THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS AND THEIR PURIFICATION BY ELECTROLYSIS
The mechanism of accumulation of dissolved iron compounds in groundwater and brines under the influence of sulfate reduction and the resulting decrease in the redox potential is considered. The mechanism under consideration has been experimentally confirmed. A method of extraction of su...
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V.I.Vernadsky Institute of General and Inorganic Chemistry
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Ukrainian Chemistry Journal| _version_ | 1871466137478234112 |
|---|---|
| author | Mykhaylenko, Volodymyr Antonov , Oleksii |
| author_facet | Mykhaylenko, Volodymyr Antonov , Oleksii |
| author_institution_txt_mv | [
{
"author": "Volodymyr Mykhaylenko",
"institution": "A.M. Pidhorny Institute of Mechanical Engineering Problems, NAS of Ukraine, 2\/10 Pozharsky St., 61046, Kharkiv, Ukraine"
},
{
"author": "Oleksii Antonov ",
"institution": "A.M. Pidhorny Institute of Mechanical Engineering Problems, NAS of Ukraine, 2\/10 Pozharsky St., 61046, Kharkiv, Ukraine"
}
] |
| author_sort | Mykhaylenko, Volodymyr |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:56Z |
| description | The mechanism of accumulation of dissolved iron compounds in groundwater and brines under the influence of sulfate reduction and the resulting decrease in the redox potential is considered. The mechanism under consideration has been experimentally confirmed. A method of extraction of sulfides and ferrum-containing compounds by electrochemical oxidation using an inert anode is proposed. The technology for obtaining an inert anode based on manganese and lead oxides, stable in most natural waters and brines, which does not contain noble metals and their compounds, is described. The specified technology involves the deposition of manganese dioxide on a titanium base by thermal decomposition of manganese nitrate. After that, the base is covered with a thin layer of PbO2 by electrodeposition from an alkaline complex electrolyte, and then with a thick layer of the same oxide by electrodeposition from a nitrate electrolyte. It has been established that the contact of an alkaline complex electrolyte with the active surface of metallic lead can significantly reduce the formation of bottom deposits during electrodeposition. It is shown how interruption of the current during the electrodeposition of such an anode can reduce its porosity and increase its stability. The process of iron removal and sulfide extraction from highly mineralized mine and quarry waters has been studied. It has been theoretically calculated and experimentally confirmed that the electricity consumption for the iron removal process of such waters does not exceed 1 kW*h/m3. An example of the application of the method of electrochemical iron removal and sulfide extraction from highly mineralized brines with their subsequent resource-saving processing and obtaining water for power supply of energy facilities and commodity mineral salts is given. |
| doi_str_mv | 10.33609/2708-129X.91.6.2025.3-14 |
| first_indexed | 2025-10-23T01:32:47Z |
| format | Article |
| fulltext |
3
UDC 621.16.087:66.087.7 doi: 10.33609/2708-129X.91.6.2025.3-14
THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS
IN HIGHLY MINERALIZED MINE AND QUARRY WATERS
AND THEIR PURIFICATION BY ELECTROLYSIS.
Volodymyr Mykhaylenko, Oleksii Antonov
1A.M. Pidhorny Institute of Mechanical Engineering Problems, NAS of Ukraine,
2/10 Pozharsky St., 61046 Kharkiv, Ukraine
e-mail: port342017@gmail.com
The mechanism of accumulation of dissolved iron compounds in groundwater and brines
under the influence of sulfate reduction and the resulting decrease in the redox potential
is considered. The mechanism under consideration has been experimentally confirmed.
A method of extraction of sulfides and ferrum-containing compounds by electrochemical
oxidation using an inert anode is proposed. The technology for obtaining an inert anode
based on manganese and lead oxides, stable in most natural waters and brines, which does not
contain noble metals and their compounds, is described. The specified technology involves
the deposition of manganese dioxide on a titanium base by thermal decomposition of man-
ganese nitrate. After that, the base is covered with a thin layer of PbO2 by electrodeposition
from an alkaline complex electrolyte, and then with a thick layer of the same oxide by elect
rodeposition from a nitrate electrolyte. It has been established that the contact of an alkaline
complex electrolyte with the active surface of metallic lead can significantly reduce the forma-
tion of bottom deposits during electrodeposition. It is shown how interruption of the current
during the electrodeposition of such an anode can reduce its porosity and increase its stability.
The process of iron removal and sulfide extraction from highly mineralized mine and quarry
waters has been studied. It has been theoretically calculated and experimentally confirmed
that the electricity consumption for the iron removal process of such waters does not exceed
1 kW*h/m3. An example of the application of the method of electrochemical iron removal
and sulfide extraction from highly mineralized brines with their subsequent resource-saving
processing and obtaining water for power supply of energy facilities and commodity mineral
salts is given.
Keywords: Sulfate reduction, ferrum removal, sulfide removal, electrolysis, mine waters
and brines.
4 ISSN 2708-129X. Укр. хім. журн., 2025
THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS
AND THEIR PURIFICATION BY ELECTROLYSIS.INORGANIC CHEMISTRY
INTRODUCTION. Almost all mining and
industrial regions of Ukraine are water-de-
ficient. For the needs of industry, in particu-
lar, thermal power engineering, a significant
amount of drinking water is used in these re-
gions. At the same time, large amounts of wa-
ter are pumped out of mines, including closed
ones, and quarries. But these waters are con-
taminated with mineral impurities and cannot
be used for technical needs without deep pu-
rification, in particular demineralization. The
calculation of possible environmental damage
from the discharge of only brines from quar-
ries and tailings ponds of the Kalush mining
and industrial region into surface water bo
dies, carried out according to the methodology
(Methodology, 2009), shows that such damage
exceeds 3 billion UAH.
There is a method for purifying highly mi
neralized waters and brines with the produc-
tion of impurities in the form of marketable
by-products (Tarelin A.O., 2018). However,
in most cases, such waters contain quantita-
tively small, but quite dangerous impurities
of soluble iron and sulfide compounds. When
attempting to subject these waters to mem-
brane demineralization without prior removal
of iron and sulfides, the latter are deposited
on the surface of the membranes, irreversibly
disabling them. When attempting to demine
ralize such waters thermally, sulfides and iron
(III) hydroxide are deposited on the heating
surfaces in the form of a rocky scale, which
can only be removed mechanically. Therefore,
preliminary deep extraction of these com-
pounds is necessary.
The mechanism of accumulation of soluble
ferrum compounds and sulfides in ground-
water and brines is currently not sufficiently
studied. There are separate publications de
scribing the mechanism of dissolution of py-
rite and chalcopyrite when groundwater flows
through restored rocks (Xinfeng Wang, 2021).
However, insufficient attention is paid to the
processes of dissolution of ferrum compounds
from oxidized rocks. These rocks make up the
majority of the surface of the earth’s crust. They
contain trivalent ferrum oxide, which is almost
insoluble at pH above 5.0. At the same time, it
is in the waters flowing through such rocks that
the concentrations of the specified element are
relatively high (Table 1).
Table 1.
Main indicators of highly mineralized waters and brines.
Name of water
Indicators, mg/dm3
Ferrous
soluble Sulfides Total
mineralization
Water from the Batkivshchyna mine of the Kryvyi Rih
iron ore basin 30,3 17,2 83920
Brine from the Dombrovsky quarry 30,7 15,6 350000
Formation water from oil production wells of the
Poltava region 270 18,0 220000
5https://ucj.org.ua
Volodymyr Mykhaylenko, Oleksii Antonov UCJ № 6 / Vol. 91
The mechanism of accumulation of so
luble ferrum compounds in low-minera
lized groundwater in the Netherlands flowing
through oxidized clays has been described
(van Beek, G.G.E.M., 2021). However, the
main focus of this article is on the dissolution
and accumulation of FeCO3 siderite in waters
under the influence of low pH, and insuffi-
cient emphasis is placed on the role of redox
processes.
The aim of the work is the theoretical and
experimental study of the causes and mecha-
nism of accumulation of ferrum compounds
in mine waters and brines, as well as the de-
velopment of methods and equipment for their
removal.
EXPERIMENT AND DISCUSSION OF RE-
SULTS. Calculations of the potentials of redox
reactions that occur in salt solutions under an-
aerobic conditions were carried out using the
well-known Nernst formula. The materials for
the research were brine taken from the Dom-
brovsky quarry at a depth of 42 m, a water sam-
ple from the Rodina mine of the Kryvyi Rih
iron ore basin, and model solutions of a com-
position similar to the brine composition and
groundwater of the Buchach horizon (mine
ralization 2.5 g/dm3). The concentrations of
the solution components were measured using
standard analytical methods.
Manganese nitrate and known nitrate and
alkaline complex electrolytes for lead dioxide
electrodeposition were used to manufacture
inert anode samples (Mykhailenko V.G., 2022).
As a result of the vital activity of bacteria of
the genus Desulfovibrio and Desulfotomacu-
lum (de Rezende J.R, 2013, Osturk M, 2021),
in sulfate-containing solutions under anaero
bic conditions, in the presence of organic
substances, microbiological sulfate reduction
occurs and hydrogen sulfide and free carbonic
acid accumulate (Basen M, 2011):
SO4
2- + 10Н++ 8e= Н2S + 4H2O;
C3H6O3 + 3H2O– 12e= 3CO2 + 12H+.
At the same time, a significant decrease
in pH and Eh of solutions occurs. Since in a
weakly acidic environment hydrogen sulfide
is extremely poorly dissociated, the content
of S2- ions is small, the solubility product of
FeS and FeS2 is not achieved, and the indicat-
ed sparingly soluble compounds cannot be
formed (Bozo-Hurtado L, 2013)
Therefore, it was necessary to establish and
experimentally substantiate the mechanism of
accumulation of iron compounds and sulfides
in highly mineralized waters, and then deve
lop a method for extracting these compounds,
which, when present together, interfere with
the low-waste processing of such waters to
obtain purified water for the energy industry
and related commercial products. Known
technologies for purifying water from such
compounds by interaction with air oxygen
or ozone (Duranceau S J, 2010 Leszczyński J.,
2019) do not work at high mineralization due
to poor solubility of gases. There is a known
method for extracting iron compounds and
sulfides from highly mineralized formation
waters by electrocoagulation using iron ano
des (Shamsiyev Sh.D, 2019). However, this
method is associated with high consumption
of anodes, which are products from commer-
cial metal sheets. In addition, it does not al-
low for deep extraction of dissolved iron com-
pounds, and is generally unsuitable for brines
with high mineralization.
Simultaneous removal of sulfides and fer-
rum compounds from highly mineralized
6 ISSN 2708-129X. Укр. хім. журн., 2025
THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS
AND THEIR PURIFICATION BY ELECTROLYSIS.INORGANIC CHEMISTRY
waters is possible using electrotreatment with
inert anodes, but at present this method is too
expensive, since it is necessary to use noble me
tals or titanium coated with a layer of such me
tals or their compounds as such anodes (Liu L.,
2024). The use of graphite as an inert anode for
the purification of highly mineralized waters
is impractical, since this material is unstable
during anodic polarization in the O2 release
mode (Sanches-Sanches T J., 2020). Thus, the
next task of the research was to develop a stable
inert anode that would not contain noble
metals and their compounds. When imple-
menting it, the authors paid attention to low-
wear anodes based on manganese and lead
dioxides.
Titanium-based anodes coated with a layer
of manganese dioxide (MnO2) do not require
a noble metal sublayer (Mohammadi M.). Du
ring the thermal decomposition of manganese
nitrate, a metallothermal reaction occurs on
the titanium surface, and the metallic man-
ganese released as a result dissolves in titani-
um, forming a penetration solution. There-
fore, manganese dioxide obtained by thermal
decomposition of manganese nitrate has good
adhesion to the titanium base and, at the same
time, creates a relief necessary to improve the
adhesion to the base of other coatings. There-
fore, before applying such a coating to titani-
um, it is possible not to apply a relief by me-
chanical treatment, as in other cases. Howev-
er, manganese dioxide itself is not sufficiently
stable during anodic polarization in chlo-
ride-sulfate solutions and gradually collapses.
Eventually, the active coating becomes porous,
the titanium base begins to be covered with a
semiconducting film of titanium dioxide, and
after that, electrolysis stops due to a significant
increase in the anode voltage.
A more stable anode material is lead dioxi
de (Mukimin A., 2013). However, when it is
applied directly to a titanium substrate, during
anodic polarization, a relatively rapid diffusion
of atomic oxygen to the titanium surface oc-
curs and the substrate is subsequently passivat-
ed by a TiO2 film with increasing voltage and
termination of electrolysis (Olesia B., 2017).
To significantly increase the service life of such
anodes, a thin coating of platinum, iridium or
other noble metals and their compounds is ap-
plied under the layer of the main oxide coating
(Devilliers D., 2003).
Solutions for electrodeposition of lead di-
oxide of various compositions are known. The
most common is an acidic nitrate electrolyte,
which is characterized by high stability, allows
high current densities (up to 1000 A/m2) and
is easy to prepare and use (Mykhailenko V.H.,
2022).
The second group of electrolytes is alkaline
plumbite (Mukimin A., 2013) and complex
(Mykhailenko V.H., 2022) solutions, which
give compact shiny deposits, but only at low
current densities (100–200 A/m2). In addition,
these electrolytes are kinetically unstable, since
after passing a certain amount of electrici-
ty (4–5 A*h/dm3 for plumbite electrolyte and
5–6 A*h/dm3 for complex) brick-red bottom
deposits fall out of them. Thus, it was necessary
to develop a method for obtaining inert anodes
and, on their basis, develop a technology for
extracting iron compounds and sulfides from
highly mineralized wastewater.
The selected water sample from the Rodina
mine has a redox potential relative to the hyd
rogen electrode of 230 mV and pH 5.5, the
brine of the Dombrovsky quarry – 270 mV
and 5.7, respectively, and the formation water
sample – 250 mV and 5.4. At this pH, trivalent
7https://ucj.org.ua
Volodymyr Mykhaylenko, Oleksii Antonov UCJ № 6 / Vol. 91
ferric compounds will not dissolve. However,
the analysis shows that significant concentra-
tions of divalent ferric compounds in ionic
form are present in the solution. According
to the Pourbe diagram for ferric compounds,
under these conditions, divalent ferric ions
are stable.
The following mechanism for the disso-
lution of oxidized iron-containing rocks was
proposed.
When a solution with a low redox potential
comes into contact with iron-containing rocks,
hydration of trivalent ferric oxide occurs and
its reduction occurs according to the reaction:
Fe2O3 + 3H2O +2e = 2Fe(OH)2 + 2OH-.
The equilibrium potential of this reaction is
+581 mV. At the same time, hydrogen sulfide is
oxidized by the reaction:
Н2S + 3H2O – 6e = SO3
2- + 8H+.
This reaction has a potential of (-500) mV.
Thus, the potential difference between the oxi
dation and reduction reactions exceeds 1 V,
which is quite sufficient for their spontaneous
occurrence.
The formed sulfite ion SO3
2- is used by sul-
fate-reducing bacteria to oxidize a new amount
of organic matter
The formed iron (II) hydroxide interacts
with carbon dioxide to form soluble iron bicar-
bonate Fe(HCO3)2. This mechanism is similar
to that described in the literature (van Beek,
G.G.E.M., 2021), however, it clearly links the
accumulation of ferrum bicarbonate (and not
siderite, which is poorly soluble) not only with
pH, but also with the low redox potential of the
system.
The described mechanism of dissolution of
Fe2O3 was experimentally confirmed during
laboratory studies.
The experiments were performed on three
model solutions, the composition of which
simulated brackish water with a mineralization
of 2.5 g/dm3 (solutions 1 and 2) and brine with
a mineralization of 305 g/dm3 (solution 3).
Sodium sulfide and sodium bicarbonate were
added to solutions 2 and 3 and then neutralized
with hydrochloric acid to pH 5.7, thus repro-
ducing the conditions in groundwater. Solu-
tion 1 was treated in the same way, but instead
of sodium sulfide, a similar amount of sodium
bicarbonate was added. The solutions were
brought into contact with an ferrum-contain-
ing substance, in this experiment with freshly
deposited trivalent ferric hydroxide. The re-
sults of the studies (Fig. 1) show that in the ab-
sence of a reducing medium, the accumulation
of iron compounds in the solution does not oc-
cur. If a strong reducing agent (H2S) appears
in the solution, dissolution of iron compounds
and their accumulation occur, and in a high-
ly mineralized environment this process pro-
ceeds much slower than in low-mineralized
solutions.
The dissolution of trivalent iron com-
pounds occurs approximately ten times slow-
er upon contact of the solution with ground
Kryvyi Rih red hematite (Fig. 2). After 5 days
of contact with the iron-containing substance,
the concentration of soluble iron compounds
increased from 0 to 0.4 mg/dm3, which, how-
ever, is a sufficient rate for geological processes.
Thus, the mechanism of accumulation of iron
compounds in natural waters and brines with
the participation of the sulfate reduction pro-
cess has been experimentally proven.
8 ISSN 2708-129X. Укр. хім. журн., 2025
THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS
AND THEIR PURIFICATION BY ELECTROLYSIS.INORGANIC CHEMISTRY
Fig. 1. Accumulation of ferrum compounds in model solutions upon contact with freshly
deposited Fe(OH)3. 1 – low-mineralized water with an admixture of hydrogen sulfide 15 mg/l;
2 – high-mineralized water with an admixture of hydrogen sulfide 15 mg/l;
3 – low-mineralized water without the addition of sulfides.
Fig. 2. Accumulation of ferrum compounds in a highly mineralized solution
containing 15 mg/l hydrogen sulfide upon contact with hematite.
9https://ucj.org.ua
Volodymyr Mykhaylenko, Oleksii Antonov UCJ № 6 / Vol. 91
The task of the next experiment was to de-
termine the rate of accumulation of soluble fer-
rum compounds upon contact of sulfide-con-
taining solutions with brown clay (Fig. 3).
From the data presented, it can be seen that
upon contact with clay, the dissolution of fer-
rum compounds occurs even more slowly, but
in geological time it is still quite fast.
Fig. 3. Accumulation of iron compounds in solutions upon contact with brown clay.
1 – concentration of iron compounds in low-mineralized water;
2 – the same in highly mineralized brine.
The next task was to develop a technology
for producing an inert metal oxide anode that
would be stable in alkaline, neutral and acidic
environments and, at the same time, would not
contain noble metals and their compounds.
The method for producing such anodes is
based on the idea of combining the advantages
of MnO2 and PbO2. It was necessary to apply
a thin layer of MnO2 to the titanium base, the
purpose of which was to prevent passivation of
the anode by titanium dioxide, and then cover
the electrode with a thick layer of active PbO2
coating.
Since alkaline electrolytes for electrodepo-
sition of PbO2 are kinetically unstable, a nitrate
electrolyte was taken as the basic option. How-
ever, it was found that PbO2 deposition does
not occur on the MnO2 surface even at high
current densities. This is explained by the great-
er positivity of the electrode potential of the
PbO2 deposition process (+1.288 V) compared
to the oxygen evolution potential (+1.053 V).
Instead, PbO2 begins to be released from the al-
kaline complex electrolyte before reaching the
oxygen evolution potential (+0.22 V and +0.41
V, respectively). Thus, at low current densities,
PbO2 is deposited on the manganese dioxide
surface without oxygen evolution. Therefore,
it is necessary to cover the manganese dioxide
surface with a lead dioxide deposit deposited
10 ISSN 2708-129X. Укр. хім. журн., 2025
THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS
AND THEIR PURIFICATION BY ELECTROLYSIS.INORGANIC CHEMISTRY
from the alkaline complex solution, and then
apply a base layer of PbO2 coating from the nit
rate electrolyte.
The reasons for the kinetic instability of al-
kaline electrolytes were established. In an al-
kaline complex electrolyte containing a high
concentration of the complexing agent EDTA,
during the oxidation of plumbite ions to
HPbO3– plumbate at the anode, the latter par-
tially dissolves in the electrolyte. At the same
time, the concentration of plumbates in the
solution increases, and when it reaches satu-
ration, which we experimentally established
at 75×10-5 mol/dm3, plumbates interact with
plumbites according to the reactions:
2HPbO2
- +HPbO3
- = Pb3O4↓ + 3OH-;
HPbO2
- +HPbO3
- = Pb2O3↓ + 2OH-,
forming bottom sediments.
The study of the kinetics of plumbates accu-
mulation during electrolysis in a conventional
cell and in a cell with a catholyte separated from
the main solution by a cation-exchange mem-
brane showed that upon contact with the catho-
de and cathode lead (which is released during
electrolysis), the accumulation of plumbates
in the electrolyte occurs several times slower.
The process of plumbates recovery upon con-
tact of the electrolyte with the active surface
of metallic lead was investigated (Fig. 4), the
experimental results were processed according
to the kinetic equation of the first order and
the criterion of kinetic stability of the alkaline
complex electrolyte during electrodeposition
of PbO2 was derived:
, (1)
where and is the electrolysis current density,
A/m2,
C is the concentration of plumbates in the
electrolyte, mol/dm3.
This criterion is actually the ratio of the areas
of the anode and the metallic lead immersed in
the solution, and under normal deposition con-
ditions (i = 100 A/m2, C = 37.5*10-5 mol/dm3)
it is equal to 5.99. Therefore, if the surface of
the metallic lead immersed in the electrolyte
during the electrodeposition of PbO2 is 6 times
larger than the area of the anode, the formation
of bottom deposits will not occur.
SPb =
Ki
SA K'C
Fig. 4. Kinetics of plumbates reduction on the active surface of metallic lead.
11https://ucj.org.ua
Volodymyr Mykhaylenko, Oleksii Antonov UCJ № 6 / Vol. 91
After the MnO2 sublayer deposited on tita-
nium by thermal decomposition of manganese
nitrate is completely covered with a thin PbO2
layer, further lead dioxide deposition can be
carried out at high current densities from a nit
rate electrolyte.
Interruption of the PbO2 electrodeposi-
tion process for more than 10 minutes leads
to passivation of the oxide surface. Therefore,
the next electrodeposition cycle begins with
the appearance of new nuclei of lead dioxide
crystals, and thus, the pores of the first coat-
ing layer are partially covered by another layer.
This increases the stability of the anode and its
service life.
Samples of bench anodes with an area of
2 dm2 were obtained, and the extraction of
sulfides and iron compounds from the brine
of the Dombrovsky quarry was performed on
these anodes (Fig. 4). The electrolysis voltage
was 4.5 V, at a current density of 1000 A/m2.
The indicated graphs show that during elec-
trolysis, sulfides are first oxidized to sulfates
and the pH of the brine decreases from 5.8 to
5.3. After that, when more positive potentials
are reached, the ferric compounds are oxidized
to form trivalent ferric hydroxide in the form
of flakes, which are easily separated from the
brine when it is clarified by filtration. The es-
timated electricity consumption for the oxida-
tion of ferric and sulfides in the brine with a
mineralization of 350 g/dm3 does not exceed
1 kWh/m3.
Fig. 5. Dependence of the residual concentration of ferrum compounds (row 1)
and sulfides (row 2) on the redox potential of the solution during the electrolysis
of the brine of the Dombrovsky quarry.
After the extraction of ferrum compounds
and sulfides, the brine was subjected to galur-
gic separation, during which technical sodium
chloride, valuable potassium fertilizer, crystal-
line magnesium chloride and purified water
with an electrical conductivity of 3–5 μS/cm
(residual mineralization 1.5–2.5 mg/dm3) were
obtained, which after further purification is
suitable for use as feed water for power boilers.
The further purification of water by electro-
deionization on a laboratory electrodeionizer
allowed to obtain deionized water with a residu-
al electrical conductivity of 0.2 μS/cm at an ad-
ditional electricity consumption of 0.1 kWh/m3.
CONCLUSIONS. A mechanism for the ac-
cumulation of soluble iron compounds during
the flow of water and brines through oxidized
iron-bearing rocks has been proposed and ex-
perimentally proven. Based on this mechanism,
a method for the extraction of iron compounds
12 ISSN 2708-129X. Укр. хім. журн., 2025
THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS
AND THEIR PURIFICATION BY ELECTROLYSIS.INORGANIC CHEMISTRY
from brines and highly mineralized waters by
electrolysis with an inert anode has been deve
loped. A technology for obtaining inert metal
oxide anodes that do not contain noble metals
or their compounds has been developed. Such
anodes can also be used for water treatment
and wastewater treatment, including in the
production of composite fuels, for the removal
of sulfides from municipal wastewater, which
will improve their further treatment, the crea-
tion of closed technological cycles by hydroly-
sis of salt solutions and other needs. These ano-
des are used to remove sulfides and iron com-
pounds from highly mineralized waters before
their demineralization to obtain purified water
for the needs of the energy industry (electrical
conductivity 2.5–5 μS/cm) and salt commodity
products. The use of electrodeionization allows
the obtained water to be further purified to a
residual mineralization of 0.2 μS/cm, which
meets the standards for feed water for power
boilers. The additional electricity consumption
in this case does not exceed 0.1 kWh/m3.
ACKNOWLEDGMENT. The descri
bed research was carried out and sum
marized within the framework of to
pic No. III-22-23 «Improvement of the
method for obtaining feed water from
brines and mine waters.»
МЕХАНІЗМ НАКОПИЧЕННЯ СПОЛУК ФЕРУМУ
У ВИСОКОМІНЕРАЛІЗОВАНИХ ШАХТНИХ
ТА КАР’ЄРНИХ ВОДАХ ТА ОЧИЩЕННЯ
ЇХ ЕЛЕКТРОЛІЗОМ
Володимир Михайленко, Олексій Антонов
1Інститут проблем машинобудування
ім. А. М. Підгорного НАН України,
вул. Пожарського, 2/10, Харків 61046,
Україна
e-mail: port342017@gmail.com
Розглянуто механізм накопичення у під-
земних водах та розсолах розчинених спо-
лук феруму під впливом сульфатредукції
та викликаного нею зниження окисно-від-
новного потенціалу. Розглянутий механізм
експериментально підтверджено. Запропо-
новано спосіб вилучення сульфідів та фе-
румвмісних сполук електрохімічним окис-
ненням із використанням інертного аноду.
Описано технологію одержання інертного
аноду на основі оксидів мангану та плюм-
буму, стійкого у більшості природних вод
та розсолів, який не містить благородних
металів та їхніх сполук. Зазначена техноло-
гія включає осадження на титанову основу
манган діоксиду шляхом термічного роз-
кладання манган нітрату. Після цього осно-
ва покривається тонким шаром PbO2 шля-
хом електроосадження з лужного комплекс
ного електроліту, а потім – товстим шаром
того ж оксиду шляхом електроосадження
з нітратного електроліту. Встановлено, що
контакт лужного комплексного електроліту
з активною поверхнею металевого плюмбу-
му дозволяє істотно зменшити утворення
донних відкладень при електроосаджен-
ні. Показано, як переривання струму при
електроосадженні такого аноду може змен-
шити його пористість та збільшити стій-
кість. Досліджено процес знезалізнення та
вилучення сульфідів із високомінералізо-
ваних шахтних та кар’єрних вод. Теоретич-
13https://ucj.org.ua
Volodymyr Mykhaylenko, Oleksii Antonov UCJ № 6 / Vol. 91
но розраховано та експериментально під-
тверджено, що витрати електроенергії на
процес знезалізнення таких вод не переви-
щують 1 кВт*год/м3. Наведено приклад за-
стосування способу електрохімічного зне-
залізнення та вилучення сульфідів із висо-
комінералізованих розсолів із подальшим
їхнім ресурсозберігаючим переробленням
та одержанням води для живлення об’єктів
енергетики та товарних мінеральних солей.
Ключові слова: сульфатредукція, знеза-
лізнення, очищення від сульфідів, електро-
ліз, шахтні води та розсоли.
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14 ISSN 2708-129X. Укр. хім. журн., 2025
THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS
AND THEIR PURIFICATION BY ELECTROLYSIS.INORGANIC CHEMISTRY
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Стаття надійшла 15.05.2025.
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-732 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:13:09Z |
| publishDate | 2025 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/28/11dbc41d1aa48ee41904bd9028331528.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-7322026-07-22T08:23:56Z THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS AND THEIR PURIFICATION BY ELECTROLYSIS Mykhaylenko, Volodymyr Antonov , Oleksii Sulfate reduction, ferrum removal, sulfide removal, electrolysis, mine waters and brines. The mechanism of accumulation of dissolved iron compounds in groundwater and brines under the influence of sulfate reduction and the resulting decrease in the redox potential is considered. The mechanism under consideration has been experimentally confirmed. A method of extraction of sulfides and ferrum-containing compounds by electrochemical oxidation using an inert anode is proposed. The technology for obtaining an inert anode based on manganese and lead oxides, stable in most natural waters and brines, which does not contain noble metals and their compounds, is described. The specified technology involves the deposition of manganese dioxide on a titanium base by thermal decomposition of manganese nitrate. After that, the base is covered with a thin layer of PbO2 by electrodeposition from an alkaline complex electrolyte, and then with a thick layer of the same oxide by electrodeposition from a nitrate electrolyte. It has been established that the contact of an alkaline complex electrolyte with the active surface of metallic lead can significantly reduce the formation of bottom deposits during electrodeposition. It is shown how interruption of the current during the electrodeposition of such an anode can reduce its porosity and increase its stability. The process of iron removal and sulfide extraction from highly mineralized mine and quarry waters has been studied. It has been theoretically calculated and experimentally confirmed that the electricity consumption for the iron removal process of such waters does not exceed 1 kW*h/m3. An example of the application of the method of electrochemical iron removal and sulfide extraction from highly mineralized brines with their subsequent resource-saving processing and obtaining water for power supply of energy facilities and commodity mineral salts is given. V.I.Vernadsky Institute of General and Inorganic Chemistry 2025-07-25 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/732 10.33609/2708-129X.91.6.2025.3-14 Ukrainian Chemistry Journal; Vol. 91 No. 6 (2025): Ukrainian Chemistry Journal; 3-14 Украинский химический журнал; ##issue.vol## 91 ##issue.no## 6 (2025): Ukrainian Chemistry Journal; 3-14 Український хімічний журнал; Том 91 № 6 (2025): Ukrainian Chemistry Journal; 3-14 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/732/370 Copyright (c) 2025 Volodymyr Mykhaylenko, Oleksii Antonov https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Mykhaylenko, Volodymyr Antonov , Oleksii THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS AND THEIR PURIFICATION BY ELECTROLYSIS |
| title | THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS AND THEIR PURIFICATION BY ELECTROLYSIS |
| title_full | THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS AND THEIR PURIFICATION BY ELECTROLYSIS |
| title_fullStr | THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS AND THEIR PURIFICATION BY ELECTROLYSIS |
| title_full_unstemmed | THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS AND THEIR PURIFICATION BY ELECTROLYSIS |
| title_short | THE MECHANISM OF ACCUMULATION OF FERRUM COMPOUNDS IN HIGHLY MINERALIZED MINE AND QUARRY WATERS AND THEIR PURIFICATION BY ELECTROLYSIS |
| title_sort | mechanism of accumulation of ferrum compounds in highly mineralized mine and quarry waters and their purification by electrolysis |
| topic_facet | Sulfate reduction ferrum removal sulfide removal electrolysis mine waters and brines. |
| url | https://ucj.org.ua/index.php/journal/article/view/732 |
| work_keys_str_mv | AT mykhaylenkovolodymyr themechanismofaccumulationofferrumcompoundsinhighlymineralizedmineandquarrywatersandtheirpurificationbyelectrolysis AT antonovoleksii themechanismofaccumulationofferrumcompoundsinhighlymineralizedmineandquarrywatersandtheirpurificationbyelectrolysis AT mykhaylenkovolodymyr mechanismofaccumulationofferrumcompoundsinhighlymineralizedmineandquarrywatersandtheirpurificationbyelectrolysis AT antonovoleksii mechanismofaccumulationofferrumcompoundsinhighlymineralizedmineandquarrywatersandtheirpurificationbyelectrolysis |