The present study investigates the regularities of synthesis of methyl glycerol ethers (MGEs) in direct intermolecular dehydration between glycerol and methanol over BEA-type zeolite. The following reaction conditions were varied during the study: temperature (140, 160, and 180°C), pressure (3.0, 5.0, and 7.0 MPa), volume hourly space velocity (0.5 and 1.0 h–1), and methanol to glycerol molar ratio (5 : 1 and 10 : 1). The compositions of the reaction mixtures prepared, as well as the isomeric compositions of the mono- and disubstituted glycerol ethers, were described. The material balances of the process were provided for each combination of operating conditions. The variations in the glycerol conversion, the yields of MGEs, the yield of dimethyl ether as a by-product, and the selectivity towards monomethyl glycerol ethers (relative to dimethyl ones) were investigated as functions of the reaction conditions.

A NiWS sulfide catalyst was generated in situ by decomposition of [(Met)(3)S](2)Ni(WS4)(2) as a precursor, and characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The obtained catalyst is active in hydrogenation of bicyclic aromatics. Heating and extending the reaction time were found to enhance the substrate conversion; the catalyst activity was further increased by adding a sulfiding agent. At a substrate/W molar ratio of 250/1, the conversion was 25% without the addition of the sulfiding agent. With the sulfiding agent it reached 65%.

The study is dedicated to the consideration of lower alkyl ethers of glycerol as potential components of low-melting technical fluids (e.g., heat transfer fluids, hydraulic fluids, aircraft de-icing fluids, etc.). Four isomeric mixtures of glycerol ethers (GMME—monomethyl; GDME—dimethyl; GMEE—monoethyl; GDEE—diethyl) were synthesized from epichlorohydrin and methanol/ethanol in the presence of sodium and subjected to detailed characterization as pure compounds and as aqueous solutions (30–90 vol%). The temperature and concentration dependencies of density, viscosity, cloud point, boiling range, specific heat capacity, thermal conductivity, and rubber swelling were obtained. On the basis of the data obtained, a comparison was made between the aqueous solutions of glycerol ethers and of other common bases for low-melting liquids (glycerol, ethylene glycol, and propylene glycol). Pure glycerol ethers could potentially be used as technical fluids in a very wide temperature range—from −114 to 150 °C. It was further demonstrated that in low temperature applications (e.g., in low-temperature chiller systems) the glycerol-ether-based aqueous heat transfer fluids could provide enhanced efficiency when compared to the glycerol- or propylene-glycol-based ones due to their lower viscosities and favorable environmental properties.

This study proposed and experimentally investigated a novel approach to hydrogenation of light cycle oil (LCO) into components of winter and arctic diesel fuels (DF) environmentally classified as K5 as per the Technical Regulation of the Customs Union (TR CU) 013/2011 “On the requirements for automotive and aviation gasoline, diesel and marine fuels, jet fuels, and heating oils”. The process design involves atmospheric distillation of LCO with EBP 300˚C followed by hydrotreating. Hydrogenates with low concentrations of total sulfur (<10 mg/kg) and arenes (28.6–38.0 wt %) and adequate low-temperature properties (CFPP≤–43˚C) were produced. An assessment of the physicochemical properties of the hydrogenates against applicable regulations for DF properties suggested that these hydrogenates can be effectively used as components of winter and arctic fuels by blending them into hydroisomerization diesel fractions (HIDF) and winter diesel fuels (WDF). An analysis of the main quality characteristics confirmed the feasibility of blending the LCO-derived hydrogenates into winter and arctic diesel fuels. Using GC×GC/MS examination, correlations were found between the hydrogenation process conditions, the physicochemical properties of the hydrogenates, and their detailed hydrocarbon compositions.

The reproducible formation, in mild conditions, of three new 1D zigzag coordination polymers using sulfonylcalix[4]arene (TCASO(2)), metal M2+ cations (M=Co or Zn) and rigid planar N-shaped linkers (stilbene-4,4 '-dicarboxylic acid (1-2H) or azobenzene-4,4 '-dicarboxylic acid (2-2H)) is reported. The obtained coordination compounds (1-TCASO(2)Zn(3), 1-TCASO(2)Co(3) and 2-TCASO(2)Zn(3)) are characterized in the crystalline phase using single crystal and powder X-ray diffraction (XRD and XRPD), TGA and IR-spectroscopy. The three compounds present the same coordination pattern and 1-TCASO(2)Zn(3) and 2-TCASO(2)Zn(3) reveal to be isostructural. Due to a high porosity and amount of accommodated solvent molecules hosted in the network, the generated rigid 1D chains are capable to undergo a reversible dynamic solid-state transformation in terms of crystal packing, accompanied with release/uptake of DMSO molecules leading to compression/stretching of the unit cell along one of the crystallographic axis which was attested by Rietveld refinement on XRPD data.

The present study is dedicated to the experimental verification of a concept for the hydrogenolysis of glycerol over in situ-generated Cu dispersed particles (Cu-DP). The Cu-DP were generated by in situ reduction of a precursor salt (Cu(OAc)2, CuSO4, CuCl2) in the presence of KOH and were active in glycerol conversion under hydrogen (T = 200–220 °C, p(H2) = 1–4 MPa), where 1,2-propylene glycol (PG) and lactic acid (LA) were detected to be the main products. The influence of the reaction conditions (temperature, hydrogen pressure, reaction time, catalyst-to-feed ratio and the KOH/Cu ratio) on the yields of the products is described. It was shown that the selectivity between the PG and LA could be tuned by changing p(H2) or by the KOH amount, i.e., higher yields of LA corresponded to lower p(H2) and higher alkalinity of the reaction media. The activity of the in situ-generated Cu-DP was found to be comparable to that of an industrial Cu-Cr2O3 catalyst. The Cu-DP catalysts were characterized by XRD, XPS, HRTEM and SEM. During the reaction, the catalyst evolved by the sintering and recrystallization of the separate Cu-DP; the crystallite sizes after 1 and 15 h reaction times amounted to 35 and 49 nm, respectively.

The formation and structural analysis of porous hexanuclear ring-like cluster complexes built from two different kind of calixarene ligands is presented, together with their stability and vapor solvent sorption properties.

The unsupported NiWS-catalyst was obtained from the precursor [Ph3S]2Ni(WS4)2 in a hydrocarbon medium (in situ) for hydrogenation bicyclic aromatic compounds. The precursor [Ph3S]2Ni(WS4)2 and the catalyst prepared on its basis were studied by the X-ray diffraction and X-ray absorption methods, XPS and TEM. It was found that the new catalyst formed in situ contains tungsten sulfide and nickel sulfide nanophases. Tungsten sulfide, which has a layered structure, partially forms an insertion compound with nickel that enters between the WS2 layers and bonds covalently to sulfur. The proposed catalyst has proved to be active in the hydrodearomatization processes of model aromatic compounds (naphthalene, methylnaphthalenes) and exhibited the maximum selectivity with the formation of decalins compared to other earlier studied catalysts formed from other precursors in the reaction medium.

Ni-Mo sulfide systems generated in situ from precursor salts were used for the hydrodeoxygenation of o-cresol. After the reaction, the catalysts were recovered and analyzed by transmission electron microscopy and X-ray photoelectron spectroscopy. It was shown that the addition of water into the reaction system affects the composition of the o-cresol conversion product due to a change in the texture and phase composition of the surface layer of the in situ sulfide particles.

In this study, an approach for the preparation of heterogeneous acid catalysts based on asphaltenes isolated from vacuum residue is proposed. Varying the conditions for the sulfonation of asphaltenes made it possible to obtain materials with an acid value of 1.16 to 2.76 meq g−1 and a total sulfur content of 6.4 to 12.3 wt%. The samples obtained were characterized by acid-base titration, nitrogen adsorption, sulfur elemental analysis and transmission electron microscopy techniques, and were studied as potential acid catalysts in the ketalization reaction between glycerol and acetone. Sulfonated asphaltenes (SA) were characterized by a homogeneous distribution of sulfonic groups over the granule surface and an almost complete absence of a porous structure. The ketalization reaction in the presence of SA proceeded without intradiffusion restrictions; as a result of which, their activity was higher than for known heterogeneous catalysts. The most active SA sample (total acid value, 1.16 meq g−1) had an apparent activation energy of 18.0 kJ mol−1, which was lower than the value obtained for the zeolite BEA-40 (29–53 kJ mol−1) and the Amberlyst 36 resin (27 kJ mol−1), and was close to the value for the homogeneous p-TSA catalyst (14.5 kJ mol−1). The SA heterogeneous catalysts did not show any acid leaching and had no loss of activity after five catalytic cycles, with the total turnover number TON = 7247.

The study investigates the activity of an in situ nanosized NiMoS catalyst in the hydrodeoxygenation of diphenyl ether. The hydrodeoxygenation product was found to primarily contain benzene, cyclohexane, and n-hexane. The study identified the effects of reaction temperature and reaction mixture composition on the conversion rate and on the quantitative composition of the product. The conversion rate reached 100% at a substrate : Mo molar ratio of 10.5 : 1. The catalysts isolated after the reaction were analyzed by transmission electron microscopy and X-ray photoelectron spectroscopy. The catalyst dispersion was 1.1.

In this study approaches for chemical conversions of the renewable compounds 1,2-propanediol (1,2-PD) and 2,3-butanediol (2,3-BD) that yield the corresponding cyclic ketals and glycol ethers have been investigated experimentally. The characterization of the obtained products as potential green solvents and gasoline components is discussed. Cyclic ketals have been obtained by the direct reaction of the diols with lower aliphatic ketones (1,2-PD + acetone → 2,2,4-trimethyl-1,3-dioxolane (TMD) and 2,3-BD + butanone-2 → 2-ethyl-2,4,5-trimethyl-1,3-dioxolane (ETMD)), for which the ΔH0r, ΔS0r and ΔG0r values have been estimated experimentally. The monoethers of diols could be obtained through either hydrogenolysis of the pure ketals or from the ketone and the diol via reductive alkylation. In the both reactions, the cyclic ketals (TMD and ETMD) have been hydrogenated in nearly quantitative yields to the corresponding isopropoxypropanols (IPP) and 3-sec-butoxy-2-butanol (SBB) under mild conditions (T = 120–140 °C, p(H2) = 40 bar) with high selectivity (>93%). Four products (TMD, ETMD, IPP and SBB) have been characterized as far as their physical properties are concerned (density, melting/boiling points, viscosity, calorific value, evaporation rate, Antoine equation coefficients), as well as their solvent ones (Kamlet-Taft solvatochromic parameters, miscibility, and polymer solubilization). In the investigation of gasoline blending properties, TMD, ETMD, IPP and SBB have shown remarkable antiknock performance with blending antiknock indices of 95.2, 92.7, 99.2 and 99.7 points, respectively.

The hydrocracking reaction of a pyrolysis fuel oil fraction using in situ generated nano-sized NiWS-sulfide catalysts is studied. The obtained catalysts were defined using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The features of catalytically active phase generation, as well as its structure and morphology were considered. The catalytic reactivity of in situ generated catalysts was evaluated using the hydrocracking reaction of pyrolysis fuel oil to obtain a light fraction to be used as a feedstock for benzene, toluene, and xylene (BTX) production. It was demonstrated that the temperature of 380 °C, pressure of 5 MPa, and catalyst-to-feedstock ratio of 4% provide for a target fraction (IPB −180 °C) yield of 44 wt %, and the BTX yield of reaching 15 wt %.