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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

AbstractResults 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 the bearing regulating and lubricating systems, the auxiliary pumping equipment of turbosets, and oil sys- tems of the main circulating pump aggregate (MCPA). At present, Fyrquel-L produced by ICL-IP Euroре B.V. (United States) is used in oil systems of turbosets of power unit nos. 3 and 4 of the Kalinin NPP and no. 3 of the Kola NPP. The conversion to using fire-resistant oils in oil systems of the MCPA electromotor and tur- bosets of new generation power units with reactor facilities BN-800 on the Beloyar NPP, VVER-1200 on the Novovoronezh NPP, etc. is examined. The synthetic fire-resistant turbine oil (further referred to as oil) is a trixylenyl phosphate [tris- (dimethylphenyl) phosphates] isomer mixture, that is, phosphoric acid esters, obtained by the etherification of technical xylenols. The turbine oil on the phosphoric acid esters' basis is subjected to hydrolysis (Fig. 1). The hydrolytic decomposition of the oil occurs in the pres- ence of water with the formation of phosphoric acid partial esters, phenolic compounds, which increase

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acid number (AN), characterizing number of the oil acid components and expressed in milligrams (mg) of the potassium hydroxide (KOH) required for titration of 1 g oil to the neutralization point. Local overheating in parts of the system with small consumptions, the violation of temperature operating regime, also leads to the degradation of the synthetic oil. Hydrolytic and thermal oil decomposition is the main cause for the acid number growth [1]. The varia- tion of the Fyrquel-L acid number during the operating time from 2004 to 2013 in the turboset lubrication oil system of power unit no. 3 of the Kalinin NPP is shown in Fig. 2. The accelerated hydrolytic oil decomposition starts when AN = 0.3–0.5 mg KOH/g. The use of the oil cleaning plants with ion-exchange technologies facilitates the acid number decrease and maintenance on a certain level and prolongs the oil operating life. The plant connection is efficient and economically reason- able when the acid number is 0.2 mg KOH/g at most. The uncontrollable formation of the degradation acid products decreases the oil operation life and dete-

778 GALIMOVA O O +H 2 O The use of the Karl Fischer coulometric titration
778
GALIMOVA
O
O
+H 2 O
The use of the Karl Fischer coulometric titration
method [3, 4] is crucially important for determination
OH
O
P O
HO
P
O
+
of the water content. This method is distinguished by
high sensitivity and allows us to determine the total
O
O
Triphenyl phosphate
Phosphoric acid
partial esters (diester)
Phenolic
compounds
Fig. 1. Scheme of the hydrolytic decomposition of the syn-
thetic fire-resistant oil on the basis of phosphoric acid
esters.
AN, mg KOH/g
0.8
0.6
0.4
0.2
0
2004
2006
2008
2010
2012
2014
Years
Fig. 2. Variation of the Fyrquel-L acid number during the
operating time in the turboset lubrication system of power
unit no. 3 of the Kalinin NPP.
riorates its quality. The decomposition products are
capable of undergoing a condensation reaction with the
formation of high-molecular compounds, which,
depending on the oil qualitative state and the operating
conditions, can precipitate on the equipment working
surfaces in the form of the loose jellylike deposit or the
dense varnished layer (Fig. 3), and they often cause
equipment failures and operating regime troubles.
The provision of regulations to the oil water con-
tent and the temperature-operating regime has a pri-
mary importance for maintenance of its operating
characteristics [2].
The analysis of the Fyrquel-L operating experience
in oil systems of the NPP equipment shows that the
main factor of its decomposition is moisture presence in
it. Sources of the moisture entry into the turboset oil
system are the turbine end seals, the supply pumps
(under the turbine starts and stops), and the oil cooler
seals. Oil on the phosphoric acid esters' basis is able to
absorb the atmospheric moisture; that is why special
demands are made to the storage conditions of the fresh
and the operating oil deposited for the maintenance.
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
under the use of the coulometric method control, is
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
depends on its chemical composition and increases
with rising aromatic hydrocarbon content. Water is
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-
phase system in the form of the fine-dispersed free
water, reacting with the synthetic oil and causing its
hydrolytic decomposition, emerges above the satura-
tion point under a redundant amount of water.
The characteristic defining conditions of the phase
transition from dissolved to free water (and the transi-
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 =
50% at the temperature range at which the oil is oper-
ated in oil systems of the equipment and is stored in
the oil supply facilities of the NPP is shown in Fig. 4.
As follows from the figure, the water solubility in the
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
case, in accordance with Henry’s law, the oil heating
at constant air temperature and water content is
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
constant air temperature and water content).
The water saturation process of two Fyrquel-L
probes in time τ is presented in Fig. 5. As follows from
the plot, the oil water content at t = 40°С and W =
49% significantly exceeds with time its value at t = 2°С
and W = 60%. The oil water solubility is affected by its
qualitative composition and the presence of the degra-
dation products and polar impurities. The higher the
acid number, the larger the amount of the dissolved
water is capable to hold oil. Therefore, the operating
oil insufficiently purified or with high acid number is
difficult to dewater [7].
Information about oil water solubility is important
for analysis of its operating conditions in oil systems of
the equipment and the organization of water content
control. It is assumed that oil state in the oil system at
t = 50°С is defined by A, when C = 2.1 g/kg, which
corresponds to the saturation 88% (see Fig. 4). The
position of A below the saturation curve means that
there is no free water in the oil. Even small tempera-
ture differences at various parts of the oil system, for
example as high as 40°С at the point B, facilitates
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2017

APPLICATION OF SYNTHETIC FIRE-RESISTANT OILS IN OIL SYSTEMS

(а)

(b)

779

OF SYNTHETIC FIRE-RESISTANT OILS IN OIL SYSTEMS (а) (b) 779 Fig. 3. (a) Jellylike deposits on

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” zones (after oil coolers or in the oil box) and further dissolution of the free water in the oil in the “hot” zones (at the bearing oil discharge). Therefore, if oil whose water content is close to the saturation state is operated in the oil system, then the temperature differ- ences promote water phase transitions to the free or dissolved state. The total released free water gradually decomposes the oil, increasing the acid number and facilitating the slime formation.

Regulated daily visual control does not allow us to identify for certain the presence of the dissolved water in the operating oil under exceeding of the normative 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 imposed water content regulations can be operated in the oil system in accordance with the long time visual control results (by taking into account periodicity of the quantitative water content control by the Karl Fischer coulometric titration). Thus, the daily water content control during the oil operation is expedient to organize with the use of automatic controls aimed at an advanced technological service and stable mainte- nance of the imposed oil quality regulations.

The measurement results with the use of the auto- matic control can be presented in the form of the water content (g/kg) or the saturation (%) [7]. An advantage of the latter parameter is that the readout is attributed to the actual saturation point and allows evaluation of the oil water saturation, and, if necessary, organiza- tion of its dewatering at any current moment. In prac-

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2017

tice, it is recommended to hold the water content at the level of 45% during the oil operation in the oil sys- tem, and a vacuum dewatering should be started if it is exceeded.

Saturation curves give important information during the choice of the dewatering technology and conditions of the oil storage. There are three possible states of the same oil with different water content during the operation (Fig. 6). At point 1, oil is oper- ated at temperature t 1 ; water content С 1 above the sat- uration curve means that there is free water in the oil. Separation methods of the oil dewatering allow

C, g/kg 2.5 B А 2.0 Free water 3 C free 1 1.5 C dis
C, g/kg
2.5
B А
2.0
Free water
3
C free
1
1.5
C dis
Dissolved
C dis
2
water
1.0
0.5
0
10 20
30 40
50 t, °C

Fig. 4. The temperature influence on the water solubility in Fyrquel-L. (1) Saturation curve; (2) normative water content; (3) water saturation point of oil.

780 GALIMOVA С, g/kg It is insufficient to extract only free water under the water
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
1
2.0
1.5
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
no extra moisture entry sources.
2
1.0
CONCLUSIONS
3
0.5
0 2
4
6
8
10
(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
compounds, which increase the acid number.

τ, day

Fig. 5. Fyrquel-L water saturation dynamics at AN = 0.11 mg KOH/g. (1) t =
Fig. 5. Fyrquel-L water saturation dynamics at AN =
0.11 mg KOH/g. (1) t = 40°С, W = 49%; (2) t = 2°С, W =
60%; (3) initial oil state.
C
C 1
1
4
Free water
C 4
C 2 , C 5
5
2
Dissolved water
C 3 , C 6
6
3
t
t 2
t 3
t 1

Fig. 6. Conditions of the use of the oil cleaning plants for the oil dewatering during the operation and storage.

extracting only free water, and the water content С 4 is achieved. The emergence of free water (point 4) is sub- sequently observed during the oil purification with the use of the separation technologies of cooling to the storage temperature t 2 . At point 3, oil is operated at temperature t 1 with the use of the vacuum dewatering plants, and the water content С 3 is significantly lower than the saturation point. The water content С 6 remains below the satura- tion curve under the oil cooling to the storage tem- perature t 2 (point 6), which allows storing the oil with- out free water release. Oil operation in the state corresponding to the point 2 requires separate consideration. At the operat- ing temperature t 1 , the water content С 2 is slightly below the saturation point, and there is no free water in the system here. Free water release, facilitating the synthetic oil decomposition (point 5), occurs at slight oil temperature decrease in the oil system to t 3 or during the transfer of such contingently dried oil to the storage at temperature t 2 .

(2) It is expedient to organize the water content monitoring with the use of automatic controls to increase the operating oil in oil system daily quality control efficiency.

(3) The oil cleaning equipment should provide complex operating oil cleaning from contaminations and water releasing. To release effectively free and dis-

solved water from the oil, it is necessary to use vacuum dewatering.

REFERENCES

1.

L.

A. Galimova, D. V. Seleznev, and S. G. Ambar-

tsumyan, “Topical issues of the organization of opera-

tion of synthetic fire-resistant oils in oil systems of nuclear power plant equipment,” in Proc. 10th Int. Sci.- Tech. Conf. on Safety, Efficiency and Economics of Nuclear Energy, Moscow, May 25–27, 2016 (Moscow, 2016), pp. 70–74.

2.

V. A. Gashenko, L. A. Galimova, D. V. Shuvarin, and

D.

V. Kurganov, “The program of measures aimed at

improving level of operation, improving the test meth- ods and quality control of turbine and transformer oils used at nuclear power plants,” in Proc. 8th Int. Sci.- Tech. Conf. on Safety, Efficiency and Economics of Nuclear Energy, Moscow, May 23–25, 2012 (Moscow, 2012), pp. 114–115.

3.

GOST R 54281-2010. Petroleum Products, Lubricating Oils and Additives. Water Determination by Karl Fischer Coulometric Titration Method (Standartinform, Mos- cow, 2012).

4.

GOST 24614-81. Liquids and Gases that Do Not Interact with Fischer’s Reactive. Coulometric Method of Water Determination (Izd. Standartov, Moscow, 1981).

5.

RD EO 1.1.2.05.0444-2016. Requirements to the Opera- tion, Organization and Testing of Transformer and Tur- bine Oils at Nuclear Power Plants (Rosenergoatom, Moscow, 2016).

6.

R.

A. Lipshtein and M. I. Shakhnovich, Transformer

Oil (Energoatomizdat, Moscow, 1983) [in Russian].

7.

V.

N. Kazanskii, A. E. Yazykov, and N. Z. Belikova,

Bearings and Lubrication Systems of Power Turbines (Tsitsero, Chelyabinsk, 2004) [in Russian].

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Translated by D. Churochkin

Vol. 64

No. 10

2017