reduction the metal in an open flow system (flow reactor) by element-hydride (E = Si, C) reagents in the temperature range of thermostability of the latter in the gas phase. The use of ethylhydridesiloxane (EHS) vapor as a silicon-hydride reagent allows not only to reduce the metal from solid oxide, but also to form a protective film on the metal with thermo- and chemically stable Si – C bonds in the film structure. The aim of the work was to develop approaches based on SHS of metals, allowing to drastically eliminate the carbon footprint in the process of metal reduction, as well as to study the features of the mechanism of metal reduction and modification using quantum chemical modeling. This work shows that the sequential reduction of metal oxides by the silicon hydride reagent EHS (stage I) and methane (stage II) under SHS conditions achieves almost complete reduction (degree of reduction α = 99.5%) to metal in stage I if no more than 2.5% vol. Н₂ is added to the EHS vapor. The CO₂ emission in this case is 0.03–0.05 tons of CO₂ per ton of metal. This parameter is more than ten times lower than in known metallurgical processes in industry. With the help of Gaussian-09, Gaussview and HyperChem software packages it has been established by calculation that the adsorption energy values on metal (Cu, Fe) of EHS reagent and modifiers in the form of quaternary ammonium compounds (QAC) are in the range of 58–127 kJ/mol. This corresponds to the chemical interaction in the metal-adsorbate system and agrees with XP-spectroscopy data obtained earlier. The developed ways of carbon footprint decrease as well as the procedures of selection and prediction of properties of dispersed metal additives to technical lubricant (industrial oil I-20) are implemented with economic effect.

The article is published as a platform for discussion.

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