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ISSN 0040-6015, Thermal Engineering, 2017, Vol. 64, No. 10, pp. 777–780. © Pleiades Publishing, Inc., 2017.

Original Russian Text © L.A. Galimova, 2017, published in Teploenergetika.

NUCLEAR POWER
STATIONS

Application of Synthetic Fire-Resistant Oils in Oil Systems


of Turbine Equipment for NPPs
L. A. Galimova
AO Electrogorsk Research and Engineering Center on NPP Safety (AO EREC), Moscow oblast, 142530 Russia
e-mail: galimova@erec.ru
Received March 17, 2017; in final form, April 26, 2017

Abstract⎯Results of the investigation of the synthetic fire-resistant turbine oil Fyrquel-L state in oil systems
of turbosets under their operation in the equipment and oil supply facilities of nuclear power plants (NPPs)
are presented. On the basis of the analysis of the operating experience, it is established that, for reliable and
safe operation of the turbine equipment, at which oil systems synthetic fire-resistant oils on the phosphoric
acid esters basis are used, special attention should be paid to two main factors, namely, both the guarantee of
the normalized oil water content under the operation and storage and temperature regime of the operation.
Methods of the acid number maintenance and reduction are shown. Results of the analysis and investigation
of influence of temperature and of the variation of the qualitative state of the synthetic fair-resistant oil on its
water content are reported. It is shown that the fire-resistant turbine oils are characterized by high hydro-
philicity, and, in distinction to the mineral turbine oils, are capable to contain a significant amount of dis-
solved water, which is not extracted under the use of separation technologies. It is shown that the more deg-
radation products are contained in oil and higher acid number, the more amount of dissolved water it is capa-
ble to retain. It is demonstrated that the organization of chemical control of the total water content of fire-
resistant oils with the use of the coulometric method is an important element to support the reliable operation
of oil systems. It is recommended to use automatic controls of water content for organization of daily moni-
toring of oil state in the oil system. Recommendations and measures for improvement of oil operation on the
NPP, the water content control, the use of oil cleaning plants, and the oil transfer for storage during repair
works are developed.

Keywords: nuclear power plant, fire-resistant oil, hydrolysis of phosphoric acid esters, acid number, total
water content
DOI: 10.1134/S0040601517100020

Synthetic fire-resistant turbine oils are utilized in acid number (AN), characterizing number of the oil
the bearing regulating and lubricating systems, the acid components and expressed in milligrams (mg) of
auxiliary pumping equipment of turbosets, and oil sys- the potassium hydroxide (KOH) required for titration
tems of the main circulating pump aggregate (MCPA). of 1 g oil to the neutralization point. Local overheating
At present, Fyrquel-L produced by ICL-IP Euroре in parts of the system with small consumptions, the
B.V. (United States) is used in oil systems of turbosets of violation of temperature operating regime, also leads
power unit nos. 3 and 4 of the Kalinin NPP and no. 3 of to the degradation of the synthetic oil.
the Kola NPP. The conversion to using fire-resistant Hydrolytic and thermal oil decomposition is the
oils in oil systems of the MCPA electromotor and tur- main cause for the acid number growth [1]. The varia-
bosets of new generation power units with reactor tion of the Fyrquel-L acid number during the operating
facilities BN-800 on the Beloyar NPP, VVER-1200 on time from 2004 to 2013 in the turboset lubrication oil
the Novovoronezh NPP, etc. is examined. system of power unit no. 3 of the Kalinin NPP is shown
The synthetic fire-resistant turbine oil (further in Fig. 2. The accelerated hydrolytic oil decomposition
referred to as oil) is a trixylenyl phosphate [tris- starts when AN = 0.3–0.5 mg KOH/g. The use of the
(dimethylphenyl) phosphates] isomer mixture, that is, oil cleaning plants with ion-exchange technologies
phosphoric acid esters, obtained by the etherification of facilitates the acid number decrease and maintenance
technical xylenols. The turbine oil on the phosphoric on a certain level and prolongs the oil operating life. The
acid esters' basis is subjected to hydrolysis (Fig. 1). The plant connection is efficient and economically reason-
hydrolytic decomposition of the oil occurs in the pres- able when the acid number is 0.2 mg KOH/g at most.
ence of water with the formation of phosphoric acid The uncontrollable formation of the degradation
partial esters, phenolic compounds, which increase acid products decreases the oil operation life and dete-

777
778 GALIMOVA

O O The use of the Karl Fischer coulometric titration


+H2O method [3, 4] is crucially important for determination
O P O HO P O OH
+ of the water content. This method is distinguished by
high sensitivity and allows us to determine the total
O O water content, that is, the total content of free and dis-
solved water. The novel requirement to the water con-
tent of the fire-resistant oil, which is 0.1% at most
Triphenyl phosphate Phosphoric acid Phenolic under the use of the coulometric method control, is
partial esters (diester) compounds imposed in the industry regulations about the organi-
zation of the turbine oils' operation on the NPP [5].
It is known [6] that oil capability to dissolve water
Fig. 1. Scheme of the hydrolytic decomposition of the syn- depends on its chemical composition and increases
thetic fire-resistant oil on the basis of phosphoric acid with rising aromatic hydrocarbon content. Water is
esters. present in the oil in the molecularly dissolved form
and makes a single-phase system with it. As water
quantity increases, the system is saturated. A two-
AN, mg KOH/g phase system in the form of the fine-dispersed free
0.8 water, reacting with the synthetic oil and causing its
hydrolytic decomposition, emerges above the satura-
tion point under a redundant amount of water.
0.6
The characteristic defining conditions of the phase
transition from dissolved to free water (and the transi-
0.4 tion of the free to dissolved water) is a saturation curve.
The water saturation curve for the Fyrquel-L with acid
number 0.11 mg KOH/g at a relative humidity W =
0.2 50% at the temperature range at which the oil is oper-
ated in oil systems of the equipment and is stored in
0 the oil supply facilities of the NPP is shown in Fig. 4.
2004 2006 2008 2010 2012 2014 As follows from the figure, the water solubility in the
Years oil C increases with rise in temperature t, and it is in
the saturated state С = 2.4 g/kg at t = 50°С. In this
Fig. 2. Variation of the Fyrquel-L acid number during the case, in accordance with Henry’s law, the oil heating
operating time in the turboset lubrication system of power at constant air temperature and water content is
unit no. 3 of the Kalinin NPP. accompanied by its dewatering [7]. A part of water dis-
solved before it is released in the form of fine droplets,
forming the emulsion, under the oil cooling (at the
riorates its quality. The decomposition products are constant air temperature and water content).
capable of undergoing a condensation reaction with the
formation of high-molecular compounds, which, The water saturation process of two Fyrquel-L
depending on the oil qualitative state and the operating probes in time τ is presented in Fig. 5. As follows from
conditions, can precipitate on the equipment working the plot, the oil water content at t = 40°С and W =
surfaces in the form of the loose jellylike deposit or the 49% significantly exceeds with time its value at t = 2°С
dense varnished layer (Fig. 3), and they often cause and W = 60%. The oil water solubility is affected by its
equipment failures and operating regime troubles. qualitative composition and the presence of the degra-
dation products and polar impurities. The higher the
The provision of regulations to the oil water con- acid number, the larger the amount of the dissolved
tent and the temperature-operating regime has a pri- water is capable to hold oil. Therefore, the operating
mary importance for maintenance of its operating oil insufficiently purified or with high acid number is
characteristics [2]. difficult to dewater [7].
The analysis of the Fyrquel-L operating experience Information about oil water solubility is important
in oil systems of the NPP equipment shows that the for analysis of its operating conditions in oil systems of
main factor of its decomposition is moisture presence in the equipment and the organization of water content
it. Sources of the moisture entry into the turboset oil control. It is assumed that oil state in the oil system at
system are the turbine end seals, the supply pumps t = 50°С is defined by A, when C = 2.1 g/kg, which
(under the turbine starts and stops), and the oil cooler corresponds to the saturation 88% (see Fig. 4). The
seals. Oil on the phosphoric acid esters' basis is able to position of A below the saturation curve means that
absorb the atmospheric moisture; that is why special there is no free water in the oil. Even small tempera-
demands are made to the storage conditions of the fresh ture differences at various parts of the oil system, for
and the operating oil deposited for the maintenance. example as high as 40°С at the point B, facilitates

THERMAL ENGINEERING Vol. 64 No. 10 2017


APPLICATION OF SYNTHETIC FIRE-RESISTANT OILS IN OIL SYSTEMS 779

(а) (b)

Fig. 3. (a) Jellylike deposits on the main oil box lubrication system construction elements and (b) the varnished layer of deposits
on the control system.

release of the free water from the oil in the “cool” tice, it is recommended to hold the water content at
zones (after oil coolers or in the oil box) and further the level of 45% during the oil operation in the oil sys-
dissolution of the free water in the oil in the “hot” tem, and a vacuum dewatering should be started if it is
zones (at the bearing oil discharge). Therefore, if oil exceeded.
whose water content is close to the saturation state is
operated in the oil system, then the temperature differ- Saturation curves give important information
ences promote water phase transitions to the free or during the choice of the dewatering technology and
dissolved state. The total released free water gradually conditions of the oil storage. There are three possible
decomposes the oil, increasing the acid number and states of the same oil with different water content
facilitating the slime formation. during the operation (Fig. 6). At point 1, oil is oper-
ated at temperature t1; water content С1 above the sat-
Regulated daily visual control does not allow us to
identify for certain the presence of the dissolved water uration curve means that there is free water in the oil.
in the operating oil under exceeding of the normative Separation methods of the oil dewatering allow
water content in the region before the saturation point,
because there is no emulsion. The oil that does not
retain free water and also does not correspond to the C, g/kg
imposed water content regulations can be operated in 2.5
the oil system in accordance with the long time visual
control results (by taking into account periodicity of B А
the quantitative water content control by the Karl 2.0 Free water Cfree 3
Fischer coulometric titration). Thus, the daily water
content control during the oil operation is expedient to 1
organize with the use of automatic controls aimed at 1.5 Cdis
an advanced technological service and stable mainte- Dissolved Cdis
2
nance of the imposed oil quality regulations. 1.0
water
The measurement results with the use of the auto-
matic control can be presented in the form of the water 0.5
content (g/kg) or the saturation (%) [7]. An advantage 0 10 20 30 40 50 t, °C
of the latter parameter is that the readout is attributed
to the actual saturation point and allows evaluation of Fig. 4. The temperature influence on the water solubility
the oil water saturation, and, if necessary, organiza- in Fyrquel-L. (1) Saturation curve; (2) normative water
tion of its dewatering at any current moment. In prac- content; (3) water saturation point of oil.

THERMAL ENGINEERING Vol. 64 No. 10 2017


780 GALIMOVA

С, g/kg It is insufficient to extract only free water under the


water detection in oil. Oil transferred to the storage
needs to be drained as a precaution to prevent water
2.0 1 release with the temperature decrease. The provision
of regulation to the oil water content 0.1% at most
allows oil storing without free water release if there are
1.5
no extra moisture entry sources.
2
1.0
CONCLUSIONS
0.5 3 (1) The decomposition of the synthetic fire-resis-
tant turbine oil occurs in the presence of water with the
formation of phosphoric acid partial esters, phenolic
0 2 4 6 8 10 compounds, which increase the acid number.
τ, day
(2) It is expedient to organize the water content
monitoring with the use of automatic controls to
Fig. 5. Fyrquel-L water saturation dynamics at AN = increase the operating oil in oil system daily quality
0.11 mg KOH/g. (1) t = 40°С, W = 49%; (2) t = 2°С, W = control efficiency.
60%; (3) initial oil state.
(3) The oil cleaning equipment should provide
complex operating oil cleaning from contaminations
C and water releasing. To release effectively free and dis-
C1 1
solved water from the oil, it is necessary to use vacuum
dewatering.
4 Free water
C4
C2, C5 5 REFERENCES
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THERMAL ENGINEERING Vol. 64 No. 10 2017