Use of synthesised ultradispersed substances in technological systems
Ultrafine calcium carbonate was synthesized by the exchange reaction and carbonation method with crystallite size of 7-44 nm. The size, polymorphic modification, and morphology of the crystallites were confirmed by X-ray diffraction analysis and scanning electron microscopy...
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| author | Bodachivska, Larysa Yu. |
| author_facet | Bodachivska, Larysa Yu. |
| author_institution_txt_mv | [
{
"author": "Larysa Yu. Bodachivska",
"institution": "V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of National Academy of Sciences of Ukraine 50 Kharkivske shausse, Kyiv, 02160, Ukraine"
}
] |
| author_sort | Bodachivska, Larysa Yu. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-02-23T14:10:37Z |
| description | Ultrafine calcium carbonate was synthesized by the exchange reaction and carbonation method with crystallite size of 7-44 nm. The size, polymorphic modification, and morphology of the crystallites were confirmed by X-ray diffraction analysis and scanning electron microscopy. The main attention is focused on development of methods for the synthesis of ultrafine calcium carbonate directly at the sites of well depressurization (microcracks) and the basics of technology for eliminating or preventing fluid manifestations in oil and gas wells. Depending on the intensity of gas occurrences, gas migration paths, the size of gas pipeline channels, the location of depressurization areas, thermobaric conditions, as well as the technical and operational condition of wells, it is proposed to perform sealing in one of two effective ways.
The first method involves sealing microscopic gas flow channels by transporting highly mobile low-viscosity solutions containing chemical reagents in a colloidal state to the depressurization sites, followed by creating conditions for their reaction and the formation of solid or gel-like sealants. To implement this method, one inverted microemulsion is prepared, the internal phase of which is an aqueous solution with the ionic reagent CaCl2, and the second – with the ionic reagent Na2CO3, which are injected together under stirring by the “jet to jet” method to form CaCO3 crystallites and are pressed by carbon dioxide into the depressurized areas. The second method of sealing microscopic gas flow channels involves transporting a low-viscosity solution containing one of the reagents in a colloidal state and the other reagent in a gaseous state to the depressurization sites, followed by creating conditions for their reaction and the formation of solid or gel-like sealants. The technical result of this method is achieved by the interaction of calcium hydroxide contained in the polar phase of the inverted micelle with carbon dioxide, which is pre-filled into the well. The permeability of CO2 through the membrane-like adsorption-solvent shell of biosynthetic surfactants around the calcium hydroxide facilitates the formation of CaCO3 and the pushing of ultrafine calcium carbonate by carbon dioxide into the gas-fluid channels. The well is treated using the “sliding tamping” method in the repression-depression mode. |
| doi_str_mv | 10.15407/kataliz2024.35.107 |
| first_indexed | 2026-03-12T15:49:41Z |
| format | Article |
| fulltext |
Каталіз та нафтохімія, 2024, №35 107
Catalysis and Petrochemistry, 2024, 35
UDC 665.372; 661.185; 661.842
https://doi.org/10.15407/kataliz2024.35.107
Use of synthesised ultradispersed substances in technological systems
Larysa Yu. Bodachivska
V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of National Academy of Sciences of Ukraine
1 Аcademiсa Kukhara Str., Kyiv, 02094, Ukraine, e-mail: bodach@ukr.net
Ultrafine calcium carbonate was synthesized by the exchange reaction and carbonation method with
crystallite size of 7-44 nm. The size, polymorphic modification, and morphology of the crystallites were
confirmed by X-ray diffraction analysis and scanning electron microscopy. The main attention is focused on
development of methods for the synthesis of ultrafine calcium carbonate directly at the sites of well
depressurization (microcracks) and the basics of technology for eliminating or preventing fluid manifestations in
oil and gas wells. Depending on the intensity of gas occurrences, gas migration paths, the size of gas pipeline
channels, the location of depressurization areas, thermobaric conditions, as well as the technical and operational
condition of wells, it is proposed to perform sealing in one of two effective ways.
The first method involves sealing microscopic gas flow channels by transporting highly mobile low-
viscosity solutions containing chemical reagents in a colloidal state to the depressurization sites, followed by
creating conditions for their reaction and the formation of solid or gel-like sealants. To implement this method,
one inverted microemulsion is prepared, the internal phase of which is an aqueous solution with the ionic reagent
CaCl2, and the second – with the ionic reagent Na2CO3, which are injected together under stirring by the “jet to
jet” method to form CaCO3 crystallites and are pressed by carbon dioxide into the depressurized areas. The second
method of sealing microscopic gas flow channels involves transporting a low-viscosity solution containing one of
the reagents in a colloidal state and the other reagent in a gaseous state to the depressurization sites, followed by
creating conditions for their reaction and the formation of solid or gel-like sealants. The technical result of this
method is achieved by the interaction of calcium hydroxide contained in the polar phase of the inverted micelle
with carbon dioxide, which is pre-filled into the well. The permeability of CO2 through the membrane-like
adsorption-solvent shell of biosynthetic surfactants around the calcium hydroxide facilitates the formation of
CaCO3 and the pushing of ultrafine calcium carbonate by carbon dioxide into the gas-fluid channels. The well is
treated using the “sliding tamping” method in the repression-depression mode.
Keywords: ultradispersed calcium carbonate, polymorphic modification, sealing, microcracks, oil and gas
wells
Introduction
Researchers are now paying increased attention to ultradispersed nanoscale substances and
compositions containing them. These are carbonate, metal and oxide nanoparticles, carbon nanotubes,
graphenes for drilling processes, hydrocarbon stimulation, elimination of inter-column and annulus gas
flow in wells, etc. [1-4].
The objects of nanotechnology research also include ultradispersed systems, such as aerosols,
micellar colloidal solutions, polymeric ashes, and gels [2]. Thermodynamically stable dispersed systems
are heterogeneous, and their micelles can be considered effective nanoreactors for the synthesis of
ultrafine substances with a narrow size distribution, morphology, and polymorphic modification [5-6].
An important advantage of using nanotechnologies is their high efficiency with a low content of
ultrafine substances in the technological system [5]. The effectiveness of nanotechnology in oil and gas
processes is associated with the known pattern of high rheological properties of nanodispersions
stabilized with ultrafine substances in a wide range of temperatures and pressures with increased thermal
conductivity, thermal stability, and reduced filtration losses [1, 2].
mailto:bodach@ukr.net
108 Каталіз та нафтохімія, 2024, №35
Catalysis and Petrochemistry, 2024, 35
The advantages of nanosystems in various technological processes are due to some basic
properties of nanoparticles [2, 7]:
1. Due to their small size (<1 µm), nanoparticles can easily penetrate porous media, which allows
for effective changes in the physical and chemical properties of the formation, as well as easily penetrate
the intercolumnar and annular space of wells, which will help restore well integrity.
2. Nanodispersions are characterized by high stability, as surface forces exceed gravity.
3. Due to the reduction of capillary forces, respectively, the interfacial tension between
hydrocarbons and the pore medium.
4. The size, polymorphic modification, and morphology of nanoparticles can be adjusted during
the synthesis process to provide the required properties.
5. The chemical properties of the nanoparticle surface can be easily modified to impart high
hydrophilicity or hydrophobicity, or other properties.
Several studies have shown that emulsion systems containing nanoparticles are more efficient
and stable in the process of hydrocarbon displacement compared to similar formulations without
nanoparticles [8-14].
It is important to synthesize dispersed calcium carbonate, which exists in crystalline
modifications such as calcite, aragonite, and vaterite, as well as in the form of an amorphous material.
The most stable of these is calcite, and the least stable is vaterite [5-6]. Equally important is the use of
calcium carbonate dispersions as technological systems in places of well depressurization (microcracks)
and their elimination or prevention of fluid manifestations in oil and gas wells.
One of the reasons for intercasing gas flows during well operation is poor quality cementing of
production strings, leaky packers and threaded connections, and high thermobaric loads on the production
string. The combination of these factors, combined with constant dynamic loads, leads to the formation of
microcracks in the cement stone itself and at the boundary with the production casing or rock, and the
radius of solid particles that could move into the depth of depressurized areas should not exceed
1-2 microns [8, 15-16]. The use of well-known water-based emulsion sealing systems is often
accompanied by their penetration into the perforated zone of a productive formation, which leads to
colmatation of the pore environment, or creates a threat of chemical contamination of drinking water
through penetration into aquifers [15]. At the same time, they have a limited sealing capacity, and high
filtration losses (4-26 cm3/30 min) because complications associated with the formation of hydrates in the
tubing. The use of high-viscosity sealant solutions, which are pumped under pressure into the defect zone,
also does not have a long-term effect. Polymeric materials do not penetrate deep into the depressurized
channels, as the films formed on the surface of the pipes are gradually destroyed by gas condensate,
condensation, and formation water, peeled off due to pipe corrosion, and brought to the surface. Even
temporarily plugging reservoir compositions based on chemically deposited calcium carbonate, which is
formed directly in the wellbore, does not provide sealing. This is because in aqueous solutions, ionic
reactions are very fast and the resulting insoluble salt molecules instantly form aggregates with a diameter
of more than 3 microns [1].
To eliminate these shortcomings, the authors of [16] proposed approaches based on the use of
organic-based solutions. According to the developed method, the sealing of gas flow channels is
achieved by pumping low-viscosity sealing systems into the annulus, the integrity and retention of which
are maintained by a gel plug with high cohesive strength, which is a suspension of a finely dispersed
water-swelling polymer in a gel solution of water-soluble polymers (polyacrylamide, carboxymethyl
Каталіз та нафтохімія, 2024, №35 109
Catalysis and Petrochemistry, 2024, 35
cellulose, hydrolyzed polyacrylonitrile, lignosulfonates) or a structured invert emulsion based on oil and
fat concentrates. The sealing compound is pumped in a liquid and hot state at a temperature of 80-90 °C,
in the form of a solution of saponified talcum pitch in diethylene glycol or its waste analog and
0.5-2.0 % of a nonionic surfactant (from the group AF9-(4÷6), ES-2, twin-80, ripox-6, savenol-NWP,
savenol-SWP, petrochem-1, phosphatidine) or cationic type (from the group of cationic fat, oleodin)
with subsequent purging with gas and injection of an aqueous solution of calcium or magnesium
chloride into the annulus until the sealing mass hardens.
For a selected group of wells (not disclosed to protect commercial secrets), a two-component
sealing was performed to eliminate intercasing and annulus gas flow in wells by the method of “sliding
tamping” with an 11-25 % water-alcohol solution of saponified talcum pitch in ethylene glycol,
diethylene glycol or in their mixture with a water content of 8-25 %, followed by hardening and film
formation of the sealant by crosslinking it with concentrated aqueous solutions of calcium chloride or
bischofite. A distinctive feature of well sealing was the introduction of a surfactant [17] into the
compositions, which is soluble in both water and hydrocarbons and improves the seepage of the water-
glycol solution.
The results of pilot tests of this method of restoring well integrity with solutions of saponified talus
pitch in diethylene glycol confirmed their effectiveness. In several wells, the company managed to
eliminate or reduce gas inflow from the interstitial space, reduce the interstitial pressure in the wells to a
safe level, and put the wells into operation.
The disadvantage of the above composition, as well as the previous ones, is still the unsatisfactory
penetration ability into depressurized migration channels. In addition, in most gas fields with reservoir
temperatures below 80 °C, pumping a relatively small (150-500 kg) viscous mass heated to 80-90 °C leads to
its rapid cooling and loss of fluidity, which not only fails to seal the gas pipeline channels of rock and cement
stone but also leads to complications due to thickening in the pipes and the bottom hole zone.
Further improvement of the quality of gas pipeline channels plugging and, as a result, an increase
in the workover period to eliminate the wellbore and intercasing gas flow in wells was achieved by
preliminary hydrophobization of the bottom hole formation zone and gas flow channels with a
hydrocarbon solution of cationic surfactants – oleodin, dorad [18]. The actual sealing is achieved by
pumping through perforations into the formation zone and gas flow channels of the sealing composition,
% wt., of phosphatide concentrate (65.00-95.00), cationic surfactant (0.1-1.5) and hydrocarbon solvent
(4.9-33.5).
The tests carried out with this method made it possible to eliminate gas leakage in all cases to
safe operating levels and to extend the overhaul period to 1-6 months. The short-term effect is likely to
be due to the surface sealing of the gas pipeline channels and the rapid destruction of the resulting hard
film. Before that, repeated treatments did not yield any results.
After a systematic analysis of the results of the good surveys, it was found that it is possible to
improve the quality of gas pipeline channel sealing by increasing the permeability and penetration depth
of sealing systems by using ultradispersed materials such as calcium carbonate, which are formed in
emulsion systems, directly in the depressurized gas pipeline sections.
Therefore, the aim of the work is to develop methods for the synthesis of ultrafine calcium
carbonate directly at the sites of well depressurization (microcracks) and the basics of technology for
eliminating or preventing fluid manifestations in oil and gas wells.
110 Каталіз та нафтохімія, 2024, №35
Catalysis and Petrochemistry, 2024, 35
Experimental
Materials
For the synthesis of biosurfactants, concentrated phosphatides (PC), a waste product from
sunflower oil refining was used. The physicochemical properties of this raw material are described in
[19-20]. Also used monoethanolamine (99.5 %), sodium carbonate, Na2CO3 (99.3), and calcium chloride,
CaCl2 (95.4).
General methods
The chemical modification of concentrated phosphatides by transamidation of fatty acids with
monoethanolamine in the presence of calcium hydroxide as a catalyst was carried out, with a molar ratio of
PC : monoethanolamine : Ca(OH)2 of 0.1 : 0.3 : 0.04. The synthesis and isolation of the product was performed
similarly to the method outlined in [19-20]. A complex mixture of biosynthetic surfactants (bioFAA) was
obtained, the active base of which is fatty acid alkanolamides and calcium glycerolphosphatides.
In terms of physical state, biosurfactants are oil-like substances of brown color with improved
solubility in organic non-polar solvents and a surface tension of 35-36 mN/m. The synthesized bioFAA
were used to create microemulsion compositions.
The synthesis of ultradispersed calcium carbonate was carried out using two methods.
The first method is microemulsion: intermicellular interaction of two microemulsions, one with
an aqueous solution of sodium carbonate, the other with an aqueous solution of calcium chloride. Then
they were mixed in an equimolar ratio and incubated for one day. A dispersion of calcium carbonate was
obtained. To isolate calcium carbonate crystallites, the dispersed system was centrifuged at 3000 rpm for
15 min. The calcium carbonate crystallites were washed several times with ethyl alcohol and distilled
water, and then dried. The dispersion medium is ethyl ester of higher fatty acids. The molar ratio of
surfactant:isopropyl alcohol : (aqueous solution of Na2CO3 or aqueous solution of CaCl2) is
0.02 : 0.4 : 0.1 (sample 1) and 0.04 : 0.4 : 0.1 (sample 2), respectively [4, 21].
The second method is based on the carbonation reaction: the interaction of calcium hydroxide,
Ca(OH)2, dissolved in the internal phase of the microemulsion at a concentration of 0.4 M, with carbon
dioxide, CO2, at a molar concentration of bioFAA (sample 3) of 0.04 M [22, 23].
The carbonation was carried out in a reactor equipped with a thermometer, a stirring device, a
CO2 supply tube and a reflux condenser. The microemulsion was loaded into the reactor, heated to 50 °C
and CO2 was supplied with intensive stirring. The CO2 flow rate was measured with a manometer. The
reactor is equipped with a hatch for loading reagents, which is hermetically sealed during the
carbonation stage. The reaction vessel during the carbonation stage is connected to the atmosphere via a
reflux condenser and a glycerine seal. The carbonation process was terminated when the absorption of
carbon dioxide by the reaction mass ceased and the pressure in the system increased. A dispersion of
calcium carbonate was obtained. To isolate calcium carbonate crystallites, the dispersed system was
centrifuged at 3000 rpm for 15 min. The calcium carbonate crystallites were washed several times with
ethyl alcohol and distilled water, and then dried.
Analytical methods
The phase identification of the products was examined under X-ray diffraction (XRD) using the
MiniFlex 300/600 diffractometer (Rigaku, Japan). The diffraction patterns were recorded using Cu-Kα
radiation (λ = 0.15418 nm), the operating voltage of 40 kV and a current of 15 mA. XRD pattern of
samples was obtained in the 2θ range between 2o and 100o with a step of 0.02o. The scanning electron
microscopy (SEM) images were taken using Zeiss Evo-10 (Carl Zeiss Microscopy, USA) microscope
Каталіз та нафтохімія, 2024, №35 111
Catalysis and Petrochemistry, 2024, 35
working at 20.0 kV. The IR spectra of products were recorded on the surface of the diamond prism of the
IR-spectrometer with Fourier transform Shimadzu IRAffinity-1Sn (Japan) with ATR-console
Speacac GS 10801-B.
Results and Discussion
X-ray diffraction phase analysis
Figures 1 a, 2 a, and 3 a show XRD patterns of the synthesized samples (1, 2, 3) of calcium
carbonate crystallites. It can be seen that with an increase in the concentration of bioFAA, the polymorphic
modification of CaCO3 crystallites changes with size from 7-15 to 32 nm for vaterite (Fig. 1 a, method 1),
15-44 nm for calcite (Fig. 2 a, method 1) and 7-39 nm for calcite (Fig. 3 a, method 2).
Scanning electron microscopy
Scanning electron micrographs Figures 1 b, 2 b, 3 b and in diminished view − Figures 1 c, 2 c,
3 c illustrate dispersed calcium carbonate in ellipsoidal, cubic, and spherical shapes.
The study of the properties of nanoparticles is one of the most important areas of physical
chemistry, the development of which is associated with the development of simple and affordable
synthesis methods that allow for the production of objects of a certain shape and a given size. The use of
microemulsions with an internal aqueous phase in which the starting reagents are dissolved makes it
possible to produce new substances and materials with dimensions down to 100 nm. Due to the
nanoscale, the starting materials are actively involved in Brownian motion, during which they
continuously collide, coalesce, and break up again. This makes it possible to carry out a variety of
chemical reactions between substances contained in the polar phase and forming insoluble ultrafine
substances in it, such as CaCO3.
The size of CaCO3 crystallites decreases after the addition of surfactant salts to aqueous solutions
as emulsifiers-stabilizers. bioFAA, adsorbed on the surface of crystallites, facilitates their dispersion and
simultaneously prevents their growth. The smallest size is achieved when a saturated monolayer of
bioFAA molecules forms around the particles. An important tool in controlling the modifications and
size of solid nanoparticles is the change in surfactant concentrations, the nature of bioFAA and co-
bioFAA, the ratio of water/surfactant concentrations, the type and concentration of reagents, the
properties of the aqueous and hydrocarbon phases, etc.
Using our own developments and information from the literature, we propose to develop
dispersions of calcium carbonate that can be used as technological systems in places of depressurization
and elimination of intercasing gas manifestations in oil and gas wells [1, 8, 19].
20 40 60 80 100
In
te
n
s
it
y
(
c
p
s
)
2-theta (deg)
V
V - Vaterite
V
V
V
V V
V
V V
a b с
Fig. 1. XRD pattern (a) and SEM image (b), diminished (c) of CaCO3 crystallites at a surfactant concentration of
0.02 M (method 1)
112 Каталіз та нафтохімія, 2024, №35
Catalysis and Petrochemistry, 2024, 35
Depending on the intensity of gas occurrences, gas migration paths, and the size of gas pipeline
channels, as well as the location of depressurized areas, thermobaric conditions, and the condition of the
wells (technical, operational, etc.), it is proposed to perform sealing in the following ways:
1. Transportation of highly mobile, low-viscosity solutions containing chemical reagents in a
colloidal state to depressurization sites, followed by the creation of conditions for their reaction and
formation of solid or gel-like sealants.
2. Transportation of a low-viscosity solution containing one of the reagents in a colloidal state
and the second reagent in a gaseous state to the depressurization sites, followed by creation of conditions
for their reaction and formation of solid or gel-like sealants.
0 20 40 60 80 100
In
te
n
s
it
y
(
c
p
s
)
2-theta (deg)
C - calcite
C
C
C
C
C
C
C C C
a b с
Fig. 2. XRD pattern (a) and SEM image (b), diminished (c) of CaCO3 crystallites at a surfactant concentration of
0.04 M (method 1)
20 40 60 80 100
In
te
n
s
it
y
(
c
p
s
)
2-theta (deg)
С - calcite
C
C
C
C
C
C
C
C
C C
C CC
a b с
Fig. 3. XRD pattern (a) and SEM image (b), diminished (c) of CaCO3 crystallites at a surfactant concentration of
0.04 M (method 2)
To implement the first method, one inverted microemulsion is prepared, the internal phase of
which is an aqueous solution with the ionic reagent CaCl2, and the second with the ionic reagent Na2CO3
(Method 1), which are injected together under stirring by the “jet to jet” method to form CaCO3
crystallites and are forced by carbon dioxide into depressurized areas [4, 8, 24]. The size of CaCO3
crystallites is 7-44 nm.
The adsorption-solvent layer of the bioFAA performs a dual function. On the one hand, it
prevents the instantaneous interaction of ionic reagents, and on the other hand, it prevents the growth of
crystallites and allows controlling these processes in the desired direction at the stage of reagent
transport and, in fact, during well-sealing.
At a constant ratio of the aqueous phase to the hydrocarbon phase, the properties of the emulsion
systems change viscosity – from 0.15 to 0.44 Pa·s; density, kg/m3 – 950-1070; resistance to phase
Каталіз та нафтохімія, 2024, №35 113
Catalysis and Petrochemistry, 2024, 35
separation in time from 4 days to 12 months; electrical stability – 125-340 V; thermal stability at 80 °C –
more than 9 days. The hydrocarbon phase is ethyl esters of higher fatty acids of oils. Due to the use of
raw materials of plant origin in biosurfactants and dispersed systems, the environmental indicator,
biodegradability, is 83-87 %.
To implement the second method of sealing microscopic gas flow channels, the technical result is
achieved by the interaction of calcium hydroxide contained in the polar phase of the inverted micelle
with carbon dioxide, which is pre-filled in the well (Method 2). The permeability of CO2 through the
membrane-like adsorption-solvent shell of biosynthetic surfactants around the calcium hydroxide
facilitates the formation of CaCO3 and the pushing of ultrafine calcium carbonate by carbon dioxide into
the gas-fluid channels. The well is treated using the “sliding tamping” method in the repression-
depression mode [4, 22-23]. Subsequently, an increase in the CO2 concentration leads to emulsion
degassing, and an increase in the rate of formation and growth of CaCO3 crystallites with the
corresponding sealing of the intercasing and annulus spaces.
The high CO2 concentration and prevention of natural gas emissions into the atmosphere are
achieved by pre-filling the well with a 2-fold volume of carbon dioxide and subsequent tamping of gas
pipeline channels with an inverted microemulsion under carbon dioxide pressure not exceeding the
production string pressure. An important feature of the process is a gradual increase in CO2 with a
simultaneous decrease in each repression-depression cycle of the microemulsion volume by 5-10 % and
a holding time of 10-15 min to form a highly dispersed sealing emulsion-suspension system in the gas
flow channels [8, 16-18].
The developed dispersed calcium carbonate systems can be used to develop high-temperature
complex lubricants with improved tribological properties and increased oxidation stability.
Conclusions
Dispersed calcium carbonate systems with CaCO3 crystallite size of 7-44 nm have been developed
for use in well depressurization sites and the elimination or prevention of fluid manifestations in oil and
gas wells. Depending on the intensity of gas occurrences, gas migration paths, the size of gas pipeline
channels, the location of depressurization areas, thermobaric conditions, as well as the technical and
operational condition of wells, it is proposed to perform sealing in one of two effective ways. The first
method of sealing microscopic gas flow channels involves transporting highly mobile low-viscosity
solutions containing chemical reagents in a colloidal state to the depressurization sites, followed by
creating conditions for their reaction and the formation of solid or gel-like sealants. The second method of
sealing microscopic gas flow channels involves transporting a low-viscosity solution containing one of the
reagents in a colloidal state and the second reagent in a gaseous state to the depressurization sites, followed
by creating conditions for their reaction and the formation of solid or gel-like sealants.
References
1. Bodachivska L.Yu., Verba A.Yu., Safronov O.I., Davitadze D.Z., Papeikin O.O., Venger I.O. Surfactants based
on lipoid biomass and their use in technological systems for gas and crude oil production. Catalysis and
Petrochemistry, 2019, 28, 1–19.
2. Shamilov V.М. Prospects for application of carbon nanomaterials in oil production. SOCAR Proceedings, 2020,
22(3), 90–107.
3. Agista M., Guo K., Yu Z. A state-of-the-art review of nanoparticles application in petroleum with a focus on
enhanced oil recovery. Appl. Sci., 2018, 8(871), 1–29.
114 Каталіз та нафтохімія, 2024, №35
Catalysis and Petrochemistry, 2024, 35
4. Niu Y., Liu J., Aymonier C., Fermani S., Kralj D., Falini G., Zhou C. Calcium carbonate: controlled synthesis,
surface functionalization, and nanostructured materials. Chem. Soc. Rev, 2022, 51, 7883–7943.
5. Ghiasi M., Abdollahy M., Khalesi M.R., Ghiasi E. Control of the morphology, specific surface area
andagglomeration of precipitated calcium carbonate crystals through a multiphase carbonation process.
CrystEngComm, 2020, 22, 1970–1984.
6. Yu W., Xie H. A review on nanofluids: preparation, stability mechanisms, and applications. J. Nanomater., 2012,
1, 1–17.
7. Serrano E., Rus G., García-Martínez J. Nanotechnology for sustainable energy. Renewable Sustainable Energy
Rev., 2009, 13(9), 2373–2384.
8. Pop G.S. New insights into the carbonation process in microemulsions. Catalysis and Petrochemistry, 2012, 20,
35–37.
9. Kazemzadeh Y., Shojaei S., Riazi M., Sharifi M. Review on application of nanoparticles for EOR purposes; a
critical of the opportunities and challenges. Chin. J. Chem. Eng., 2018, 27(2), 237–246.
10. Gbadamosi A. O., Junin R., Manan M. A., Yekeen N., Agi A., Oseh J.O. Recent advances and prospects in
polymeric nanofluids application for enhanced oil recovery. J. Ind. Eng. Chem., 2018, 66, 1–19.
11. Giraldo, J., Benjumea, P., Lopera, S., Cortés F.B., Ruiz M.A. Wettability alteration of sandstone cores by alumina-
based nanofluids. Energy Fuels, 2013, 27(7), 3659–3665.
12. Hammond P.S., Unsal E. Spontaneous imbibition of surfactant solution into an oil-wet capillary: wettability
restoration by surfactant-contaminant complexation. Langmuir, 2011, 27(8), 4412–4429.
13. Cao N., Mohammed A., Babadagli T. Wettability alteration of heavy-oil/bitumen containing carbonates using
solvents, high pH solution and nano/ionic liquids. OTC-26068-MS. In Offshore Technology Conference. Society of
Petroleum Engineers, 2015, 1–18.
14. Yu J., An C., Mo D, Liu N., Lee R. Study of adsorption and transportation behavior of nanoparticles in three
different porous media. In SPE Improved Oil Recovery Symposium. Society of Petroleum Engineers, 2012, 1–13.
15. Pop G.S., Vecheric R.L., Haeckiy Yu.B., Bodachivska L.Yu. Elimination of man-made gas leaks in the course of
operation of natural gas fields and underground storage facilities. IFNTUOG, 2004, 2(8), 173–175.
16. Patent 88740 Ukraine. Е21В33/138. Pop G.S., Bodachivska L.Yu., Коstiv V.V., Gebura М.D., Shabo М.G.
A method for eliminating inter-column and bottom hole gas flow in wells. 2009.
17. Patent 89577 Ukraine. Е21В33/138, С09 К8/50. Pop G.S., Bodachivska L.Yu., Shabo М.G. A method for
eliminating inter-column and bottom hole gas flow in wells. 2010.
18. Patent 65646 Ukraine. Е21В 33/138, Е21В 43/32. Pop G.S., Bodachivska L.Yu., Govdun V.V., Perepichay V.О.
A method for eliminating inter-column and bottom hole gas flow in wells. 2011.
19. Bodachivska L.Yu. Biodegradable surfactants from side streams of the vegetable oils production in technical
systems. Issues of Chemistry and Chemical Technology, 2022, 6, 3–11.
20. Bodachivska L.Yu. Sidestreams from the vegetable oilproduction as feedstock for surfactantsand treir derivative
technical systems. Catalysis and Petrochemistry, 2021, 31, 55–61.
21. Kumar A.R., Hota G., Mehra A. Modeling of nanoparticles formation by mixing of two reactive microemulsions.
AIChE, 2004, 50, 1556–1560.
22. Ghiasi M., Abdollahy M., Khalesi M.R., Ghiasi E. Control of the morphology, specific surface area and
agglomeration of precipitated calcium carbonate crystals through a multiphase carbonation process.
CrystEngComm, 2020, 22, 1970–1984.
23. Bayoumi R.A., Ahmed T.S., Soliman A., Ismail I.M. Nanocalcium carbonate production utilizingsolvay-process
industrial waste water and carbondioxide. Key Eng. Mater., 2019, 821, 350–358.
24. Shen Y., Hao S., Suonan A., Liu Y., Li H., Ma W., Zhao L., Zhang Y. Controllable Synthesis of Nano-Micro
Calcium Carbonate Mediated by Additive Engineering. Crystals, 2023, 13(10), 1432–1443.
Надійшда до редакції 25.04.2024
Каталіз та нафтохімія, 2024, №35 115
Catalysis and Petrochemistry, 2024, 35
Bикористання синтезованих ультрадисперсних речовин в технологічних системах
Лариса Ю. Бодачівська
Інститут біоорганічної хімії та нафтохімії ім.В.П. Кухаря Національної академії наук України
вул. Академіка Кухаря, 1, Київ, 02094, Україна, e-mail: bodach@ukr.net
Синтезовано ультрадисперсний карбонат кальцію реакцією обміну та методом карбонатації з
розміром кристалітів 7-44 нм. Розмір останніх, поліморфну модифікацію та морфологію підтверджено
рентгенофазовим аналізом та скануючою електронною мікроскопією. Основну увагу сфокусовано на
розробленні способів синтезу ультрадисперсного карбонату кальцію безпосереднього в місцях
розгерметизації свердловин (утворених мікротріщин) та основи технології ліквідації чи попередження
ними флюїдопроявів в нафтогазових свердловинах. Залежно від інтенсивності газопроявів, шляхів міграції
газу, величини газопровідних каналів, положення розгерметизувальних ділянок, термобаричних умов, а
також технічного та експлуатаційного стану свердловин, пропонується проводити герметизацію одним із
двох ефективних способів. За першим способом герметизації мікроскопічних газоплинних каналів
здійснюється шляхом транспортування в місця розгерметизації високорухливих малов’язких розчинів, що
містять хімічні реагенти в колоїдному стані, з подальшим створенням умов для їх реагування та утворення
твердих або гелеподібних герметиків. Для реалізації даного способу готують одну інвертну
мікроемульсію, внутрішня фаза якої є водний розчин з іонним реагентом CaCl2, другу − з іонним
реагентом Na2CO3, які разом закачують при перемішуванні методом «струмина в струмину» з утворенням
кристалітів CaCO3 і протискуються вуглекислим газом в розгерметизовані ділянки. За другим способом
герметизації мікроскопічних газоплинних каналів відбувається транспортування в місця розгерметизації
малов’язкого розчину, що містить один з реагентів в колоїдному стані, другий реагент в газоподібному
стані, з подальшим створенням умов для їх реагування та утворення твердих або гелеподібних герметиків.
Технічний результат даного способу досягається взаємодією гідроксиду кальцію, що містяться у полярній
фазі інвертної міцели, з вуглекислим газом, яким попередньо заповнюють свердловину. Проникність CO2
через мембраноподібну адсорбційно-сольватну оболонку біосинтетичних поверхнево-активних речовин
навколо гідроксиду кальцію сприяє процесу утворення CaCO3 і протискування ультрадисперсного
карбонату кальцію вуглекислим газом в газоплинні канали. Обробка свердловини проводять методом
«ковзаючого тампонування» в режимі репресія-депресія.
Ключові слова: ультрадисперсний карбонат кальцію, поліморфна модифікація, герметизація,
мікротріщини, нафтогазові свердловини
mailto:bodach@ukr.net
|
| id | oai:katalizorgua:article-115 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:49:41Z |
| publishDate | 2024 |
| 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/0f/e6efd55ed5fd556ee8c26bed906edd0f.pdf |
| spelling | oai:katalizorgua:article-1152026-02-23T14:10:37Z Use of synthesised ultradispersed substances in technological systems Use of synthesised ultradispersed substances in technological systems Bodachivska, Larysa Yu. ultradispersed calcium carbonate, polymorphic modification, sealing, microcracks, oil and gas wells ультрадисперсний карбонат кальцію, поліморфна модифікація, герметизація, мікротріщини, нафтогазові свердловини Ultrafine calcium carbonate was synthesized by the exchange reaction and carbonation method with crystallite size of 7-44&nbsp;nm. The size, polymorphic modification, and morphology of the crystallites&nbsp;were confirmed by X-ray diffraction analysis and scanning electron microscopy.&nbsp;The main attention is focused on development of methods for the synthesis of ultrafine calcium carbonate directly at the sites of well depressurization (microcracks)&nbsp;and the basics of technology for eliminating or preventing fluid manifestations in oil and gas wells. Depending on the intensity of gas occurrences, gas migration paths, the size of gas pipeline channels, the location of depressurization areas, thermobaric conditions, as well as the technical and operational condition of wells, it is proposed to perform sealing in one of two effective ways. The first method involves sealing microscopic gas flow channels by transporting highly mobile low-viscosity solutions containing chemical reagents in a colloidal state to the depressurization sites, followed by creating conditions for their reaction and the formation of solid or gel-like sealants. To implement this method, one inverted microemulsion is prepared, the internal phase of which is an aqueous solution with the ionic reagent CaCl2, and the second –&nbsp;with the ionic reagent Na2CO3, which are injected together under stirring by the “jet to jet”&nbsp;method to form CaCO3&nbsp;crystallites and are pressed by carbon dioxide into the depressurized areas. The second method of sealing microscopic gas flow channels involves transporting a low-viscosity solution containing one of the reagents in a colloidal state and the other reagent in a gaseous state to the depressurization sites, followed by creating conditions for their reaction and the formation of solid or gel-like sealants. The technical result of this method is achieved by the interaction of calcium hydroxide contained in the polar phase of the inverted micelle with carbon dioxide, which is pre-filled into the well. The permeability of CO2&nbsp;through the membrane-like adsorption-solvent shell of biosynthetic surfactants around the calcium hydroxide facilitates the formation of CaCO3&nbsp;and the pushing of ultrafine calcium carbonate by carbon dioxide into the gas-fluid channels. The well is treated using the “sliding tamping”&nbsp;method in the repression-depression mode. Синтезовано ультрадисперсний карбонат кальцію реакцією обміну та методом карбонатації з розміром кристалітів 7-44&nbsp;нм. Розмір останніх,&nbsp;поліморфну модифікацію та морфологію підтверджено&nbsp;рентгенофазовим аналізом та скануючою електронною мікроскопією.&nbsp;Основну увагу сфокусовано на розробленні способів синтезу ультрадисперсного карбонату кальцію безпосереднього в місцях розгерметизації свердловин (утворених мікротріщин) та основи технології ліквідації чи попередження ними флюїдопроявів в нафтогазових свердловинах. Залежно від інтенсивності газопроявів, шляхів міграції газу, величини газопровідних каналів, положення розгерметизувальних ділянок, термобаричних умов, а також технічного та експлуатаційного стану свердловин, пропонується проводити герметизацію одним із двох ефективних способів. За першим способом герметизації мікроскопічних газоплинних каналів здійснюється шляхом транспортування в місця розгерметизації високорухливих малов’язких розчинів, що містять хімічні реагенти в колоїдному стані, з подальшим створенням умов для їх реагування та утворення твердих або гелеподібних герметиків. Для реалізації даного способу готують одну інвертну мікроемульсію, внутрішня фаза якої є водний розчин з іонним реагентом CaCl2, другу − з іонним реагентом Na2CO3, які разом закачують при перемішуванні методом «струмина в струмину» з утворенням кристалітів CaCO3&nbsp;і протискуються вуглекислим газом в розгерметизовані ділянки. За другим способом герметизації мікроскопічних газоплинних каналів відбувається транспортування в місця розгерметизації малов’язкого розчину, що містить один з реагентів в колоїдному стані, другий реагент в газоподібному стані, з подальшим створенням умов для їх реагування та утворення твердих або гелеподібних герметиків. Технічний результат даного способу досягається взаємодією гідроксиду кальцію, що містяться у полярній фазі інвертної міцели, з вуглекислим газом, яким попередньо заповнюють свердловину. Проникність CO2 через мембраноподібну адсорбційно-сольватну оболонку біосинтетичних поверхнево-активних речовин навколо гідроксиду кальцію сприяє процесу утворення CaCO3 і протискування ультрадисперсного карбонату кальцію вуглекислим газом в газоплинні канали. Обробка свердловини проводять методом «ковзаючого тампонування» в режимі репресія-депресія. V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2024-12-10 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/115 10.15407/kataliz2024.35.107 Catalysis and petrochemistry; No. 35 (2024): Catalysis and petrochemistry; 107-115 Каталіз та нафтохімія; № 35 (2024): Каталіз та нафтохімія; 107-115 2707-5796 2412-4176 10.15407/kataliz2024.35 en https://kataliz.org.ua/index.php/journal/article/view/115/105 Copyright (c) 2024 Catalysis and petrochemistry |
| spellingShingle | ультрадисперсний карбонат кальцію поліморфна модифікація герметизація мікротріщини нафтогазові свердловини Bodachivska, Larysa Yu. Use of synthesised ultradispersed substances in technological systems |
| title | Use of synthesised ultradispersed substances in technological systems |
| title_alt | Use of synthesised ultradispersed substances in technological systems |
| title_full | Use of synthesised ultradispersed substances in technological systems |
| title_fullStr | Use of synthesised ultradispersed substances in technological systems |
| title_full_unstemmed | Use of synthesised ultradispersed substances in technological systems |
| title_short | Use of synthesised ultradispersed substances in technological systems |
| title_sort | use of synthesised ultradispersed substances in technological systems |
| topic | ультрадисперсний карбонат кальцію поліморфна модифікація герметизація мікротріщини нафтогазові свердловини |
| topic_facet | ultradispersed calcium carbonate polymorphic modification sealing microcracks oil and gas wells ультрадисперсний карбонат кальцію поліморфна модифікація герметизація мікротріщини нафтогазові свердловини |
| url | https://kataliz.org.ua/index.php/journal/article/view/115 |
| work_keys_str_mv | AT bodachivskalarysayu useofsynthesisedultradispersedsubstancesintechnologicalsystems |