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2024, №1

pp. 3-16

Articles

Key words: supercritical fluid extraction; shrinking core model; multicomponent extract; Maxwell—Stefan approach

The paper presents a model of supercritical fluid extraction of plant triglycerides from seeds of high-oil raw material. Oil is considered in a two-component approximation. A three-component solution with CO2 is described within the framework of the theory of regular solutions. The sign of the interaction energy of the molecules of the oil components makes it possible to distinguish between two thermodynamic equilibrium modes. Mass transfer through the transport channels of an individual particle is described within the framework of the shrinking core model. Constitutive relations between diffusion fluxes and gradients of chemical potentials are formulated within the framework of the Maxwell— Stefan approach. Each component of the oil has its own front and a pair of shrinking core/transport zone. It is shown that the concentration profiles of the oil components are determined not only by diffusion processes, as is typical in the framework of the one-component approximation, but also by the material two-phase equilibrium of individual components.

doi:10.34984/SCFTP.2023.19.1.001

2024, №1

pp. 17-29

Articles

Key words: saturation line, density, sulfur hexafluoride, order parameter, rectilinear diameter

Information on the behavior of the SF6 density on the binodal in the asymptotic vicinity of the critical point 3·10-6  < τ < 2 · 10 -4, where τ = (Tc - T)/T , — relative temperature is presented. The densities of the liquid (ρl) and vapor (ρg) phases were calculated based on the experimental data of Garrabos et al. (2018) about the height h at which the meniscus is located separating the two phases of the sample in a horizontal cell with a diameter d at a temperature T under conditions of Earth gravity. As the second component of the method, the order parameter fs(τ) is considered in analytical form, which corresponds to the scale theory (ST) of critical phenomena and is based on (ρl, ρg,T -data from Funke et al. (1998) for SF6 in the range 10-3 < τ <0,3. Several problems are formulated, including the construction of dependencies ρl(τ) и ρg(τ), corresponding to ST and correlating with (h,T)-data for  10-6 < τ < 10-3. The relationship between (h,T) data and the functions fs(τ) и fd(τ) (where fd is the average or rectilinear diameter) is investigated. The dependences of ρl(τ) and ρg(τ) on temperature in the range 10-6 < τ < 10-3 were calculated. The dependences ρl(τ) and ρg(τ) that correspond to ST and working satisfactorily in the range 10-6< τ < 10-3 were constructed.

doi:10.34984/SCFTP.2023.19.1.002

2024, №1

pp. 30-43

Articles

Key words: supercritical carbon dioxide, molecular dynamics, Raman spectroscopy, Widom delta

An approach to modeling the Raman spectra of supercritical carbon dioxide based on Fourier analysis of the autocorrelation function of the dipole moment calculated by the molecular dynamics method is demonstrated. On its basis, Raman spectra of carbon dioxide were simulated along the 310 K isotherm in the pressure range 0.1–15 MPa. It has been established that in the Widom delta there is a broadening of spectral lines, as well as extrema in the dependences of Raman shifts on pressure. The results obtained are in good agreement with known experimental data and indicate a significant influence of cluster formation on the macroscopic properties of carbon dioxide in the vicinity of the critical point.

doi:10.34984/SCFTP.2024.19.1.003

2024, №1

pp. 44-55

Articles

Key words: avermectin, yield, Streptomyces avermitilis, supercritical fluid extraction, carbon dioxide, rotatable uniform plan, optimization.

The process of supercritical fluid extraction of avermectin from the bacterial biomass of Streptomyces avermitilis with carbon dioxide was optimized by the method of a full factorial experiment using a second-order rotatable uniform plan. When planning, the main levels chosen were a pressure of 25 MPa, a temperature of 60°C, and an extraction duration of 100 min. The analysis of the regression equation made it possible to establish the optimal process parameters: 30 MPa, 85°C, and 133 min. In the control experiment, an extract was obtained with a yield of 13 %, containing 41 % avermectin. The yield of avermectin was 5.36 % of absolutely dry biomass, which exceeds the extraction yields obtained using organic solvents.

doi:10.34984/SCFTP.2024.19.1.004

2024, №1

pp. 56-67

Articles

Ferrocene-modified siloxane aerogels

L.V. Panova, D.A. Lemenovskii, M.I. Afanasov, M.A. Popkov, R.O. Burlutsky, M.M. Brusova, V.N. Talanova, D.N. Kholodkov.

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Key words: supercritical carbon dioxide, siloxane aerogels, ferrocene

An effective method for the synthesis of hybrid structure siloxane aerogels with ferrocene fragments built into polymer structure has been developed. At the initial stage, a gel was obtained by polycondensation of tetraethoxysilane and ferrocene-containing alkoxysilanes, catalyzed by BF3 · Et2O in acetone. The transformation of gels into aerogels was carried out using SC-CO2. The aerogel samples were characterized in detail by Mossbauer spectroscopy and nitrogen adsorption methods, and the density of the materials was determined. The iron content in the resulting aerogels varies in the range of 3.6—8.7 % by weight of iron (or 11.9—28.7 % by weight of ferrocene units).

doi:10.34984/SCFTP.2024.19.1.005

2024, №1

pp. 68-82

Articles

Supercritical fluid extraction of the lichen thallus Hypogymnia physodes

O.S. Brovko, A.D. Ivakhnov, D.V. Zhiltsov, T.A. Boitsova, A.A. Sloboda.

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Key words: Hypogymnia physodes, supercritical fluid extraction, low molecular weight phenols, flavonoids, atranorine, antibacterial activity

The process of supercritical fluid extraction of the thallus of the lichen species Hypogymnia physodes with carbon dioxide in the presence of acetone as a co-solvent has been studied. An assessment of extraction conditions (temperature, pressure and duration) on the yields of extract, phenolic compounds, including low molecular weight phenols, atranorine and flavonoids was carried out. It has been shown that the main amount of extractives (up to 90 %) is extracted within 40 minutes of extraction. The extract yield reaches 156.5 mg/g, with a content of phenolic compounds up to 87.3 %. The extracts obtained have high antiradical activity (up to 225 rmol Trolox-equiv/g). A positive correlation has been established between the antiradical activity of extracts and the content of phenolic compounds in them, including atranorine. Antibacterial activity of the extracts was revealed against gram-positive (Bacillus subtilis) and gram-negative (Escherichia coli, Proteus mirabilis) strains of microorganisms.

doi:10.34984/SCFTP.2024.19.1.006

2024, №2

pp. 16-26

Articles

Key words: carbon nanotubes, rapid expansion of supercritical suspensions, dispersion

The dependence of the degree of CNT deagglomeration on the multiplicity of their treatment by the method of rapid expansion of supercritical suspensions (RESS) under various conditions has been studied. It was shown that double treatment by the RESS method makes it possible to increase the degree of CNT deagglomeration more effectively than a single one. Three-fold treatment in the case of nitrogen leads to a slight increase in the degree of dispersion compared to two-fold. In the case of CO2, three-fold treatment can lead to both an increase and a decrease in the degree of dispersion compared to twofold. When nitrogen is used as a dispersion medium, changes in temperature and pressure do not lead to a change in the degree of dispersion of CNTs. When using CO2, a decrease in fluid density ensures greater efficiency of CNT processing.

doi:10.34984/SCFTP.2023.19.2.002

2024, №2

pp. 6-15

Articles

Solubility of betulin in supercritical CO2
and CO2 + ethanol mixture

L.Y. Sabirova, L.Y. Yarullin, I.Sh. Khabriev, V.F. Khairutdinov, T.R. Bilalov.

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Key words: supercritical carbon dioxide, betulin, solubility, co-solvent, equation of state

The results of experimental investigation of betulin solubility in pure and modified supercritical carbon dioxide in the range of temperature (313.15 -333.15 K) and pressure (8.00-30.00 MPa) using the dynamic method are presented. It was found that in pure supercritical carbon dioxide betulin does not dissolve but only swells. The addition of 5 % ethanol as a co-solvent increases the solubility. The pressures corresponding to the first and second crossover points of - (7.7-8.3) MPa and -(27.1-27.6) MPa, respectively, are established in this work. The results of the descri ption of the experimental data using a model based on the Peng-Robinson equation of state are presented.

doi:10.34984/SCFTP.2023.19.2.001

2024, №2

pp. 27-43

Articles

Key words: adsorption, palladium hexafluoroacetylacetonate, hypercrosslinked polystyrene, aluminum oxide, supercritical fluid

The paper discusses the adsorption of palladium hexafluoroacetylacetonate (Pd(hfa)2) onto porous carriers (γ-Al2O3 and hypercrosslinked polystyrene) in supercritical CO2 to obtain supported palladium catalysts. The transition conditions of the Pd(hfa 2/CO2 system into the single-phase region have been studied. It is shown that due to the sufficiently high solubility of the palladium precursor in CO2, its deposition can be carried out at relatively low pressures in the system (- 8,5 MPa). The adsorption of Pd(hfa)2 on chosen carriers can be well characterized by the Langmuir equation. The system pressure increase under isothermal conditions negatively affects the amount of adsorbed precursor, due to the competitive COadsorption and the distribution shift in the system. The system temperature increase under isochoric conditions leads to an increase in the adsorption limit.

doi:10.34984/SCFTP.2023.19.2.003

2024, №2

pp. 44-58

Articles

Synthesis of pr-doped GeO2 aerogels by impregnation method

D.A. Khvoshchevskaya, V.O. Veselova, S.V. Golodukhina, S.Yu. Kottsov, A.G. Son, O.M. Gajtko.

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Key words: aerogel, germanium oxide, praseodymium, soakage, impregnation, luminescence

An easy-to-implement technique for obtaining REE-doped GeO2 aerogels is proposed. Optimal synthesis conditions have been determined to achieve a uniform distribution of the ion-dopant in the matrix. The effect of praseodymium on the luminescent characteristics of GeO2 aerogels when excited by radiation with wavelengths of 240, 255 and 390 nm has been established.

doi:10.34984/SCFTP.2023.19.2.004

2024, №2

pp. 59-81

Articles

Pair correlation function for equilibrium critical state of fluids on the mesoscopic space scale

Yu.A. Chaikina, А.S. Vetchinkin, М.G. Golubkov, А.А. Lundin, I.D. Rodionov, A.I. Shushin, S.Ya. Umanskii.

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Key words: critical phenomena, paired correlation function, scale transformations, scale invariance, optical diagnostics of the critical state of fluids

In this paper we have solved the «fluctuation theorem» on the mesoscopic length scale for the first time in a direct way. An analytical expression for the pair correlation function of the critical state of fluid was obtained, where the density variance is the parameter that could be easily defined by optical measurements. By comparison of our result with the Ornstein—Zernike pair correlation function we have got the Fisher index η= 0.25 to increase the convergence. It was shown that the obtained results provide a reliable theoretical basis for optical diagnostics of the critical state of fluids.

doi:10.34984/SCFTP.2023.19.2.005

2024, №2

pp. 82-94

Articles

Two-stage thermal and heterogeneous catalytic transformation of hydrolysis lignin in supercritical n-hexane

N.A. Bobrova, A.E. Koklin, T.V. Bogdan, N.V. Mashchenko, A.M. Korotaeva, S.E. Bogorodskiy, V.I. Bogdan.

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Key words: hydrolysis lignin, depolymerization, n-hexane, supercritical conditions, hydrogenation, Ru/C

Depolymerization of hydrolysis lignin in supercritical n-hexane medium was carried out in two stages: 1) lignin treatment in an autoclave at 250°C and 15 MPa; 2) hydrogenation of the solution obtained in the first stage at 250°C and 9 MPa on a Ru/C catalyst. The products of the first and second stages were analyzed by HPLC, GPC, gas chromatography, chromatography-mass spectrometry, and elemental analysis. At the first stage, the degree of depolymerization was 17 %, the mono- and oligomeric fragments of lignin that passed into solution as a result of depolymerization have an MMD from 65 Da to 270 kDa. Monomer composition of the solution: mono-, di-, tri- and tetraalkyl derivatives of benzene (2.8 wt. %), guaiacol and its alkyl derivatives (0.6 wt. %), including coniferyl alcohol (0.06 wt. %). At the second stage of transformation the following processes occur: 1) depolymerization of oligomers to monomers; 2) hydrogenation of monomeric phenols to derivatives of cyclohexane and its oxo derivatives; 3) formation of gas products, mainly methane (95 vol. %), as a result of hydrocracking of the solvent.

doi:10.34984/SCFTP.2023.19.2.006

2024, №3

pp. 4-12

Articles

Key words: supercritical fluid, solubility, prediction, machine learning

A review of researches devoted to the application of machine learning methods and neural network technologies in the prediction of solubility of various substances in supercritical (SC) fluids. Using a simple neural network of three layers a prototype of a solubility prediction system was developed based on the example of an existing data set on the solubility of aromatic hydrocarbons in SC carbon dioxide. Its efficiency has been shown and further directions of research in this field have been identified.

doi:10.34984/SCFTP.2024.19.3.001

2024, №3

pp. 13-29

Articles

Preparation magnetite-containing composite aerogels based on alginate-chitosan complex

N.A. Gorshkova, I.A. Palamarchuk, O.S. Brovko, A.A. Sloboda, A.D. Ivakhnov, A.V. Malkov, N.I. Bogdanovich, T.I. Lovdina.

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Key words: chitosan, alginate, magnetite, aerogel, supercritical fluid technologies.

Composite aerogels were obtained based on two-component sodium alginate—chitosan hydrogels with the inclusion of magnetite and subsequent drying in supercritical carbon dioxide. The optimal concentration of magnetite introduced into the sodium alginate— chitosan system and the mode of supercritical drying of composite hydrogels in the carbon dioxide were experimentally established, making it possible to obtain the aerogel with a maximally developed porous structure. Using the method of low-temperature nitrogen adsorption, it was shown that the resulting aerogels are characterized by a developed mesoporous structure with open cylindrical pores, the maximum specific surface is 300 m2/g. Experimental studies have shown that the developed composite magnetite-containing aerogels have high bactericidal activity against S. aureus, E. coli and B. subtilis, due to which they have great potential for creating various medical products based on them, including wound dressings, carriers active medicinal substances, hemostatic or sorption materials.

doi:10.34984/SCFTP.2024.19.3.002

2024, №3

pp. 30-46

Articles

Composites of graphitic carbon nitride with silica aerogel – recyclable immobilized photocatalysts for sulfides oxidation by oxygen in SC-CO2

E.A. Ivanova, M.N. Zharkov, V.G. Merkulov, V.I. Gladilina, I.V. Kuchurov, P.S. Artemova, E.O. Pentsak, S.G. Zlotin.

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Key words: aerogels, gC3N4, sulfides, photocatalysis, oxidation

Composites of gC3N4 particles immobilized in monolithic silica aerogel have been obtained and their physicochemical photocatalytic properties have been studied. Their manifold recyclability and higher, compared to the gC3N4 in its free form, photocatalytic activity in reactions of alkyl aryl sulfides oxidation by molecular oxygen in SC-CO2 medium have been shown. The results presented in this work can serve as a basis for the development of sustainable and efficient processes of organic compounds oxidation.

doi:10.34984/SCFTP.2024.19.3.003

2024, №3

pp. 47-65

Articles

Key words: polylactide, foaming, supercritical carbon dioxide, laser radiation, dynamic scattering, mobility of interphase boundaries

Multiple scattering of laser radiation on the structure of forming porous matrices results in spatiotemporal fluctuations of intensity in the scattered radiation field (dynamic speckle modulation). Using the effect of dynamic scattering of laser radiation in the volume of evolving foams, the process of formation of highly porous polylactide matrices during their synthesis by the supercritical (SC) fluid foaming method in a carbon dioxide medium is analyzed. The average lifetime of dynamic speckles, τlt, which are recorded using a high-speed CMOS camera, is considered as a parameter carrying information on the ensemble-averaged mobility of scattering centers (boundaries of developing pores). A phenomenological model has been developed that establishes the relationship between the current values of τlt, macroscopic parameters of the foam (volume and rate of its change) and the ensemble-averaged microscopic mobility of interphase boundaries (the first derivative of the average pore size over time). The experimental data interpretation using the developed model on the dynamics of polylactide foam expansion during rapid (0.03 MPa/s) and slow (0.006 MPa/s) pressure release of SC-CO2 in the reactor are presented. It is established that in the case of rapid pressure release, structural
rearrangements in the foam volume continue even after it reaches the maximum value of
the expansion factor. A qualitative interpretation of this feature is given based on the
concepts of thermodynamic nonequilibrium of porous matrices during their formation.

doi:10.34984/SCFTP.2024.19.3.004

2024, №3

pp. 66-78

Articles

Key words: mixed oxides, synthesis, water fluid, lanthanum, group IIA elements, aluminates, catalytic oxidation, oxidative coupling of methane

The formation of mixed oxides in La2O3/MO—Al2O3 systems (M is a group IIA element: Mg, Ca, Sr or Ba) during high-temperature treatment and treatment with water fluids (WF) has been studied. It has been shown that high-temperature treatment of the corresponding group IIA metal aluminate with supported lanthanum nitrate leads to the formation of LaAlO3 only in the case of the Mg-containing system. In other cases, there is no transformation of the initial aluminates, and lanthanum oxide is formed. When treating La/M—Al ternary systems with WF, the formation of LaAlO3 is observed in all cases. Also, in all samples, except for Ba-containing, phases of free metal oxides of group IIA elements appear. The increase in activity and selectivity in the OCM process in La/M—Al ternary oxide systems compared to double M—Al systems is associated with the presence of a separate La2O3 oxide phase.

doi:10.34984/SCFTP.2024.19.3.005

2024, №3

pp. 79-92

Articles

Key words: subcritical water, agro-industrial complex wastes, buckwheat husk, polyphenols, anti-acetylcholinesterase activity

The effect of the extraction method and conditions on polyphenol composition of buckwheat (Fagopyrum esculentum) husk extracts and their acetylcholinesterase (AChE) inhibition activity was studied. The extracts were obtained both by the traditional method of water-ethanol extraction and in a subcritical water (SBW) medium at 120—220 °C. A direct correlation was found between anticholinesterase activity and the content of polyphenols in the extracts. The highest activity in inhibiting AChE was demonstrated by the extract obtained in the SBW medium at 220 °C, which contains the maximum amounts of the sum of polyphenols and flavonoids. This indicates the decisive role of these compounds in AChE inhibition. The obtained data allow us to consider such extracts as inexpensive and renewable sources of polyphenolic compounds and flavonoids with P-vitamin and neuroprotective activity.

doi:10.34984/SCFTP.2024.19.3.006

2024, №3

pp. 93-106

Articles

Key words: carbon dioxide, N-isopropylacrilamide, solubility, solubility isotherms, phase equilibrium, Chrastil’s model.

Solubility isotherms of N-isopropylacrylamide (NIPAM), obtained via visual synthetic method at temperatures 304.8—353.0 K and pressures 0.1—40.0 MPa, are reported in the current paper. The maximal solubility of NIPAM within this range of parameters is determined as well. The crossover region in regards to the  mix = ƒ (x, mol. %) isotherms is located and the nature of the phenomenon is discussed further. Predictive ability of the Chrastil’s model is evaluated in relation to the NIPAM-CO2 system.

doi:10.34984/SCFTP.2024.19.3.007

2024, №4

pp. 3-24

Reviews

Key words: supercritical fluids, group composition, asphaltenes, supercritical fluid extraction, carbon dioxide, anti-solvent, fractionation

The review article examines information on modern methods of separating oils and oil residues in the analysis of group composition using supercritical fluids. The features of the influence of the composition and properties of individual group components of oil samples on further processing has been shown. Traditional methods of separating petroleum feedstock into group components has been briefly reviewed. The results of modern studies of extraction methods for separating oil samples using supercritical fluids has been shown. Information is presented on new methods for the extraction of asphaltenes and fractionation of heavy oils and oil residues using СО2.

doi:10.34984/SCFTP.2024.19.4.001