R-Oxo hydroformylation processes on rhodium phosphite complexes developed at LLC «RN-RD CENTER» are described – selective production of n-butyral from propylene (R-Oxo I), production of a mixture of n-butyral and isobutyral in equal parts (R-Oxo II), selective production of n-pentanal from a mixture of linear butenes (R-Oxo III). A scheme for the hydroformylation of propylene with membrane separation of the catalyst from the heavy reaction products is described.The analysis of the direction of using C3–C5 oxosynthesis products as raw materials for the production of ester lubricants is carried out.

The data review of low molecular olefin C2-C4 hydroformylation as a key step of oxygenate compound oxosynthesis is presented. The industrial and perspective cobalt and rhodium organometallic catalytic systems modified with phosphine and phosphite ligands as well as the industrial technological schema of hydroformylation assisted with such a catalysts are demonstrated.

A review of scientific and patent data on the hydroformylation of lower C2–C4 olefins in the oxo synthesis of oxygen-containing products is presented. Industrial and prospective catalytic systems based on organometallic compounds of cobalt and rhodium modified with phosphine and phosphite ligands and also industrial technological schemes involving such catalytic systems are examined.

A method is proposed for the regeneration of fire-resistant triaryl phosphate oils by heat treatment with anhydrous neutralizing agents with subsequent distillation of the reaction mixture. This treatment leads to the elimination of aging products in used triaryl phosphate oils such as acids, phenols, condensation products, wear metals, introduced sludge, and water. This method gives high yields of the regenerated oils meeting the standard requirements of fire-resistant triaryl phosphate oils for reuse.

According to the data of 1 H NMR spectroscopy, trimethylolpropane, di(trimethylolpropane), linear formals, and structures including a fragment of a cyclic formal are the main components of the bottom residue after vacuum distillation of raw trimethylolpropane yielded in the technological process of n -butyral condensation with formaldehyde proceeding by the Cannizzaro–Tishchenko reaction. The content of other impurities is minor. The heavy bottoms can be converted in high yield to a mixture of esters of trimethylolpropane and di(trimethylolpropane) by esterification with n -pentanoic acid. Such esters are characterized by a low pour point, high chemical resistance, thermal stability, and good viscosity-temperature properties, as well as sufficient compatibility with various plastic materials, and therefore, can be employed as lubricants, polymer plasticizers, and other products.

The method for the regeneration of used fire-resistant oils based on treating oils with an anhydrous neutralizing agent at heating, followed by rectification has been developed. As a result of such treatment, used triaryl phosphate oils are purified from a complex of aging products (acids, phenols, sealing products, wear metals, introduced sludge, water). The method provides high yieldsof regenerated oils with quality that meets the regulatory requirements for fire-resistant triaryl phosphate oils for reuse.

The physicochemical properties and production of fire-resistant oils derived from triaryl phosphates are discussed. The method for obtaining butylated oil developed at the Rosneft United Research and Development Center is described. The application of this method for resuming the production of fire-resistant oils and hydraulic fluids using raw materials available in the Russian Federation is examined.

The possibility of controlling the composition of a mixture of triphenyl phosphate, p-tert-butylphenyl diphenyl phosphate, di(p-tert-butylphenyl)phenyl phosphate, and tri(p-tert-butylphenyl) phosphate, formed by transesterification of triphenyl phosphate withp-tert-butylphenol, was demonstrated. The amount ofp-tert-butylphenol necessary for transesterification of triphenyl phosphate to yield a mixture of phosphates of required composition was determined. If necessary, the composition of the phosphates can be adjusted by selective distillation of triphenyl phosphate in a vacuum.

In this review, published information on the nature and molecular compositions of organochlorine compounds (OCCs), which are found in crude oil and in its refined products, is systematized. The native and added OCCs are reviewed. The formers are concentrated predominantly in high molecular weight resinous-asphaltene substances of crude oil, the latter’s, referred to as light organochlorine compounds, are present in the gasoline fractions. The following chemicals that are used for oil production are regarded as possible sources of OCCs: inhibited hydrochloric acid, acid compounds; organic solvents of asphalt-resin-paraffin deposits, organic solvents served for oil production stimulation, and possible products of a mutual solvent chlorination with hydrochloric acid.

Alcohols were obtained by the one-stage hydroformylation of olefins from the hydrocarbon fraction C 6 –C 9 , which was produced in the Fischer—Tropsch synthesis followed by the hydrogenation of aldehydes yielded by the hydroformylation products. The process is carried out on the cobalt catalyst modified by tertiary phosphines under the synthesis gas pressure 85 bar and temperature 180 °C. The role of the solvent is performed by paraffins of the hydrocarbon fraction from the Fischer—Tropsch synthesis. Cobalt acetylacetonate Co(acac) 2 , acetate Co(OAc) 2 , and carbonate CoCO 3 can serve as catalyst precursors. The complexes with bulky and basic phosphines were shown to possess satisfactory activity and high selectivity to alcohols. Tricyclohexyl- and triphenylphosphines are the most promising for the implementation of the process. The full conversion is achieved within 8 h at the cobalt concentration ∼0.2 wt.%: the residual olefin content is <1% and the selectivity to alcohols is ⩾97%.

Based on systematized collection of Raman spectra of about 40 monounsaturated olefins, spectral patterns and invariant relations were established that formed the basis of the method for determining total olefins (total unsaturation per 100 carbon atoms) and their main classes in solutions of saturated hydrocarbons. Self-tuning of the model by calculating the proportion of spectrally unresolvable C=C components using the intensity of conjugated methyl groups increased its accuracy. In terms of repeatability, speed and cost-effectiveness of the analysis, the Raman-method is superior to standard methods of gas and adsorption chromatography and other modern spectralcorrelation methods. The accuracy and stability of the results repeatability is confirmed by more than annual series of parallel comparisons with the data of known method. It is shown that five types of olefins in paraffin model solutions are sufficient to construct calibration curves in units of the number of C=C bonds per 100 carbon atoms. These units make it possible to transform the data to the iodine scale and unify the calibration model for different fractions regardless of the hydrocarbon chain length. The Raman technique can be extended to analyze other mixtures of nonaromatic hydrocarbons and be used for remote control of processes via fi ber optic cables in industrial production.

Based on the systematized collection of the Raman spectra of about 40 monounsaturated olefins, spectral regularities and invariant relations were established that formed the basis of the method for determining total olefins (total unsaturation per 100 carbon atoms) and their main classes in solutions of saturated hydrocarbons. Self-adjusting of the model by calculating the proportion of spectrally unresolvable C=C components with the use of the intensity of conjugated methyl groups increased its accuracy. In terms of repeatability, speed and cost-effectiveness of the analysis, the Raman-method is superior to standard methods of gas and adsorption chromatography and other modern spectral-correlation methods. The accuracy and stability of the results repeatability is confirmed by more than annual series of parallel comparisons with the data of known method. It is shown that five types of olefins in paraffin model solutions are sufficient to construct calibration curves in units of the number of C=C-bonds per 100 carbon atoms. These units allow recalculating data to the iodine scale and unifying the calibration model for different fractions regardless of the length of the hydrocarbon chains. The Raman technique can be extended to analyze other mixtures of non-aromatic hydrocarbons and be used for remote control of processes via fiber optic cables in industrial production.

According to the results of the comparative study performed of the littoral sediments sampled in small inlets of Kandalaksha Bay (the White Sea in the Russian Arctic), the metals (Fe, Mn, Cu, Zn, Pb, Cr, and Li) occur mainly in a biogeochemical-stable mineral-incorporated form, which comprises 77–99% of the total metal content. The ratio of the liable form, which is easily extracted by a weak acid, is on average 3.2% for the total Fe, 2.0% for Mn, 1.7% for Cr, 5.6% for Pb, 5.8% for Zn, 6.5% for Cu, and is negligible for Li. The concentrations of the most studied trace metals are below the threshold level according to the environmental quality guidelines (the sediment analysis). The ratio of the metal forms evidences the natural origin of the elevated concentrations of both Zn and Cr in the sediments.

The kinetics of propene hydroformylation in the presence of the catalytic system Rh(acac)(CO) 2 / n L (L = 2,2′-bis[(1,1′-diphenyl-2,2′-diyl)phosphito]-3,3′,5,5′-tetra- tert -butyl-1,1′-diphenyl, 0.5 < n < 20) in para -xylene at 90°C is reported. At n ≥ 2, the rate and regioselectivity of the process are independent of the L concentration. The reaction is of positive fractional order with respect to propene and hydrogen and of negative order with respect to CO. The molar ratio between the linear product and the branched product decreases with an increasing CO pressure and increases with an increasing H 2 pressure. The kinetic data are consistent with a process mechanism involving irreversible propene addition to the unsaturated hydride complex HRh(CO)L with the formation of the π-complex HRh(CO)L(C 3 H 6 ). The insertion of coordinated propene into the H-Rh bond of this complex is reversible in the linear aldehyde formation route and is quasi-equilibrium in the branched isomer formation route. The conclusions as to the character of these reaction steps are corroborated by the compositions of the but-1-ene and but-2-ene hydro-formylation products.

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Oxygen exchange at the water-bottom interface in the northeastern Black Sea was studied using bottom tanks (fluxes and oxygen consumption for organic matter mineralization and for respiration of soil and water organisms). The relationship of biogenic fluxes and patterns of biochemical (enzyme) destruction of organic matter by the components of the bacterial and microproducer community was established. The prevalence of microbial oxidation of organic matter correlated with high proteolytic activity in near-bottom water. The principal significance of organic matter oxidation in near-bottom water for the phytoplankton and its respiratory expenditures was demonstrated both in the open system of the near-bottom layer and in the closed tank system. A similar trend was demonstrated for benthic organisms.

The key lines of research in a new field of the membrane science and technology, viz., organic solvent nanofiltration, are considered. The prospects for its use in chemical, petrochemical and food industries are discussed. Attention is focused on membranes developed for this method.

Time variations in the main hydrochemical indices of water, organic matter forms, and hydrolytic enzyme activities in aquatic environment have been studied in winter in the southeastern Kara Sea (Yenisey Estuary with depths from 29 to 31 m). The abundance of some components of microproducer (pico-, nano-, and microphytoplankton) and bacterial plankton communities has been analyzed. High functional activity of microcommunities has been demonstrated in winter hydrobiological period. The hydrological, hydrochemical, biochemical, and biological indices of aquatic environment considerably varied in time while their stratification remained stable. The total resources of biologically accessible dissolved organic matter was evaluated by splitting the biological oxygen demand curves obtained under standard conditions (at 22°C).