Home – Home – Jornals – Chemistry for Sustainable Development 2019 number 2

In the past few years, the number of studies regarding the application of ionic liquids (IL) as alternative solvents to extract value-added compounds from crude oil fractions has been growing. Ionic liquids can be considered as green solvents due to their very low vapor pressure and wide range of applications with unique physical and chemical properties. In petroleum and hydrocarbon industries, various solvents have been used for treating purposes. However, these solvents have their own limitations as environmental and economical issue. These limitations can be overcome by use of ionic liquids. This paper gives a survey on the latest most popular IL, from their applications to their feasible results in refinery and petrochemical streams. Especially the selective treatment of the Azerbaijan’s crude oil fractions by IL was highlighted and achieved practicable and suitable results were indicated.

The rheological properties of a two-component aqueous solution of polyvinyl alcohol (PVA), as well as emulsions consisting of water, PVA and hydrophobic filler, have been studied. The dispersed phase of the emulsions was transformer oil (TO) or polymeric petroleum resin (PPR), and the dispersion medium was an aqueous solution of PVA. To increase the adhesion of the PPR to the soil particles, the resin was pre-oxidized with hydrogen peroxide H₂O₂ to produce an oxidized polymeric petroleum resin (OPPR). After the freezing/thawing cycle, cryogels were formed from liquid systems and their mechanical, thermal, and physicochemical properties were studied. It has been established that cryogels containing TO have more elastic properties as compared with two-component cryostructured systems (PVA - water), but have less elasticity than cryogels containing PPR. The latter are also characterized by better thermal insulation properties compared to two-component cryogels. A particular feature of cryogels filled with OPPR is their hydrophobicity. It was revealed that after the soil was impregnated by a polymer emulsion with OPPR and a cryogel was formed subsequently after a freezing/thawing cycle, a water-proof shield was formed. Materials based on cryogels with hydrophobic properties, filled with OPPR, are promising and can be recommended for practical use in the oil and construction industry.

Potentially bioactive dialkyl(4-hydroxybut-2-ynyl)(3-phenyl-2,3-dichloroallyl)ammonium chlorides were synthesized. By base-catalyzed intramolecular cyclization of these salts and subsequent intramolecular recyclization of cyclic products 4-dialkylaminomethyl-5-chloro-1,3-dihydronaphto[1,2-c]furans were obtained. According to biological studies, dimethyl(4-hydroxybut-2-ynyl)(3-phenyl-2,3-dichloroallyl)ammonium chloride has anticoagulant and strongly pronounced antioxidant properties.

The dec-1-ene transformations were studied in the presence of Y, Beta, ZSM-12 and ZSM-5 zeolites in the H-form. It is established that the main products of the reaction in the presence of zeolites H-Y, H-Beta, H-ZSM-12 are dec-1-ene isomers and its oligomers, while in the presence of zeolite H-ZSM-5 dec-1-ene isomerization predominantly occurs. The mentioned catalytic systems can be arranged in the following series by the activity: H-Beta > H-Y > H-ZSM-12 >> H-ZSM-5, and by the selectivity of oligomers: H-ZSM-12 > H-Beta ~ H-Y >> H-ZSM-5 in the temperature range of 150-220 °С. Among oligomers the dimers of decene are predominant, have an alkyl-naphthenic structure, contain unsaturated hydrocarbons with tri- and tetra-substituted double bonds of 2.2-3.2 % was established. Physicochemical properties of the synthesized decene oligomers are similar to the hydrogenated poly-α-olefins obtained on the catalytic AlCl₃ complexes.

Native and modified humic acids (HA) isolated from brown coals of Russia and Mongolia were studied. Their composition was characterized using technical and elemental analyses, and 13C NMR (CPMAS) spectroscopy. A destructive alkylation of humic acids with butanol followed by debitumination, which changes the structural group composition of HA has been held. The biological activity of humic preparations in the form of sodium and potassium humates is investigated depending on the structural group parameters: the degree of aromaticity fа, hydrophilic-hydrophobic parameter fh/h and parameter reflecting the ratio of aromatic and aliphatic fragments of organic mass of humic acids far/al. It is shown that an increase in the degree of aromaticity HA leads to an increase in their biological activity.

It was shown that mechanochemical activation of a mixture of gibbsite and lithium carbonate in a ball mill for 2–4 hours, followed by heat treatment of activation products in air at 650 °С, allowed obtaining highly dispersed monophasic α-LiAlO2 with a specific surface area more than 10 m²/g.

The annual dynamics of composition and content of groups of phenolic compounds (hydroxybenzoic acids, hydroxycinnamic acids and flavonols) and individual phenolics (gallic, protocatehuic, chlorogenic, caffeic, p-coumaric and cinnamic acids, hyperoside, isoquercitrin, rutin and avicularin) in the leaves of Spiraea media Fr. Schmidt, S. chamaedryfolia L. и S. hypericifolia L., growing in Novosibirsk in the areas with high and background levels of transport and industrial pollution were studied. The peculiarities of effects of environmental contamination and meteorological conditions on the content of phenolic compounds and their groups are revealed. The concentrations of the major constituents in leaves of the species decreased significantly in the urban area in comparison with the background one. The most stable annual decrease in the concentrations was found in the leaves of S. hypericifolia. The level of the annual variability of the number of phenolic components under the conditions of pollution increased (S. media, S. chamaedryfolia) or slightly changed (S. hypericifolia) compared with the control, and the level of variation in the concentrations of most constituents, on the contrary, decreased.

This paper presents the results of the studies of cyclic aromatic compounds composition in gas condensates of Maloyamalskoye and Myldzhinskoye gas fields of Western Siberia. The composition of aromatic compounds in gasoline cuts of gas condensates was analyzed by GC method. Data on group composition of С7–С10 aromatic compounds in gasoline cuts demonstrate that the gas condensates of Maloyamal’skoye gas field are enriched with toluene (С7) and xylenes (С8) while in the samples of Myl’dzhinskoye gas field the contents of trimethyl- (С9) and tetramethyl benzenes (С10) are high. The composition of aromatic compounds of benzene, naphthalene and phenanthrene series in the non-fractionated condensates was studied using GCMS method. It has been shown that alkyl benzenes of condensates are represented predominately by low-molecular compounds (С7–С10), content of long-chain n-alkylbenzenes and n-alkyltoluenes is very low. In addition to alkyl-substituted benzenes the naphthene-substituted benzenes (methyl- and dimethyltetralines) are identified in gas condensates. The relative concentrations of cadalene, retene, ethyl benzene, 1,2,3- and 1,2,4-trimethylbenzenes are used as genetic factors on the composition of aromatic compounds. It has been established that humic organic matter contributed to the formation of the studied fluids. The evidences of that are: higher than usual values of Prystane/Phytane ratio; high content of xylene; increased content of 1,2,5- and 1,2,7-trimethylnaphthalenes and the presence of aromatic hydrocarbons – biomarkers (cadalene, retene). Parameters calculated from the composition of alkyl benzenes and alkyl naphthalenes determine the thermal maturity of condensates. According to the values of ratio (m- + p-xylene)/o-xylene, naphthalenic indexes (MNR, DNR2 and TNR6) and low content of long-chain С11+ alkyl benzenes the catagenic maturity level of the studied fluids corresponds to the main gas generation phase.

Solid dispersions of plant flavonoids (dihydroquercetin, puerarin, rutin and genistein) with the arabinogalactan polysaccharide and the glycyrrhizic acid disodium salt are obtained by mechanochemical treatment. Ways of increasing their solubility and transmembrane permeability on artificial membranes have been studied. The formation of supramolecular systems – intermolecular complexes and micelles – was established by NMR relaxation upon dissolution of solid dispersions in water, their stability constants and thermodynamic parameters were estimated. The possibility of increasing the solubility of the studied flavonoids by a factor of 1.9–30 was shown. It was revealed that the measured rate of transmembrane transfer of flavonoid molecules through an artificial hydrophobic membrane did not correlate with an increase in their solubility. It is assumed that this is due to the structural features of the complexes, as well as the specificity of the flavonoid molecules themselves. The results obtained are qualitatively close to the available data on bioavailability and transmembrane transfer in vivo.

The paper presents the assessment of the spatial distribution of the dust load, macroelement (Ca, Na, Fe, Al, Si, Mg) and mineral-phase composition of particulate matter deposited in snow cover in the impacted area of cement production plant (Topki, Kemerovo region). It was determined that the dust load exceeded the background from tens to hundreds times. The dust load was estimated from allowable to highly hazardous pollution levels. The main crystalline phases included calcite and quartz in the particulate phase of snow and emitted dust from the plant. Additionally, the particulate phase of snow contained the minerals of Portland cement clinker such as brownmillerite and hatrurite. The content of these four minerals mainly controlled the dust load. The content of Ca (10-12 times higher than background values) in the particulate phase of snow showed the anthropogenic geochemical specificity of the samples and it is comparable to the content in the emitted dust from the plant and portland cement. We identified fine particles of Ca ferrites, Fe oxides as most abundant particles in the samples, as well as trace amounts of Ca aluminate and Fe sulphide particles. The main types of particulate matter were suggested to be pit operation, transport and load handling works in the plant. The long-range transport of particulate matter was revealed in the north direction at 2 km distance from the plant. The dust load decreased with the distance from the plant. The identified crystalline phases and fine particle types can be used as tracers for cement production plant emissions.

The temperature-programmed reduction with hydrogen was used to identify the phase composition of the active component and to study redox properties of MnOx-containing honeycomb monolithic catalysts prepared by two different methods: 1) “solution combustion synthesis” (SCS) on monolith surface; and 2) Co-extrusion of MnOx powder with oxide components of the monolith. It is assumed that both monolithic catalysts contain predominantly MnO and some amount of MnO2/Mn2O3. Among the studied catalysts, the monolithic catalyst obtained by the SCS method has the maximum activation energy of the second stage of the reduction of MnO2/Mn2O3, which consists in the reduction of Mn3O4 to MnO. This explains its high activity in the oxidation of methane.

Within the methodology of perception of the fundamentals and regularities of nano-dimensional world functioning, the phenomenon “physical and chemical nano-robot” (PCNR) has been proposed. Its purpose consists in the investigation and organization of nanotechnologies to produce novel substances and materials. The system capable to perform the PCNR functions is offered, evidence-based and realized in the form of the working model. This model is the nanodispersed polycrystalline particle of Ni, one of the metals of iron subgroup (Fe, Co, Ni). We have studied the specific conditions under which such Ni particles possess a set of various functions crucial in the operation of nanotechnologies focused on the synthesis of new substances and materials. The multistage mechanism of PCNR action in the nanotechnological synthesis of materials with different functions is discovered. Scientific bases for the organization of new PCNR as well as the short review of already characterized PCNR-based nanotechnologies have been presented. The basic model of PCNR nanoscale system allowing one to operate technology and control the range of nano-products is developed.