EFFECT OF H Y D R O C A R B O N COMPOSITION OF T R A N S F O R M E R

O I L ON D I E L E C T R I C LOSSES

R. A. L i p s h t e i n and E. N. S h t e r n UDC 665.821.5

According to [1], aromatic hydrocarbon fractions isolated from oils have higher conductivities than the paraf-
finic-naphthenic fractions.

In cracking out this statement, we demonstrated as early as 1989 [2] that, by very thorough removal of con-
taminants, it was possible to obtain aromatic hydrocarbon fractions characterized by very low vatues of the d i e l e c -
tric loss-angle tangent at a frequency of 50 Hz (tan 670 < 0.01%).

However, more recently, additional e x p e r i m e n t a l data have been published [3, 4] indicating that the tan 6 at
80 Hz is higher for a r o m a t i c hydrocarbon fractions than for paraffinic-naphthenic hydrocarbon fractions. Moreover,
in [4], the higher values of tan 6 at 50 Hz or the aromatic hydrocarbons were predicated on their higher polarities,
i.e., on large dipole moments.

This idea conflicts with theoretical concepts of the nature of d i e l e c t r i c losses [5, 6]. According to [6], there
are no p o l a r i z a t i o n - r e l a t e d d i e l e c t r i c losses at 60 Hz with a transformer oil at normal operating temperatures, since
the oil viscosity is low and hence the r e l a x a t i o n t i m e is short, Therefore, under these conditions, tan 6 cannot be
related to the dipole m o m e n t of the hydrocarbons comprising the oil.

This is also supported by our e x p e r i m e n t a l data indicating that tan 6 at 50 Hz is determined entirely by the
conductivity (o). The function tan 6 ( a ) proves to be linear, and o / t a n 8 = 1/(1,63.101~ [7]. At high frequencies
and for more viscous oils, d i e l e c t r i c losses are governed not only by direct conductivity, but also by d i p o l e - r e l a x a -
tion polarization [5, 1].

Since the question of optimum hydrocarbon composition is of basic significance in determining trends in i n -
s u l a t i n g - o i l production technology, we returned to this question, bringing in new e x p e r i m e n t a l data.

The objects of investigation were fractions separated chromatographically on silica g e l from a transformer
oil d i s t i l l a t e from Anastasievka crude.

During the first days after the hydrocarbon fractions were prepared, all of them (including the aromatic frac-
tions) were colorless and were characterized by very low values of tan 6, less than 0.008% at ?0~ *

At the t i m e the basic experiments were conducted, the aromatic hydrocarbon fractions had developed some
resins and had acquired a yellowish-greenish color as a result of the prolonged storage (about one year). Supple-
mentary treatment with silica gel and activated carbon did not give c o m p l e t e decolorization.

The experiments were conducted as follows: the dried test sample was poured into the plane eIectrode, which
was mounted in an a i r - b a t h thermostat; this was heated gradually over 6.8 h to t25~ and the s a m p l e was held at
128 :k 0.5~ for 30 rain. The sample was then cooled and ieft in the thermostat until the following day; on t h e n e x t
day, these operations were repeated, etc. The results of these experiments are shown in Fig. 1.

On heating the samples to 70~ during the first day of test, tan 6 remained very low (less than 0.005%, i.e.,
within the e x p e r i m e n t a l error) except in the case of the fraction of heavy monocyclic a r o m a t i c hydrocarbons. With
further heating to 128~ tan 6 increased m a r k e d l y - t o 0.14-0.16% for the paraffinic-naphthenic fraction,t 0.56%
for the light monocycIic aromatics, 3.30% for the heavy m o n o c y c l i c aromatics, and 0.86% for the b i c y c l i c aro-
matics.

* The tan 3 determinations were performed with a plane electrode with c h r o m e - p l a t e d surfaces, using a MDP bridge.
The samples were predried 48 h in a crystallizing dish placed in a desiccator containing freshly calcined c a l c i u m
chloride in the bottom.
t" Figure 1 contains no data for the paraffinic-naphthenic fraction in the Russian o r i g i n a l - P u b l i s h e r .
VTI ira. F. E. Dzerzhinskogo IF. E. Dzerzhinskii All-Union Scientific-Research Power Engineering Institute].
Translated from Khimiya i Tekhnologiya Topliv i Maset, No. 5, pp. 51-53, May, 1967.

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TABLE I. Variation in tan 6 and Color of Paraffinic-Naphthenic and Aromatic Fractions and Blends in the Process
of Prolonged Heating (Testing ,conditions: oil in plane electrode, heated to 100~ for 6 h in air thermostat first
three days, and to 125~ on fourth day)

paraffinic-naph- I Medium aromatic Hydrocarbon blends

thenic fraction, / fraction, 15% aromatic, 50% aromatic,
n ~ = 1.4762 ~ n ~ = 1.5281 85% naphthenic 50% naphthenic

tan 6, %
After first day of test, at 100"C 0.010 O. 560 0.012 0.023
Calculated tan 6 at 100~ 0.080 0.240
After three days of test, at 100~ 0.019 0.750 0.013 0.042
Calculated tan 5 at 100~ 0.130 0.380
After four clays of test, at 125~ 0.160 3. 340 0.140 0.240
Calculated tan 6 at 125~ 0.530 1.750

Color (optical density)

Optical density before test 0.000 0.552 0.080 0.280
Optical density after 4 days of test 0.001 1.000 O. 370
Change in optical density (AD) 0.001 0.450 0.090
Calculated AD* 0.220

~ a i c u l a t e d on basis of additivity of properties for blends.

C
- b 1
~6- ~d

f,2 - 2 9

g8- o,~ 1 o~
6
1
~4 o,4

50 75 /UO f25 50 75 /00 12S 50 7E I00 125

Temperature, ~

Fig. 1. Variation of tan 5 of aromatic hydrocarbons during test: a) fraction of monocyclic aromatic hydrocarbons
(n~ = 1.4979); b) same (n~ = 1.5281); c) fraction of bicyclic aromatic hydrocarbons (n~ = 1.5505). 1) First day of
test of hydrocarbon fractions without additive; 2) second day of test of same hydrocarbon fractions; 3) first day of
test of hydrocarbon fractions with 0.3% ionol; 4) second day of test of hydrocarbon fractions with 0.3% ionol; 5)third
day of test of hydrocarbon fractions with 0.3% ionol; 6) first day of test of hydrocarbon fractions without additive,
in nitrogen medium.

During the second heating to 125~ on the following day, tan 6 remained essentially constant over the entire
temperature range in the case of the paraffinic-naphthenic fraction but increased substantially in the case of the
aromatic fractions.
These data would appear to support the conclusions of the authors cited [1, 3, 4] as to the higher tan 5 of
aromatic hydrocarbons. Such a statement would be premature.
The increase in tan 5 for the aromatic hydrocarbon fractions in the second day and still more in the third day
of test furnishes support for the belief that the source of dielectric losses is not the hydrocarbons themselves butrather
conversion products. We had demonstrated previously that, in dry petroleum oils, dielectric losses at 50 Hz are
proportional to conductivity and are governed by the presence of resins, acidic products, and soaps that form a col-

364
 0,~ l o i d a l solution in the liquid d i e l e c t r i c , and also by the presence
of low m o l e c u l a r weight acids if they p r e c i p i t a t e in the form
0,G of a microemulsion [7].

0,~ According to the d a t a of [8], the naphthenic hydrocarbons

of oils age with the formation of oxygen-containing compounds
of nonresinous nature, whereas the aromatic hydrocarbons age
~O with the formation of resinous condensation products.
o,3 0,e g Since no metals were d e t e c t e d in any of these fractions
after t h r e e - d a y tests (ash contents zero), nor were any low m o l -
e c u l a r weight acids present (water extract reaction neutral), it
m a y be assumed that, in accordance with [8, 2], the substances
o,1

o,2
9
0,4, 0,e ga I,o
1;
r
increasing tan 6 for the aromatic hydrocarbon are resins. This
hypothesis is supported by the fact that the a r o m a t i c hydrocar-
bon fractions b e c a m e yellow during the course of the test, where-
Resin concentration, % as the paraffinic-naphthenic hydrocarbon fraction remained
p r a c t i c a l l y colorless.
Fig. 2. O p t i c a l density and tan ~ of oil is func-
tions of resin concentration. This hypothesis could be confim~ed by experiments in
which the a r o m a t i c hydrocarbon fractions are not subjected to
condensation reactions, under which conditions tan 6 shouId
r e m a i n unchanged over long periods of heating.

T e c h n i c a l difficulties are involved in the direct d e t e r m i n a t i o n of tan 6 for degassed fractions in vacuum or
in a nonoxidizing gas m e d i u m , owing to the lack of any h e r m e t i c a l l y sealed electrode. However, it was found
feasible to conduct an e x p e r i m e n t in which the thermostat containing the open electrode with a pre-degassed s a m -
ple of heavy m o n o c y c l i c aromatics was purged continuously with bottled nitrogen for a seven-hour test period; under
these test conditions, tan 5 at 125~ c a m e out one-sixth of the value without nitrogen purge, i.e., 0.52% vs. 3.30%

It is well known that the oxidation inhibitor 2 , 6 - d i - t e r t - b u t y l - 4 - m e t h y l p h e n o l (ionol) is e x t r e m e l y effective

in retarding resin and sludge formation processes in oils and at the same t i m e has no effect on the conductivity of
the o i l
The results of tan 6 determinations under the given test conditions for aromatic hydrocarbon fractions with
0.3% of this additive are shown in Fig. 1. It can be seen that the additive prevented resin formation in the aromatic
fractions; this showed up in the form of a lower first-day tan 5 (0.02 vs. 0.56% for the tight monocyclics and 0.10
vs. 3.30% for the heavy monocyclics).

It is important to note that tan 5 at 125~ for the m o n o c y c l i c aromatics inhibited with ionol was even lower
than for the uninhibited fractions of paraffinic-naphthenic hydrocarbons.

On the basis, it can be affirmed that tan /5 at 50 Hz over a wide range of operating t e m p e r a t u r e s (from 20 to
125~ is e x t r e m e l y low not only for the paraffinic and naphthenic hydrocarbons but also for the a r o m a t i c hydro-
carbons of transformer oils, and that the increase in tan /5 during test under conditions of oxygen "starvation" is
caused by the formation of condensation products that give a c o l l o i d a l solution in the oil.

The quality of a liquid d i e l e c t r i c is rated not only by the magnitude of tan ~ in the initial state, but also by
the constancy of tan i5 during service.

From this point of view, paraffinie and naphthenic hydrocarbons have an advantage over aromatic hydrocar-
bons in their lesser tendencies toward resin formation. However, paraffinic-naphthenic hydrocarbon fractions with-
out aromatics cannot be used, becuase of their tow c h e m i c a l stability [8] and low resistance to gassing in an e l e c -
tric field [1].

At the same t i m e , a r o m a t i c hydrocarbon fractions without naphthenes, even with antioxidants, are not neces-
sarily usable. In the first place, the b i c y c l i c aromatic hydrocarbons present in oils are poor in additive response
(see Fig. 1); in the second place, the effective life of additives is l i m i t e d because of additive consumption in the
process of oxidative aging of the o i l

In this connection, it was of interest to study the question of interaction of aromatic and paraffinic-naphthenic
fractions with respect to change in tan /5 under the indicated conditions (see table). It was found that the paraffinic-

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naphthenic fraction acted as a stabilizer of the aromatic fraction; it retarded the processes leading to increase in
tan 5 with prolonged heating of the sample in the electrode, i.e., with thermal aging under conditions of oxygen
"starvation."
Thus, the addition of the paraffinic-naphthenic fraction to the aromatic fraction in i/I ratio eliminated
changes in the sample during three-day heating in the electrode to 100~ Under these conditions, tan 5 was 0.02%
for the paraffinic-naphtenic fraction, 0.75% for the aromatic fraction, and 0.04%0 for the blend. If the blend prop-
erties were additive, tan 5 would have been 0.38%, i.e., some I0 times the experimental value.

Additivity of tan 5 for blends (based on wt. %o) has been demonstrated for oils of differing origin and for blends
of white oil with resins recovered from a transformer oil distillate of Balakhany crude (see Fig. 2).

After three days of heating the samples in the electrode to 100~ and one day to 125~ tan 5 had increased
to 0.16% for the paraffinic-naphthenic fraction, 3.340/0for the aromatic fraction, and to only 0.24% for the blend.
Based on additivity of properties, tan 5 of the blend should have increased to 1.75%.

The nonadditive lowering of tan 5 of aromatic hydrocarbons by naphthenic hydrocarbons is related to retarda-
tion of the final processes of resin formation, i.e., apparently ~etardation (in accordance with the dilution principle
of Ruggli-Ziegler [9]) of the reactions of polycondensation and polyaddition of difunctional or polyfunctional mole-
cules and an increase in intramolecular reactions with ring closure without the formation of macromolecules.

CONCLUSIONS

1. It has been shown experimentally that the hydrocarbons making up petroleum-derived transformer oils
(isoparaffinic, naphthenic, naphthenic-aromatic, and aromatic hydrocarbons) are characterized by very low values
of tan 5 (within the experimental error) at 50 Hz and temperatures from 20 to 125~

2. In the process of determining tan 5 during prolonged heating to high temperatures (100-125~ aromatic
hydrocarbons from resins, causing an increase in tan 5. This explains the lack of agreement with the data of [1,
3, 4].

3. When the additive 2 , 6 - d i - t e r t - b u t y l - 4 - methylphenol (ionol) is used in a fraction of monocyclic aromatic

hydrocarbons isolated from a transformer oil distillate, it retards the processes of resin formation and the increase
in tan 5. A fraction of bicyclic aromatic hydrocarbons has iittle response to the action of ionol.

4. When aromatic hydrocarbons are diluted with substantial amounts of naphthenes, the tendency of the aro-
matics toward resin formation during aging under conditions of oxygen "starvation" is decreased sharply, out of pro-
portion to the amount of dilution. This phenomenon can serve as the basis for producing oils that will change little
in dielectric properties during service.

LITERATURE CITED
1. S. ~. Krein and R. V. Kulakova, petroleum Insulating Oils [in Russian, Gos~nergoizdat (1959).
2. IL A. Lipshtein and M. I. Shakhnovich, Trnasformer Oil [in Russian], Izd. ~nergiya, 161 (1964).
3. R. V. Kulakova and M. G. Kopkin, Vestnik ~lektropromyshlennosti, No. 12 (1962).
4. N. G. Kalantar, Vestnik ~lektropromyshlennosti, No. 7 (1961).
5. G. I. Skanavi, Physics of Dielectrics [in Russian], Gostekhteorizdat (1949).
6. B. M. Vul, ~lektrichestvo, No. 1 (1949).
7. R. A. Lipshtein and E. N. Shtern, Inzhenerno-fizicheskii Zhurnal, No. 2 (1962).
8. N. I. Chernozhukov and S. ~. Krein, Oxidizability of Mineral Oils [in Rnssian],Gostoptekhizdat, p. 162.
9. P. Karrer, Course in Organic Chemistry [in Russian], Goskhimizdat (1962).

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