Kontsevoi Sergii

Associate Professor (2014), Faculty of Chemical Technology

Igor Sikorsky Kyiv polytechnic institute

serkon157@ukr.net

Graduated from the KPI in 1994

Worked in the heating supply systems of "Kyivenergo" since

1994 (operator of boiler equipment), process engineer
(1995-1996), to 1999 (head of the chemical service)

Consultant of Dow Chemicals in Ukraine - 2001

Employee (Assistant Professor) of the KPI since 2005

Defended the PhD thesis in 2011

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 Scientific activity

I continue (from 1993) to deal with the problems of preventing scale

and corrosion in heating supply systems of Kyiv. Since 2001, I have
been researching in this area. Here is an abstract of the dissertation.

Kontsevoi S.A. Theoretical and practical bases of carbonate

scaling prevention in the aquatic heat exchange systems. –
Manuscript.

The dissertation for obtaining the PhD degree in technical

sciences in speciality 05.17.21 – Technology of water treatment. -
National Technical University of Ukraine «Kyiv Polytechnic Institute»,
Kyiv/Kiev, 2011.
Keywords: calcspar, potential of carbonate scaling, admissible
temperature of water, thermal networks, cooling systems, inhibitors of
scale formation, oxygen reducers, utilization of retentate, coefficient of
evaporation.
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 Abstract
The dissertation is devoted to the development of theoretical bases and
experimental methods for determining composition of water that precludes
formation of calcium carbonate in the water and, as a result, on heat-exchange
surfaces. We investigated properties of the water was heated without boiling and
without air contact, as in cooling systems (40÷80 oC) and thermal networks (70÷190
o
C).
Based on the developed experimental procedure, determination of the
mechanism of HCO3- decomposition in a heated (in stainless reactors without air
contact) to a predetermined temperature of water (40÷190 oC) takes 1-2 days.
Decomposition of HCO3- ions by ОН-mechanism (with formation of ОН- and CO2)
leads to an increase of рН (ΔрН<0), and by an Н-mechanism (with formation of Н+
and CO32-) leads to a decrease of рН (ΔрН>0).
The designed procedure includes determination of hardness change
(subsequent to the formation of СаCO3), that allows to define the admissible value
ΔрНadm and, as a result, define necessary (with a minimum cost) treatment of water
in which there is no calcspar after heating.
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 Generally accepted approach
non-equilibrium states in water depend on
carbonate (carbonic) equilibrium in water chemical composition of water and temperature: LSI Calculator

LSI = pH - pHs
Where:
- pH is the measured water pH
- pHs is the pH at saturation in
calcite or calcium carbonate
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 Hydrocarbonate equilibrium

Generally accepted equation of carbonic acid equilibrium:

2HCO3- = CO32- + H2O + CO2 (1)
and acid decomposition (рН 4,2 ÷ 8,35):
HCO3- + H+ = [H2CO3 ]= OH- + CO2 (2)
K1*= [H+]*[HCO3-] / [CO2] (3)

New hydrocarbonate equilibrium equations:

(рН 4,2 – 11,2; рНch 8,35):
рН < рНch: рН > рНch:
HCO3- = OH- + CO2 (4) HCO3- = H+ + CO32- (5)
(ОН-mechanism) (Н-mechanism)
KOH = [OH-]*[CO2] / [HCO3-] = Kw / K1* (6)
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 Complex method for determining the possibility of scale formation

Scale potential in
nonequilibrium conditions
(after heating):
ΔрН = рН1 – рН2
0 > ΔрН > 0
OH-mech. > 0.0 > H-mech.
HCO3- → OH- + CO2 sign corresponding with
HCO3- → H+ + CO32-
Са2+ + CO32- → СаСО3↓
LSI
2HCO3- ≈ CO2 + CO32- + H2O

The same sign (>0) for delta electrical conductivity (Cond) and
water hardness (WH) => because calcium carbonate is formed =>
decrease of WH and Cond parameters 6
Determination of the conditional temperature of water saturation
(tap water of Kyiv) - TS = 82oC

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Determination of the permissible hardness of water
at temperature of 150 °C and pH of 7.6

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 The actual water hardness determination Four types of water samples were studied:
(after Na-cationization) water after the laboratory filter with a cation
exchanger, which is used for determining the dynamic
Water sample WH AWH
before after thermostating, capacity of the cation resin by students. The raw
thermostating, μmol /l water is tap water in 162-4 laboratory of KPI;
μmol/l
water after filters (one stage only) of the Darnytska
KPI laboratory 0÷40 400÷ 600
Power Station (DPS) in Kyiv. Raw water from the
DPS 40 60 Dnipro pumping station (at Rusanovski Canal), then
sedimentation (with coagulation) tanks and
HSS-1 (after 1 40 360
stage) mechanical filters;
HSS-1 (after 2 20 140 water after filters of the 1st and 2nd stages of the Heat
stage)
supply station №1 (HSS-1) of the Kyivenergo Heat
Networks. Raw water from the Dnipro pumping
station and after mechanical filters HSS-1.
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 Determining the admissible water hardness at 150oC

ΔWH2,
WH before, WH after, ΔWH1,
№ D calc.: ΔWH1-ΔWH2
mmole/l mmole/l actual
-D*0.6

1 2 3 4 5 6 7

1 0 5,10 4,4 0,7 0 0,7

2 0,25 3,80 3,6 0,2 -0,15 0,35

3 0,50 2,55 2,6 -0,05 -0,3 0,25

4 0,75 1,28 1,8 -0,52 -0,45 -0,07

5 1 0 0,6 -0,6 -0,6 0

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 Efficiency of any reducing agent

2Na2SO3 + O2 -> 2Na2SO4

Hermetic Reactor with:
water
+ Samples of steel
+ Na2SO3 (in excess)
+ with or not
catalyst:
ΔC(RA)1 - change in the concentration of the reducing agent
Cu2+ (0.1 mg / L) or
Co2+ (0.01 mg / L)
Competing reactions:
2Fe + O2 + 2H2O -> 2Fe2+ + 4OH-
Fe2+ + 2OH- = Fe(OH)2
Fe(OH)2 + O2 = Fe(OH)3
ERAt = ΔC(RA)1/ ΔC(RA)0 * 100,
t - set temperature of thermostating;
(sodium sulphite) in the presence of steel samples;
ΔC(RA)0 – the same without steel samples.
ERA60 ”steel 20” with tap water at рН = 7.6:
without catalyst 90%, with it 99%
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 Improvement of the water-chemical
regime of heat sources

Heat is generated by KYIVENERGO at TPS-5, TPS-6 as well as in 4 heat supply

stations and 181 boiler plants. The total heat sources capacity is 8 814,6 Gcal/hr. Heat
is transferred through the heat network of total length around 2 600 km (two-pipe
dimension). Kyivenergo

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Methods for determining the effectiveness of anticorrosion actions

WH in micro mole/L d = Graw / Gtrd = (WHnet - WHtrd) / (WHraw - WHnet) (1)

WHraw = 5000
С(О2)act = (С(О2)trd + d ∙ С(О2)raw) / (1 + d) (2)
WHnet = 285-500
WHtrd = 50
Degree of oxygen reduction by steel's iron:
d = 0.05 - 0.10
С(О2) in micro g/L Xred = (С(О2)act - С(О2)net) / С(О2)act ∙ 100 (3)
С(О2)trd = 50 The actual effectiveness of the protective film
С(О2)raw = 8000 (carbonate and iron oxides in industrial conditions):
С(О2)net = 20 AEpf = 100 – Xred (4)
С(О2)act = 400-800
raw - raw water from damaged hot water boilers
Xred = 95-97.5 %
net - water in heat network
trd - treated water from heat source
AEpf = 5-2.5 % act - actual make up water of heat networks (trd + raw)
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 Main problem for a drainless scheme and its solution
The main problems are related to the internal corrosion of the equipment, especially for HSS
“Poznyaki” (HSS 4). This is due to the implementation of a drainless scheme on the HSS 4,
in which effluents from Na-cation exchanger filters are fed to the clarifier. In the clarifier (with
lime added), calcium carbonate is formed, but the chloride ions pass through the whole
water purification scheme and enter the heat network.
As a result, their concentration increases from 50 to 300-400 mg / L, which leads to
increased oxygen corrosion.
Solution: At temperatures up to 100 °C, it is possible to exclude Na-cationization of water at
pH of about 8.5 (determined by our method).

The low cost (about 1 euro cent per m3) of sulphiting (2Na2SO3+O2->2Na2SO4), simplicity of
implementation and high efficiency can recommend this method of minimizing the corrosion
activity of water (at any concentration of Cl-) and preventing surface contamination of water
heating equipment by iron oxides (up to 90% of all contamination) for the all heating supply
systems in “Kyivenergo”.
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The heat supply station (Kyiv)

From the minutes of the Kyivenergo-KPI

working meeting (30.11.2016):

The results of the work performed under the

Contract from June 26, 2016, No. 918-16

"Development of organizational and technical

solutions and performance of pilot tests to
improve the water-chemical regime of the heat
sources of "KYIVENERGO" in the conditions
of reduced temperature regime of the coolant"

are in accordance with the Technical Task and

allow to improve the water-chemical regime
both in terms of reducing the corrosion activity
of water, and in the part of the ability of the
network water to form carbonate scale.

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New research interests

The topic

Study of technical sciences by programming expert

systems and creating models of appropriate
systems (chemical processes, apparatus and
process flowsheets for chemists and engineers).

Additional result

The use of the Python language and relevant

libraries at all stages as a way of obtaining
programmer education while studying chemistry
and chemical technology.
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 Components
The programming of expert systems (strong AI, artificial intelligence) is
based on the visual language Drakon with the Python (automatically
generated code) implementation language (Drakon-editor).
http://web.snauka.ru/issues/2018/06/87078
The use of a functional approach to the modeling of apparatus
parameters in chemical technologies (Python and VBA). A universal
methodology for calculating any process flowsheets on this basis.
http://web.snauka.ru/en/issues/2018/05/86532
[http://web.snauka.ru/issues/2016/06/68504]
Use of machine learning technologies (weak AI) to solve such
problems as the definition of the mechanisms of complex chemical
reactions within the formal kinetics methods. In particular, the use of
trained neural networks to calculate the rate constants of the reactions
(Matlab, Python).

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 Thank you all for your attention and I hope to cooperate!
Дякую всім за увагу і сподіваюся на співпрацю!

Спасибо всем за внимание и надеюсь на сотрудничество!

Dziękuję wszystkim za uwagę i mam nadzieję na współpracę! 18