Development of nanosized catalysts for processing synthesis gas to methanol

Conversion of carbon dioxide into chemical waste-free feedstock (carbonates, cyclocarbonates, synthesis gas) requires the use of a two-stage reaction (conversion of carbon monoxide under pressure, followed by purification of the converted gas from carbon dioxide with hot potash or monoethanolamine and removal of residual carbon oxides by catalytic hydrogenation) of the reaction. The main problem with this transformation is that, for energetic reasons, these reactions are difficult to coordinate with each other. To ensure the compatibility of the processes from a thermodynamic point of view, appropriate nanocatalysts are needed to obtain a useful product in the course of the reactions. The authors carried out field tests of various catalysts, discovered the compatibility of the reaction with two catalysts with the required properties: a copper compound for the first stage of the reaction and a compound of zinc oxide for the second stage, and also demonstrated the feasibility of this reaction using phenylethylene contained in a hydrocarbon compound. The numerous processes that can be used to produce methanol can be divided into three categories: indirect, direct, and biofuel. Indirect conversion is widespread throughout the world. This conversion takes place in a process in which biomass, coal or natural gas is converted to a mixture of hydrogen and carbon monoxide known as synthesis gas. The syngas is converted to methanol using a variety of conversion methods. Research on the development and improvement of nanocatalysts for the chemical processing of carbon dioxide into methanol has been carried out. An algorithm has been developed for modeling the composition, structure, and properties of nanocatalysts, and a number of new compounds have been synthesized that are capable of retaining cations with different oxidation states and sizes in the crystal lattice. Work has been carried out to improve nanocatalysts based on nickel for deep methanol hydrotreating.

Acid-basic properties of chromium(III) oxide surface

The article is devoted to the study of the nature and number of acid-base centers on the surface of chromium(III) oxide obtained by precipitation from an aqueous nitrate solution. The curve of the distribution of the number of acidbase centers of the samples is plotted depending on the indicator of the ionization constant of indicators. It was determined that the main Lewis centers make the main contribution to the acidity of the samples; there are also Bronsted centers of different acidity. A comparative analysis of the structural features of the surface of oxides of chromium, zinc and binary systems Cr (III)–Zn (II) was carried out according to the results of X-ray phase analysis of oxides and thermolysis of the corresponding hydroxides. Based on this, the possibility of obtaining nanosized catalysts based on oxide-hydroxide systems of chromium with a number of 3d-metals obtained in the process of polynuclear hydroxocomplexation is predicted.

Combustion Characteristics of Nanoaluminium-Based Composite Solid Propellants: An Overview

The nanosized powders have gained attention to produce materials exhibiting novel properties and for developing advanced technologies as well. Nanosized materials exhibit substantially favourable qualities such as improved catalytic activity, augmentation in reactivity, and reduction in melting temperature. Several researchers have pointed out the influence of ultrafine aluminium (∼100 nm) and nanoaluminium (<100 nm) on burning rates of the composite solid propellants comprising AP as the oxidizer. The inclusion of ultrafine aluminium augments the burning rate of the composite propellants by means of aluminium particle’s ignition through the leading edge flames (LEFs) anchoring above the interfaces of coarse AP/binder and the binder/fine AP matrix flames as well. The sandwiches containing 15% of nanoaluminium solid loading in the binder lamina exhibit the burning rate increment of about 20–30%. It was noticed that the burning rate increment with nanoaluminium is around 1.6–2 times with respect to the propellant compositions without aluminium for various pressure ranges and also for different micron-sized aluminium particles in the composition. The addition of nano-Al in the composite propellants washes out the plateaus in burning rate trends that are perceived from non-Al and microaluminized propellants; however, the burning rates of nanoaluminized propellants demonstrate low-pressure exponents at the higher pressure level. The contribution of catalysts towards the burning rate in the nanoaluminized propellants is reduced and is apparent only with nanosized catalysts. The near-surface nanoaluminium ignition and diffusion-limited nano-Al particle combustion contribute heat to the propellant-regressing surface that dominates the burning rate. Quench-collected nanoaluminized propellant residues display notable agglomeration, although a minor percentage of the agglomerates are in the 1–3 µm range; however, these are within 5 µm in size. Percentage of elongation and initial modulus of the propellant are decreased when the coarse AP particles are replaced by aluminium in the propellant composition.

Ni–Mo sulfide nanosized catalysts from water-soluble precursors for hydrogenation of aromatics under water gas shift conditions

The unsupported catalysts were obtained during hydrogenation by in situ high-temperature decomposition (above 300 °C) of water-soluble metal precursors (ammonium molybdate and nickel nitrate) in water-in-oil (W/O) emulsions stabilized by surfactant (SPAN-80) using elemental sulfur as sulfiding agent. These self-assembly Ni–Mo sulfide nanosized catalysts were tested in hydrogenation of aromatics under CO pressure in water-containing media for hydrogen generation through a water gas shift reaction (WGSR). The composition of the catalysts was determined by XRF and active sulfide phase was revealed by XRD, TEM and XPS techniques. The calculations based on TEM and XPS data showed that the catalysts are highly dispersed. The surfactant was found to affect both dispersion and metal distribution for Ni and Mo species, providing shorter slab length in terms of sulfide particle formation and stacking within high content of NiMoS phase. Catalytic evaluation in hydrogenation of aromatics was performed in a high-pressure batch reactor at T = 380–420 °С, p(CO) = 5 MPa with water content of 20 wt.% and CO/H2O molar ratio of 1.8 for 4–8 h. As shown experimentally with unsupported Ni–Mo sulfide catalysts, the activity of aromatic rings depends on the substituent therein and decreases as follows: anthracene>>1-methylnaphthalene≈2-methylnaphthalene>1,8-dimethylnaphthale-ne>>1,3-di-methylnaphthalene>2,6-dimethylnaphthalene≈2,3-dimethylnaphthalene>2-ethyl-naphthalene. The anthracene conversion reaches up to 97–100% for 4 h over the whole temperature range, while for 1MN and 2MN it doesn’t exceed 92 and 86% respectively even at 420 °С for 8 h. Among dimethyl-substituted aromatics the higher conversion of 45% was achieved for 1,8-dimethylnaphthalene with 100% selectivity to tetralines at 400 °С for 6 h. Similar to 1- and 2-methylnaphtalenes, the hydrogenation of asymmetric dimethyl-substituted substrate carries out through the unsubstituted aromatic ring indicating that steric factors influence on the sorption mechanism over active metal sites. The catalysts were found to be reused for at least six cycles when the hydrogenation is sulfur-assisted preventing metal oxide formation. It was established, that at the first 2–3 h known as the induction period, the oxide catalyst precursors formed slowly by metal salt decomposition, which reveals that it is the rate-determining step. The sulfidation is rather fast based on high catalytic activity data on 2MN conversion retaining at 93–95% upon recycling.