Вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на мінімізування випаровування вуглеводневих рідин
Highly efficient stable aerated hydrophilic compositions containing fluorotensides and ultralight microdisperse systems using gas-filled glass, aluminosilicate and polymer microspheres have been developed. Designing the compositions of PAS based on the surface activity of surfactants, their solubili...
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V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
2021
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Catalysis and petrochemistry| _version_ | 1872008960128581632 |
|---|---|
| author | Spas'ka, O.A. Chumak, V.L. Maksymyuk, M.R. Rudenko, V.M. Kosenko, O.I. Polunkin, E.V. Gaidai, O.O. |
| author_facet | Spas'ka, O.A. Chumak, V.L. Maksymyuk, M.R. Rudenko, V.M. Kosenko, O.I. Polunkin, E.V. Gaidai, O.O. |
| author_institution_txt_mv | [
{
"author": "O.A. Spas'ka",
"institution": "National Aviation University, Ukraine 03058, Kyiv, Lubomyr Husar Avenue, 1"
},
{
"author": "V.L. Chumak",
"institution": "National Aviation University, Ukraine 03058, Kyiv, Lubomyr Husar Avenue, 1"
},
{
"author": "M.R. Maksymyuk",
"institution": "National Aviation University, Ukraine 03058, Kyiv, Lubomyr Husar Avenue, 1"
},
{
"author": "V.M. Rudenko",
"institution": "National Aviation University, Ukraine 03058, Kyiv, Lubomyr Husar Avenue, 1"
},
{
"author": "O.I. Kosenko",
"institution": "National Aviation University, Ukraine 03058, Kyiv, Lubomyr Husar Avenue, 1"
},
{
"author": "E.V. Polunkin",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine, Ukraine 02160, Kyiv, Kharkivske Shosse, 150"
},
{
"author": "O.O. Gaidai",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine, Ukraine 02160, Kyiv, Kharkivske Shosse, 150"
}
] |
| author_sort | Spas'ka, O.A. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2021-12-10T12:38:08Z |
| description | Highly efficient stable aerated hydrophilic compositions containing fluorotensides and ultralight microdisperse systems using gas-filled glass, aluminosilicate and polymer microspheres have been developed. Designing the compositions of PAS based on the surface activity of surfactants, their solubility in water and the ability to bind water and the formation of hydrogen bonds between the components. The main condition for the stability of the coating when mixing the components - the chemical interaction between them and the formation of a system that does not dissolve in hydrocarbons and does not break down in terms of use. The best film-forming characteristics necessary for the operation of the coating (simultaneous reduction of surface tension and film formation) active substances (FPAR), the non-polar part of the molecules of which contains a fluorocarbon chain, so they are insoluble in hydrocarbons, well soluble in water and easily distributed on the surface of hydrocarbon liquids, creating a protective film. The choice of co-surfactants was based on the ability to stabilize hydrophilic films on the surface of hydrocarbons not only at favorable HLB, but also at the lowest, although higher than the critical concentration of micelle formation (CCM), concentrations for forming a mixed adsorption layer of increased strength. This surfactant was water-oil-soluble twin80, which will significantly increase the hydrophilic part and enhance the stability of the PAS and the stability of the aerated system. The introduction of glass microspheres into the components of the system has significantly enhanced its strength and stability. In the study of the stability and gas permeability of the developed surfactant systems, it was found that the insulating ability of the coating increases with increasing hydrophilic-lipophilic balance of the system and due to chemical interaction between the carboxyl group of fluorotenside and hydroxyl groups of surfactants. |
| doi_str_mv | 10.15407/kataliz2021.31.084 |
| first_indexed | 2026-03-12T15:49:48Z |
| format | Article |
| fulltext |
84 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Influence of physico-chemical parameters of surface-active systems
components for minimization of evaporation of hydrocarbon liquids
_____________________________________________________________________________________________________________
O.A. Spas`ka1, V.L.Chumak1, M.R.Maksymyuk1, V.M. Rudenko1, O.I. Kosenko1,
E.V. Polunkin2, O.O. Gaidai2
1 National Aviation University, Ukraine 03058, Kyiv, Lubomyr Husar Avenue, 1, spaskaolena@ukr.net
2 V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine, Ukraine
02160, Kyiv, Kharkivske Shosse, 150, polunkin@i.ua
Highly efficient stable aerated hydrophilic compositions containing fluorotensides and ultralight microdisperse
systems using gas-filled glass, aluminosilicate and polymer microspheres have been developed. Designing the
compositions of PAS based on the surface activity of surfactants, their solubility in water and the ability to bind water
and the formation of hydrogen bonds between the components. The main condition for the stability of the coating
when mixing the components - the chemical interaction between them and the formation of a system that does not
dissolve in hydrocarbons and does not break down in terms of use. The best film-forming characteristics necessary for
the operation of the coating (simultaneous reduction of surface tension and film formation) active substances (FPAR),
the non-polar part of the molecules of which contains a fluorocarbon chain, so they are insoluble in hydrocarbons,
well soluble in water and easily distributed on the surface of hydrocarbon liquids, creating a protective film. The
choice of co-surfactants was based on the ability to stabilize hydrophilic films on the surface of hydrocarbons not only
at favorable HLB, but also at the lowest, although higher than the critical concentration of micelle formation (CCM),
concentrations for forming a mixed adsorption layer of increased strength. This surfactant was water-oil-soluble twin-
80, which will significantly increase the hydrophilic part and enhance the stability of the PAS and the stability of the
aerated system. The introduction of glass microspheres into the components of the system has significantly enhanced
its strength and stability.
In the study of the stability and gas permeability of the developed surfactant systems, it was found that the
insulating ability of the coating increases with increasing hydrophilic-lipophilic balance of the system and due to
chemical interaction between the carboxyl group of fluorotenside and hydroxyl groups of surfactants.
Keywords: evaporation of hydrocarbon liquids, stability of surface-active system, hydrophilic-lipophilic
balance, glass microspheres
_________________________________________________________________________________________________
Introduction
During storage of the liquid fuels, a significant
part of them is lost (80% of all losses) because of
evaporation. For example, for the tank with a volume of
5000 m3, about the 4 t of gasoline are lost, during 1 year
these losses may increase up to 230 t. Improvement of
the fuel storage is one of the most important problems.
Its solution will allow not only to save the fuel
quantitative and qualitative composition, but also to
prevent complex of emergencies at tankfarms [1,2].
Petroleum products are known to be a
multicomponent mixture of hydrocarbon compounds
having different boiling points. The lightest of them are
automobile (boiling point - 35-40 oC) and aviation
gasoline (boiling point – above 40 oC). During storage,
the quality of gasoline deteriorates, mainly due to the
evaporation of light fractions of hydrocarbons C5-C7,
which are the most volatile [3]. This leads to an increase
of the boiling point and an increase of density due to the
weighting of the fractional composition of the fuel.
Although the problem of loss of liquid
hydrocarbon fuels during storage has been worked on
for a long time, it is still relevant, because of the low
research of the processes to prevent evaporation and to
prevent the occurrence of explosive concentrations of
hydrocarbon liquids [4], as well as the lack of effective
technological systems and tools to minimize them.
Solving the problem of preventing evaporation of liquid
hydrocarbon fuels by targeted production of surface-
active systems (SAS) with certain protective properties
is relevant in general scientific terms, and the creation of
technological aspects of their use is extremely important
in practice: environmental and economical.
The goal of the work. The aim of the work is to
develop an effective protective coating to prevent
evaporation of hydrocarbon liquids, to increase the
safety of their storage and protect the environment. To
detect the relationship between the structure and
insulating ability of surfactant molecules, to research of
UDC 544.1
https://doi.org/10.15407/kataliz2021.31.084
mailto:spaskaolena@ukr.net
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ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
stability and gas permeability, the insulating ability of
the developed surfactant systems when comparing the
evaporation of individual hydrocarbon liquids C5-C10,
model mixture and technical gasoline A-95 from the
open surface and when applied to the surface of the
ultralight surfactant system with the inclusion of glass
microspheres.
Materials and methods
Industrial unfinished and finished microspheres
with a size of 25 μm with a bulk density of 0.30 g / cm3
were used in the work.
Unfinished microspheres are white, thin-walled
spheres made of sodium borosilicate glass according to
TU 6-48-108-94 type MS group A1 with a density of
240 g / cm3 and a hydrostatic compressive strength of 8
MPa.
Finished microspheres are glass beads with a
mixture of gamma- and beta-aminoisopropyltriethoxy-
silane (product AGM-9; TU 6-02-724-77) type MS-A9
group A1 applied to their surface (0.3%) Fig.1.
Fig.1. Microphotography of the surface of the
hydrocarbon liquid partially covered with microspheres.
Surfactants (surfactants): nonionic surfactant
sorbitan monooleate polyethylene glycol, fluorinated
surfactant 2- (N-ethylperfluorooctansulfamide) acetic
acid, polymer-polyvinyl alcohol (PVA), stabilizer. The
experiment was carried out as follows: at the same time
studied the evaporation by analytical method, placed in a
thermostat of cylindrical tanks with a volume of 100 ml
at a temperature of 25 oC model samples of volatile
individual hydrocarbon liquids C5-C10 (gasoline
components) from an open surface of 20 cm2
microspheres on the same surface with a monolayer and
a layer that exceeded the surface area of hydrocarbons
twice or three times. The studies were performed under
identical conditions for 5 h, weighing the samples every
10 min. Under the same conditions, the evaporation of
hydrocarbon liquids during the application of an
ultralight surfactant system was investigated.
The study of the effectiveness of the developed
ultralight surfactant systems (USAS) to prevent
evaporation of the model mixture, simulating the
composition of gasoline, and gasoline A-95 was
performed on an experimental setup using the
chromatographic method of analysis. Hydrocarbons
invert microdispersions were prepared by gradually
adding an aerated hydrophilic solution of FPAR
(fluorotensides), tween-80, and PVA to a pre-prepared
solution of basic surfactant (emultal, oleodin,
phosphatidine) in a hydrocarbon solvent, followed by
stirring for 10 min.
To obtain emulsion-suspension systems, gas-filled
microspheres were introduced into the finished highly
structured inverse emulsion with constant stirring for 7-
10 min. According to previous studies, this time was
sufficient to establish the equilibrium adsorption of
surfactant molecules and obtain a stable emulsion-
suspension composition.
Research results: highly effective stable aerated
hydrophilic fluorotensin-containing compositions and
ultralight microdisperse systems using gas-filled glass,
aluminosilicate and polymer microspheres were created.
Discussion of results. When designing SAS
compositions, were used the surface activity of
surfactants, their solubility in water and the ability to
bind water and the formation of hydrogen bonds
between the components. The main condition for the
stability of the coating when mixing the components is
the chemical interaction between them and the formation
of a system that does not dissolve in hydrocarbons and
does not break down in use. Based on the above stated,
the priority was given to surfactants of the anionic type,
containing in the alkyl chain of 6-12 carbon atoms,
which are available at the market and have a high
surface activity. Among our surfactants tested, the best
film-forming characteristics required for the coating to
function (simultaneous reduction of surface tension and
film formation) showed fluorinated surfactants (FPAR),
the non-polar part of the molecules of which contains a
fluorocarbon chain, so they are insoluble in
carbohydrates, but are well soluble in water and are
easily distributed on the surface of hydrocarbon liquids,
creating a protective film. Perfluorocarboxylic and
perfluoroalkane-sulfonic acids containing 6-12 carbon
atoms in the fluorinated chain were used. The
hydrophobic chain of such compounds is immersed in
liquid hydrocarbons, and hydrophilic groups of four S-
N-C-C atoms with a functional carboxyl group are
concentrated on the interface with air. Air was pumped
through aqueous solutions to ensure buoyancy.
.
86 Каталіз та нафтохімія, 2021, № 31
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C8F14SO3H
RfSO2NH2
When applying such an aerated system based on
AFFF-3M foaming agent on the surface of gasoline, the
insulating capacity of the foam, as expected, increases,
but the integrity and stability of the surface structure
and, accordingly, protective properties are lost after a
short time [6]. Therefore, there was a need to stabilize it,
increasing the hydrophilic-lipophilic balance of the
system by connecting other molecules with a large
number of hydrophilic groups.
The choice of co-surfactants was based on the
ability to stabilize hydrophilic films on the surface of
hydrocarbons not only at favorable HLB, but also at the
lowest, although higher than the critical concentration of
micelle formation (CCM), concentrations for forming a
mixed adsorption-MES layer on the surface strength.
This surfactant was water-soluble twin-80 [8]. This
nonionic surfactant does not dissociate into ions, is
hydrophilic, oil-soluble and insoluble in hydrocarbons.
The molecular structure of the compound includes a
tetrahydrofuran ring with three hydrocarbon chains
containing a carbonyl group, 20 oxymethylene groups
and two hydroxyl groups. After studying the structure of
tween-80, it is assumed that when mixed with FPAR due
to the chemical interaction of tween-80 on hydroxyl
groups with carboxyl groups FPAR esters are formed,
which will significantly increase the hydrophilic part and
enhance the stability of SAS and the stability of the
aerated system.HLB = (4 + 15) / 2 = 9.5 Stability - 3
hours.
However, the stability of such a layer does not
meet the stated requirements. In fact, if the half-life of
the aerated system formed by fluortenside AFFF-3M
does not exceed 8 minutes, then in conjunction with
tween-80 a satisfactory protective layer of foam (at least
10 mm) is stable for more than 3 hours. However, these
results are insufficient for practical use.
It is established that the only way to ensure long-
term stability of aerated systems is the formation of
three-phase solid systems [6]. Typically, such systems
are obtained by introducing into the composite
composition of the surfactant polymeric structurant.
Combinations of surfactants with polymers are used for
many practical purposes, which provides stability and
the necessary rheological properties of the compositions
[8]. The properties of the solutions of the individual
components are important, but the performance of the
composite product largely depends on the interaction
between the components. That is, knowledge of
physicochemical properties of components and features
of interaction between them is essential not only for the
correct combination of the best properties of
components, but also for creation of composite systems
with fundamentally new properties, which is a
combination of science and art [7]. It was found that the
stretching of the surfactant polymer increases the
stability of the coating. When introducing a polymer into
the coating composition, it should be borne in mind that
the viscosity of polymer solutions is usually higher than
the viscosity of solutions of low molecular weight
compounds with the same concentrations. The swelling
process is a diffusion process caused by the gradient of
the chemical potential of the liquid.The cause of
swelling is that molecules that differ by many orders of
magnitude in size and mobility mix and interact. Low
molecular weight solvent molecules rapidly infiltrate the
polymer structure, pushing the chains apart and
increasing the volume. From this point of view, swelling
is a thermodynamic process with a unilateral equilibrium
shift, in which the solvation of its macromolecules
occurs (polar polymers swell in a polar solvent),
accompanied by heat release, ie ΔH < 0. At this stage,
the entropy of the system does not change or decreases
slightly due to the ordering of solvent molecules due to
solvation, ie ΔS < 0. If ΔH < TΔS, then G < 0 is an
spontaneous process. The amount of solvent absorbed at
this stage is 20-40% by weight of dry matter, and despite
the increase in the volume of the polymer sample, the
total volume of the system (polymer and solvent) at this
Каталіз та нафтохімія, 2021, № 31 87
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
stage decreases, i.e. there is a contraction and the
interaction of polymer with solvent – solvation, which
results in compaction of the system. In this case, the
spatial grid is created not by vanderwaals, but by
chemical or hydrogen bonds. For this reason, gellies are
not characterized by thixotropy and destruction of the
structure of gels due to mechanical impact, which in
most cases is irreversible. Gels formed by polymers
exhibit elastic and resilient properties due to the strength
and flexibility of the macromolecular network, as well as
the hardness of the oriented layers of solvent molecules.
For this reason, conventional gels are not capable of
plastic flow, while globular gels are able to flow. The
mechanical properties of gels are strongly influenced by
their concentration. Due to the compaction of gels, their
strength increases.
Given the described set of general properties of
polymers, after a careful search among high-molecular
water-soluble surfactants: natural – cherry gum, gelatin,
egg white, and synthetic - polyacrylamide, copolymers
of maleic anhydride and, we focused on polyvinyl
alcohol, which is synthesized exclusively by the method
of polymeranalogical transformations. The matrix
polymer is polyvinyl acetate, the ester groups of which
are subjected to hydrolysis.
X-ray films of PVA become insoluble even in
boiling water and can withstand heating up to 200 °C.
Elongated films, despite the presence of plasticizer, have
increased strength (tensile strength - 600 kgf / cm) and
high abrasion resistance. The gas permeability of PVA
films is 15-20 times (depending on the degree of
plasticization) is lower than the gas permeability of the
vulcanized natural rubber film and is a consequence of
the orientation of macromolecules due to numerous
hydrogen bonds between neighboring macromolecules.
The combination of a polymer matrix PVA with many
centers that can form hydrogen bonds, with an aerated
solution of SAS allowed to develop compositions of
stable three-phase systems that form on the surface of
hydrocarbons strong three-dimensional elastic systems
that provide gas-tight coatings and provide reliable
liquids (Fig. 2).
The formed complex forms on the surface of
hydrocarbons structured elastic films. The great practical
value of PVA in a peculiar combination of a number of
advantageous properties. Due to the high gas
impermeability of this thermoplastic microcrystalline
structure, its hydrophilicity, solubility in water and at the
same time insolubility in hydrocarbons, on the basis of
previously created SAS we were able to develop durable
coatings to protect hydrocarbon liquids from evaporation
systems in combination with surfactants are glass
microspheres [8].
The formed complex forms on the surface of
hydrocarbons structured elastic films. The great practical
value of PVA in a peculiar combination of a number of
advantageous properties. Due to the high gas
impermeability of this thermoplastic microcrystalline
structure, its hydrophilicity, solubility in water and at the
same time insolubility in hydrocarbons, on the basis of
previously created SAS we were able to develop durable
coatings to protect hydrocarbon liquids from evaporation
systems in combination with surfactants are glass
microspheres [8].
Fig. 2. Scheme of the coating formed by the interaction of 2- (N-ethylperfluorooctane sulfamide) acetic acid,
sorbitan monooleate, polyethylene glycol and polyvinyl alcohol.
88 Каталіз та нафтохімія, 2021, № 31
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Fig.3. IR spectrum of 2-(N-ethylperfluorooctansulfamide) acetate.
Fig.4. IR -spectrum of polyethylene glycol sorbitan monooleate.
The IR-spectrum of 2-(N-
ethylperfluorooctansulfamide) acetate is shown in Fig.3.
The hydrophobic part of this molecule includes one
fluoromethyl and 7 fluoromethylene groups. In the
spectrum they correspond to the absorption bands of
deformation oscillations CF2, CF3 groups in the range of
1168 cm-1, 1149 cm-1, respectively. The hydrophilic part
of the molecule consists of four S-N-C-C atoms with a
functional carboxyl group, which includes a carbonyl
group C = O with a corresponding absorption band of
1730 cm-1, and a hydroxyl group characterized by a wide
absorption band in the range of 3100-3700 cm-1.
To approximate the oscillation frequency of the
valence bond according to Hooke's law, the relative
contributions of the bond strength and atomic masses
must be considered. For example, a superficial
comparison of a CH group with an F-H group based on
atomic masses may lead to the conclusion that the F-H
valence frequency should occur at a lower frequency
than for the C-H bond. However, the increase in the
force constant from left to right in the first two periods
of the periodic table has a greater effect than the increase
in mass. Thus, the group F-H absorbs at a higher
frequency (4138 cm-1) than the C-H group (3040 cm-1),
because the energy of the chemical bond C-F
significantly exceeds the energy of the bond C-H. In
general, functional groups that have a strong dipole give
strong absorption in the IR-spectrum.
Figure 4 shows the IR-spectrum of tween-80,
which shows the oscillations of functional groups and
their bonds, in particular, the strong absorption band of
valence oscillations of the C=O bond at 1735 cm-1. This
band is very sensitive to changes in the physical state of
the compound. The highest value of frequencies νС = О is
observed for compounds in pairs, then for solutions of
carbonyl compounds in nonpolar or low-polar solvents
(CS2, ССl4) and, finally, even less value of frequencies
νС = О acquires in solutions of polar solvents (СНС13,
СНВг3). The lowest values of the frequencies of the
carbonyl group are observed in the solid state, where
intermolecular interactions play a significant role. If the
carbonyl group is involved in the formation of
intermolecular hydrogen bonds, the frequency νС = О
decreases to 1545 cm-1.
The intermediate part of the spectrum in the range
of 1300-900 cm-1, is usually referred to as the range of
«fingerprints». The absorption of the sample in this area
is often complex, with bands of oscillations in the
Каталіз та нафтохімія, 2021, № 31 89
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
interaction of oscillatory modes. This part of the
spectrum is extremely valuable in the study with
reference to other ranges [9].
Fig.5. IR spectrum of a mixture of 2- (N-ethylperfluorooctansulfamide) acetic acid and polyethylene glycol
sorbitan monooleate.
The assignment of a carbonyl group in the ester is
confirmed by the observation of a strong band in the
region of 1300-1100 cm-1, which indicates a CO-valence
oscillation.
The НO-valence oscillation νОН, one of the most
characteristic of the IR spectra, forms the most intense
band in the range of 3200-3600 cm-1. The position and
nature of the band also depend on the degree of
participation of the hydroxyl group in the hydrogen
bond. The hydrogen bond changes the force constant of
the bond -OH and, accordingly, leads to a decrease in
wave oscillations, which is traced in the spectrum after
the introduction into the SAS of a polymeric structurant
- polyvinyl alcohol. As can be seen from Fig.3.6, in a
pure liquid and in concentrated solutions, the hydroxyl
group participates in the intermolecular hydrogen
bond. It is characterized by a wide (3200-3600cm-1)
intense absorption maximum. Intramolecular bond is
possible in hydroxyl-containing compounds. In dilute
solutions, the formation of intermolecular hydrogen
bonds is almost impossible. In the IR-spectrum of such
solutions, the hydroxyl group is manifested by narrow
intensive band, but for the bound hydroxyl group this
band is located in the range of 3610-3620cm-1, whereas
for the HO-group forming an intramolecular bond, in the
range of much lower frequencies ≈ 3500cm-1.
The oscillation of unbound hydroxyl νOH in
alcohols has a frequency of 3600-3615cm-1, inherent in
the hydrogen bond. Thus, the vibrational spectra can not
only reliably prove the presence of a hydroxyl group, but
also to determine its participation in the hydrogen bond.
This allows you to solve a number of structural and
analytical problems. The valence vibrations of the
carbonyl group, regardless of which functional group it
belongs to, are found to have an intense maximum in the
range of 1650-1859 cm-1, in which other bands are
practically absent. These fluctuations are the most
characteristic and allow us to confidently state the
presence or absence of a carbonyl group in the
substance. For carboxylic acids, the value of νCO is in the
range of 1750-1770 cm-1. Due to the induction effect (-1)
decreases the bond length C=O, respectively, increases
its power constant and wave number. The conjugation
effect due to delocalization of π-electrons leads to a
decrease in the wave number νCO. For systems C=C and
C=O oscillations are in the range of wave numbers
1665-1685cm-1. It means, that the nature of the
corresponding functional group can be predicted from
the wave number of the carbonyl group.
The experimental data agree well with the results
of quantum chemical calculations of each SAS
component separately and with the attribution of
absorption bands of IR-spectrum to the corresponding
oscillations of groups of atoms in molecules using the
Hiperchem software package.
Conclusions
The stability and steadiness of the created systems
largely depends on the correct selection of components,
their concentrations and selected carrier. First of all, this
applies to surfactants, their chemical structure and
structure in solutions of different polarity and
scientifically sound compositional selection of the
composition, which is much more effective than
individual substances. Glass beads are used as a carrier,
which is chemically inert and mechanically strong, and
the system of which it is part, stable to hydrocarbon
liquids and completely impermeable to liquids and
gases, and has a low thermal conductivity, resistance to
cracking, satisfactory adhesion, low cost. The density of
90 Каталіз та нафтохімія, 2021, № 31
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the developed protective coating does not exceed the
density of the oil product, i.e. is lower than 0.6g/cm3.
This condition is mandatory for the application of a
floating coating on the surface of the petroleum product.
The composition of the aerated hydrophilic coating,
including polymer, nonionic surfactant, crosslinker and
water, maximizes the electrical attraction between mixed
surfactant micelles and polymer, without causing
deposition of the coating, and the inclusion of gas-filled
microspheres capable of providing excellent buoyancy
of ultralight technological systems and their mechanical
properties and also increasing the reliability of the
protective barrier against the diffusion of hydrocarbon
vapors during storage, high mechanical strength and fire
safety. Thus, knowledge of physicochemical properties
of components and features of interaction between them
is essential not only for the correct combination of the
best properties of components, but also for creation of
composite systems with essentially new properties. A
number of ultralight surfactant systems have been
developed that interact with the surface of microspheres
and prevent the evaporation of hydrocarbon liquids by
98-99.6%. both due to the chemical interaction of
monooleatsorbitan polyethylene glycol with 2-(N-
ethylper-fluorooctanesulfamide) acetate, and due to the
formation of multicenter hydrogen bonds of this system
with polyvinyl alcohol and the surface of the
microspheres.
Література
1. Енергетична стратегія України на період до
2035 року. Центр Разумкова. 2020. 67 с.
2. Письменна У., Трипольська Г. Елімінація
енергетичної бідності та її вплив на енергетичну
сталість. Вісник Одеського національного
університету. Економіка. 2020. Т. 25. Вип. 1(80). с.
25-32.
3. Ковальов І. В. Досвід створення стратегічних
запасів нафти і нафтопродуктів у державах – членах
ЄС. Формування ринкових відносин в Україні. 2009.
№ 6. с. 106-110.
4. Clean energy for all. Europeans. Режим доступу
- https:// ec.europa.eu/energy/en/topics/energy-strategy-
andenergy-union/clean-energy-all-europeans/
5. Kwon K. C. Pseudo-binary molecular diffusion
of vapors into air. Advances in Environmental Research
128. 2004. V. 8. pp. 667-678.
6. Fingas M. F. Modeling oil and petroleum
evaporation. Petroleum Science. 2013. Is. 3 Vol. 2. pp.
104-115.
7. Holmberg К. Surface-active substances and
polymers in aqueous solutions. М.: Бином, 2007. 530 с.
8. Larking D. M. Effective degradation polivinyl
alcohol by combined chemical and microbial processes.
Біотехнологія. 2012. Т. 5. № 5. c. 54-64.
9. Поп Г.С., Спаська О.А., Бодачівська Л.Ю.
Полегшені інвертні мікродисперсії для мінімізації
випаровування вуглеводневих рідин. Каталіз і
нафтохімія. 2011. №19. c. 95-100.
10. Спаська О.А., С.В. Іванов, Г.С. Поп, Л.Ю.
Бодачівська, Ю.В. Білокопитов. Спосіб запобігання
випаровуванню летких вуглеводневих рідин при їх
тривалому зберіганні. Патент №29641 Україна, МПК
В65D 90/22 № u 2007 08495. Заявл. 24.07.2007.
Надрук. 25.01.2008. 60 с.Бюл. № 2.
11. Spas’ka O.A. Ultralight surface-active systems for
preventing liquid hydrocarbons evaporation. Chemistry
and chemical technolodgy. 2016, № 1. pp. 63-66.
References
1. Enerhetychna stratehiya Ukrayiny na period do
2035 roku. Tsentr Razumkova, 2020. 67 s.
2. Pysʹmenna U., Trypolʹsʹka H. Eliminatsiya
enerhetychnoyi bidnosti ta yiyi vplyv na enerhetychnu
stalistʹ. Visnyk Odesʹkoho natsionalʹnoho universytetu.
Ekonomika. 2020. T. 25. Vyp. 1(80). S. 25-32.
3. Kovalʹov I. V. Dosvid stvorennya stratehichnykh
zapasiv nafty i naftoproduktiv u derzhavakh – chlenakh
YeS. Formuvannya rynkovykh vidnosyn v Ukrayini.
2009. № 6. S. 106-110.
4. Clean energy for all Europeans. URL:
https://ec.europa.eu/energy/en/topics/energy-strategy-
andenergy-union/clean-energy-all-europeans/
5. Kwon K.C., Ibrahim T.H., Park YoonKook and
Simmons C.M. Pseudo-binary molecular diffusion of
vapors into air. Advances in Environmental Research.
2004. V. 8. pp. 667-678. https://doi.org/10.1016/S1093-
0191(03)00039-X
6. Fingas M. F. Modeling oil and petroleum
evaporation. Journal of Petroleum Science Research
(JPSR). 2013. V. 2. pp. 104-115.
7. Holmberg K., Jonsson B., Kronberg B. and
Lindman B. Surfactants and Polymers in Aqueous
Solution. 2nd edition. John Wiley & Sons, Ltd. 2003. P.
547
8. Larking D. M., Mitik-Dineva N., Ivanova E. P.,
Lonergan G.T. and Crowford R. J. Effective degradation
of polyvinyl alcohol by combined chemical and
microbial processes. Biotekhnolohiya. 2012. T. 5. № 5.
S. 54-64.
9. Pop H.S., Spasʹka O.A., Bodachivsʹka L.YU.
Polehsheni invertni mikrodyspersiyi dlya minimizatsiyi
vyparovuvannya vuhlevodnevykh ridyn. Kataliz i
naftokhimiya. 2011. №19. S. 95-100.
10. Patent №29641 MPK B65D 90/22. Ivanov S.V.,
Spasʹka O.A., Bilokopytov Yu.V. Sposib zapobihannya
vyparovuvannyu letkykh vuhlevodnevykh ridyn pry yikh
tryvalomu zberihanni. Ukraina. 24.07.2007. Byul. № 2.
11. Spas’ka O.A. Ultralight surface-active systems
for preventing liquid hydrocarbons evaporation.
Chemistry and chemical technolodgy. 2016, № 1. pp.
63-66.
Надійшла до редакції 11.06.2021 р.
Каталіз та нафтохімія, 2021, № 31 91
ISSN 2707-5796. Kataliz ta naftohimia. 2021, 31
Вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на
мінімізування випаровування вуглеводневих рідин
O.О. Спаська1, В.Л. Чумак1, М.Р. Максимюк1, В.М. Руденко1, О.І. Косенко1,
Є.В. Полункін2, О.О. Гайдай2
1Національний авіаційний університет, Україна 03058, Київ, Проспект Любомира Гузара 1, spaskaolena@ukr.net
2 Інститут біоорганічної хімії та нафтохімії ім. В.П. Кухаря НАН України,Україна 02160, Київ, Харківське
шоссе 150, polunkin@i.ua
Були розроблені високоефективні стабільні аеровані гідрофільні композиції, що містять фтортензиди та
надлегкі мікродисперсні системи з використанням газонаповнених скляних, алюмосилікатних та полімерних
мікросфер. Розробка композицій поверхнево-активних систем грунтується на поверхневій активності ПАР, їх
розчинності у воді, здатності зв'язувати воду та утворення водневих зв'язків між компонентами. Основна
умова стійкості покриття при змішуванні компонентів - хімічна взаємодія між ними та утворення системи, яка
не розчиняється у вуглеводнях і не руйнується з точки зору використання. Найкращі плівкоутворюючі
характеристики, необхідні для функціонування покриття (одночасне зменшення поверхневого натягу та
утворення плівки) характерні для фторованих поверхнево-активних речовин (ФПАР), неполярна частина
молекул яких містить фторвуглецевий ланцюг, завдяки чому вони нерозчинні у вуглеводнях, добре розчинні у
воді і легко розподіляються по поверхні вуглеводневих рідин, створюючи захисну плівку. Вибір спів-ПАР
ґрунтувався на здатності стабілізувати гідрофільні плівки на поверхні вуглеводнів не тільки при сприятливому
гідрофільно-ліпофільному балансі, але і при найнижчих, хоча і вищих за критичну концентрацію
міцелоутворення (ККМ), концентраціях для утворення змішаних адсорбційного шару підвищеної міцності.
Цією поверхнево-активною речовиною був розчинний у воді і маслі твін-80, що значно збільшує гідрофільну
частину та підвищує стабільність ПАС та стабільність аеросистеми. Введення скляних мікросфер у
компоненти системи значно підвищило її міцність та стабільність.
При дослідженні стабільності та газопроникності розроблених систем поверхнево-активної речовини
було встановлено, що ізоляційна здатність покриття зростає зі збільшенням гідрофільно-ліпофільного балансу
системи та внаслідок хімічної взаємодії між карбоксильною групою фтортензиду та гідроксильними групами
ПАР.
Ключові слова: випаровування вуглеводневих рідин, стабільність поверхнево-активної системи,
гідрофільно-ліпофільний баланс, скляні сферичні мікрокульки
|
| id | oai:katalizorgua:article-18 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:49:48Z |
| publishDate | 2021 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/1d/695d3717d234f2d3d7a3865bb77d311d.pdf |
| spelling | oai:katalizorgua:article-182021-12-10T12:38:08Z Influence of physico-chemical parameters of surface-active systems components for minimization of evaporation of hydrocarbon liquids Вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на мінімізування випаровування вуглеводневих рідин Spas'ka, O.A. Chumak, V.L. Maksymyuk, M.R. Rudenko, V.M. Kosenko, O.I. Polunkin, E.V. Gaidai, O.O. evaporation of hydrocarbon liquids stability of surface-active system hydrophilic-lipophilic balance glass microspheres випаровування вуглеводневих рідин стабільність поверхнево-активної системи гідрофільно-ліпофільний баланс скляні сферичні мікрокульки Highly efficient stable aerated hydrophilic compositions containing fluorotensides and ultralight microdisperse systems using gas-filled glass, aluminosilicate and polymer microspheres have been developed. Designing the compositions of PAS based on the surface activity of surfactants, their solubility in water and the ability to bind water and the formation of hydrogen bonds between the components. The main condition for the stability of the coating when mixing the components - the chemical interaction between them and the formation of a system that does not dissolve in hydrocarbons and does not break down in terms of use. The best film-forming characteristics necessary for the operation of the coating (simultaneous reduction of surface tension and film formation) active substances (FPAR), the non-polar part of the molecules of which contains a fluorocarbon chain, so they are insoluble in hydrocarbons, well soluble in water and easily distributed on the surface of hydrocarbon liquids, creating a protective film. The choice of co-surfactants was based on the ability to stabilize hydrophilic films on the surface of hydrocarbons not only at favorable HLB, but also at the lowest, although higher than the critical concentration of micelle formation (CCM), concentrations for forming a mixed adsorption layer of increased strength. This surfactant was water-oil-soluble twin80, which will significantly increase the hydrophilic part and enhance the stability of the PAS and the stability of the aerated system. The introduction of glass microspheres into the components of the system has significantly enhanced its strength and stability. In the study of the stability and gas permeability of the developed surfactant systems, it was found that the insulating ability of the coating increases with increasing hydrophilic-lipophilic balance of the system and due to chemical interaction between the carboxyl group of fluorotenside and hydroxyl groups of surfactants. Були розроблені високоефективні стабільні аеровані гідрофільні композиції, що містять фтортензиди та надлегкі мікродисперсні системи з використанням газонаповнених скляних, алюмосилікатних та полімерних мікросфер. Розробка композицій поверхнево-активних систем грунтується на поверхневій активності ПАР, їх розчинності у воді, здатності зв'язувати воду та утворення водневих зв'язків між компонентами. Основна умова стійкості покриття при змішуванні компонентів - хімічна взаємодія між ними та утворення системи, яка не розчиняється у вуглеводнях і не руйнується з точки зору використання. Найкращі плівкоутворюючі характеристики, необхідні для функціонування покриття (одночасне зменшення поверхневого натягу та утворення плівки) характерні для фторованих поверхнево-активних речовин (ФПАР), неполярна частина молекул яких містить фторвуглецевий ланцюг, завдяки чому вони нерозчинні у вуглеводнях, добре розчинні у воді і легко розподіляються по поверхні вуглеводневих рідин, створюючи захисну плівку. Вибір спів-ПАР ґрунтувався на здатності стабілізувати гідрофільні плівки на поверхні вуглеводнів не тільки при сприятливому гідрофільно-ліпофільному балансі, але і при найнижчих, хоча і вищих за критичну концентрацію міцелоутворення (ККМ), концентраціях для утворення змішаних адсорбційного шару підвищеної міцності. Цією поверхнево-активною речовиною був розчинний у воді і маслі твін-80, що значно збільшує гідрофільну частину та підвищує стабільність ПАС та стабільність аеросистеми. Введення скляних мікросфер у компоненти системи значно підвищило її міцність та стабільність.При дослідженні стабільності та газопроникності розроблених систем поверхнево-активної речовини було встановлено, що ізоляційна здатність покриття зростає зі збільшенням гідрофільно-ліпофільного балансу системи та внаслідок хімічної взаємодії між карбоксильною групою фтортензиду та гідроксильними групами ПАР V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2021-11-07 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/18 10.15407/kataliz2021.31.084 Catalysis and petrochemistry; No. 31 (2021): Catalysis and petrochemistry; 84-91 Каталіз та нафтохімія; № 31 (2021): Каталіз та нафтохімія; 84-91 2707-5796 2412-4176 10.15407/kataliz2021.31 en https://kataliz.org.ua/index.php/journal/article/view/18/9 Copyright (c) 2021 Catalysis and petrochemistry |
| spellingShingle | випаровування вуглеводневих рідин стабільність поверхнево-активної системи гідрофільно-ліпофільний баланс скляні сферичні мікрокульки Spas'ka, O.A. Chumak, V.L. Maksymyuk, M.R. Rudenko, V.M. Kosenko, O.I. Polunkin, E.V. Gaidai, O.O. Вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на мінімізування випаровування вуглеводневих рідин |
| title | Вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на мінімізування випаровування вуглеводневих рідин |
| title_alt | Influence of physico-chemical parameters of surface-active systems components for minimization of evaporation of hydrocarbon liquids |
| title_full | Вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на мінімізування випаровування вуглеводневих рідин |
| title_fullStr | Вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на мінімізування випаровування вуглеводневих рідин |
| title_full_unstemmed | Вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на мінімізування випаровування вуглеводневих рідин |
| title_short | Вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на мінімізування випаровування вуглеводневих рідин |
| title_sort | вплив фізико-хімічних параметрів компонентів поверхнево-активних систем на мінімізування випаровування вуглеводневих рідин |
| topic | випаровування вуглеводневих рідин стабільність поверхнево-активної системи гідрофільно-ліпофільний баланс скляні сферичні мікрокульки |
| topic_facet | evaporation of hydrocarbon liquids stability of surface-active system hydrophilic-lipophilic balance glass microspheres випаровування вуглеводневих рідин стабільність поверхнево-активної системи гідрофільно-ліпофільний баланс скляні сферичні мікрокульки |
| url | https://kataliz.org.ua/index.php/journal/article/view/18 |
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