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Methanol: A Novel Approach to Power Transformer Asset Management

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DOI: 10.1109/TPWRD.2012.2185957

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Jocelyn Jalbert Yves Denos

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514
Methanol: A Novel Approach to Power
Transformer Asset Management
Jocelyn Jalbert, Senior Member, IEEE, Roland Gilbert, Yves Denos, and Pierre Gervais
Abstract—All electrical utilities deal with the task of determining
the residual life of their in-service power transformers. Given the
difficulties experienced with the use of first and second generations
of markers (carbon oxides and 2-furfuraldehyde), several organi-
zations are now considering the use of methanol for this purpose.
Hydro-Québec, which discovered this approach, uses this molecule
on a regular basis to evaluate the state of the cellulose insulation
of in-service power transformers and applies it to Électricité de
France’s nuclear power plant transformers. In this paper, some
examples of the application of methanol in the field are presented
against the information received from the early marker genera-
tions.
Index Terms—Asset management, carbon oxides, cellulose
degradation, insulating paper, methanol, 2-furfuraldehyde,
residual life.
I. INTRODUCTION
HE END OF THE useful life of an in-service transformer
T strongly correlates to the degree of its insulation paper
degradation. Concerning the diagnosis of transformer internal
insulation, the first efforts focused on the use of CO and CO ,
quantified by dissolved gas analysis (DGA) analysis, for the de-
tection of faults occurring in the paper or oil components. How-
ever, the situation is more complex with respect to useful life
due to the potentially long aging time an apparatus may experi-
ence ( 20 years). For example, in open breathing transformers,
the presence of a sufficient amount of oxygen is favorable to the
generation of CO/CO from the oil and the paper degradation
processes, with the paper moisture being a parameter of prime
importance [1].
Moreover, in open-breathing transformers, the carbon oxides
can escape from the systems and completely disappear during
operations, such as oil degassing or regeneration; the low sol-
ubility of CO/CO in the insulation paper compared to the one
Manuscript received July 07, 2010; revised February 10, 2011, April 13,
2011, May 19, 2011, December 13, 2011; accepted January 22, 2012. Date of
publication March 06, 2012; date of current version March 28, 2012. This work
was supported in part by Hydro-Québec TransEnergie and in part by Electricité
de France. Paper no. TPWRD-00515-2010.
J. Jalbert is with the Institut de recherche d’Hydro-Québec (IREQ), Varennes,
QC J3X ISI Canada (e-mail: Jalbert.jocelyn@ireq.ca).
R. Gilbert, retired, was with the Institut de recherche d’Hydro-Québec,
Varennes, QC J3X ISI Canada.
Y. Denos was with Electricité de France (EDF R&D) Themis Group, Clamart
92141, France. He is now with the ENERBAT Department, Monet sur Loing
77818, France (e-mail: denos.yves@edf.fr).
P. Gervais, retired, was with Hydro-Québec TransEnergie, Montreal, QC
H5B 1H7 Canada.
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TPWRD.2012.2185957
0885-8977/$31.00 © 2012 IEEE
IEEE TRANSACTIONS ON POWER DELIVERY, VOL. 27, NO. 2, APRIL 2012
in the oil [2] prevents marker re-equilibration in the oil, after
which its correlation with the insulation paper degradation be-
comes meaningless. Since a transformer most likely experiences
some maintenance work during its useful life and some leaks
may be observed in sealed transformers, the use of the CO/CO
content to detect or predict the end of useful life becomes highly
questionable.
An alternative approach consists in considering a family of
furan compounds, especially 2-furfuraldehyde (2-FAL), more
specifically linked to paper insulation breakdown [3], though
many drawbacks have to be taken into account. In particular,
the presence of a very small amount of 2-FAL for thermally up-
graded insulation paper (TU paper) renders its detection a la-
borious process [4], [5]; the high production rate from hemi-
celluloses compared to cellulose [6], the thermal instability of
the compound [7], and the effect of moisture on the rate of pro-
duction [5] are among the concerns utilities are facing. Conse-
quently, the use of 2-FAL as a chemical marker for establishing
the remaining life of cellulose insulation is under scrutiny by the
scientific community.
Recently, the use of methanol (CH OH) has been reported
for the first time in the literature by Jalbert et al. [8] for es-
timating the degree of cellulose insulation degradation. Labo-
ratory tests showed that methanol is mainly produced during
the aging of oil-impregnated paper insulation at 60 C–120 C
(inhibited naphthenic oil under air), regardless of whether the
specimens are thermally upgraded. This work revealed the exis-
tence of a direct relationship between CH OH production and
the scission of 1,4-ß-glycosidic bonds (bonds that link the cel-
lulose glucose units). Moreover, methanol was detected in the
aging tests in the early scissions of the bonds even at temper-
atures as low as 60 C. More recently, a kinetics study car-
ried out by the same research group on standard-Kraft paper
(std) [9] and on TU-Kraft paper [10] showed that depolymer-
ization and methanol production required an activation energy
of about 104 kJmol , thus confirming the link between
the two processes. Moreover, the production of methanol and
broken cellulose chains showed about the same value for the
exponential factors of the Arrhenius expression, which in-
troduces the possibility that the rate of production of CH OH
from chopped chains is much higher than the rate of depolymer-
ization, so that the latter becomes the rate determining step of
the overall reaction. This means that contrary to the 2-FAL, the
methanol is instantaneously produced after the opening of the
1,4-ß-glycosidic bonds and, consequently, detected early in the
oil. These authors also demonstrated the role played by oxygen
and moisture on the exponential factors as obtained from the
application of different degradation models: pseudozero Eken-
stam’s rate constants [11], first-order time-dependent decrease
JALBERT et al.: METHANOL: A NOVEL APPROACH TO POWER TRANSFORMER ASSET MANAGEMENT 515

of k [12], power law [13], and single first-order evolution equa- TABLE I
tion [14] by comparing paper aging in naphthenic oil under air INSTRUMENTAL CONDITIONS FOR THE HSGC/MS ANALYSIS OF METHANOL
with paper aging in uninhibited paraffinic oil under nitrogen.
Finally, the oil of different pieces of equipment from Hydro-
Québec’s grid (e.g., transformers, shunt reactors, current trans-
formers) was sampled and assessed for CH OH and 2-FAL. The
results showed that methanol is detected in more than 94% of the
900 units studied, compared to 56% for 2-FAL. In this survey,
the data showed a marked decrease in 2-FAL concentrations
around the 1970s, which corresponded to the introduction of
TU-Kraft paper in Hydro-Québec’s equipment [8]. In addition,
to demonstrate the advantages of methanol over the earlier gen-
erations of markers, another thorough survey was conducted by
comparing all of the molecules (methanol, carbon oxides, and
2-FAL) in oil samples collected from about 290 power trans-
formers currently operated by EDF. A comparison of the as-
sessed concentrations was used to establish the limits of each
marker. This paper reviews some of the results obtained from
these field surveys.

II. EXPERIMENTAL
Transformer Oil Sampling: The transformer oil samples were
collected on load in accordance with the ASTM D 923 test
method or IEC 60475 (the oil temperature was noted during the
sampling). One aliquot sample was sent to an external labora-
tory for DGA and moisture analysis while the remaining volume
was used at IREQ for the CH OH and 2-FAL measurements.
Apparatus and Methods: A G1888 static headspace sam-
pler, coupled with a 6890N gas chromatograph equipped with
a 5973N mass selective detector at 70-eV ionization energy in
the electron impact mode (all from Agilent Technologies), was
used to assess the methanol. The instrument interface was main-
tained at 250 C and a mass range 300 amu, in a
0.21-s cycle, was scanned in total ion count mode (TIC). The Fig. 1. Insulation transformer life curve using methanol.
separation was performed with a 60-m-long Stabilwax (Restek)
polar column, 0.25 mm in diameter and with 0.5- m film thick-
ness; the instrumental conditions are given in Table I. The signal Fig. 1 illustrates the signal intensity of the methanol content in
was calibrated by injecting a series of dilutions prepared from a oil versus the effective service time of transmission power trans-
mother solution of methanol in oil at a maximum concentration formers of known average loading. The -axis corresponds to
level of 10 ppm (w/w) (6-point calibration curves). Quantifica- the effective service time in years as defined elsewhere [15]
tion was carried out in the selected ion monitoring (SIM) mode. (1)
2-FAL was assessed using high-performance liquid chro-
matography (Agilent Technologies, 1100 Series). The signal where Y is the number of years in service and L is the average
was calibrated (6-point calibration curves) by injecting a series operating load factor. This relationship enables a comparison
of dilutions prepared from a mother solution of 2-furfuralde- on the same basis of equipment operating under different load
hyde in oil at a maximum concentration of 2.5 ppm (w/w). levels. For example, the of a 10-year-old apparatus oper-
The carbon–oxide content was obtained by an external lab- ating under 100% of its rated load is 10 years (e.g., applicable
oratory using a normalized technique, such as ASTM D 3612 to generator transformers) while that of a 10-year-old apparatus
Method C or IEC 60233. at 50% of its rated load is 5 years (e.g., applicable to transmis-
sion-line transformers).
III. RESULTS AND DISCUSSION The use of methanol data in conjunction with DGA diag-
nosis makes it possible to identify the units affected by an ab-
A. Survey of Field Transmission Transformers normal paper aging rate. Some points illustrated in Fig. 1 corre-
The difficulty associated with transmission transformers spond to equipment with signs of low energy arcing or hot spots
arises from the fact that their loads are not constant (i.e., the during operation according to DGA measurements, most likely
internal temperature varies) and, in addition, they may have with/without any insulating paper problems. For example, the
been offload many times while in service. For this reason, the six data points corresponding to the very large signal intensity
paper insulation aging may be poorly related to service time. values of the methanol content (note the break in the Y axis)
516
Fig. 2. Diagnosis of paper damage using methanol in the CT.
point to the presence of hot spots at the paper level from DGA
measurements. The presence of abnormal cellulose aging was
further supported by cooling problems which were manifested
during several days for the equipment under consideration.
However, the present approach used for the diagnosis of
power transformers may not be extrapolated to current trans-
formers (CTs). For the latter, no significant load is generally
observed, which means that the correlation with methanol
signal intensity and is irrelevant, as illustrated in Fig. 2.
As expected, the signal intensity in relative units is very low
for CTs compared to those for the power transformers, and
no particular trends may be conducted for these systems. The
only cases showing a significantly higher content for methanol
are those where a corona discharge or a hot spot is present,
suggesting that paper damage occurred in these CTs (see
Fig. 2). These examples show the applicability of methanol for
detecting paper aging in different pieces of equipment.
Finally, Fig. 3 presents a comparison of the relative concen-
trations of the three markers under consideration as obtained
from the units of a given substation. (Each unit’s in-service year
is given at the top of the respective bar graph.) The concen-
trations were normalized by adjusting the maximum concen-
tration to 100%. These core-open-breathing transformers were
from different manufacturers, with some units equipped with
TU-Kraft paper (units #1, 3, and 9). As expected, all of the
markers show a quantitative response for the apparatus in op-
eration from 1961 to 1962 (units #2, 5, 7, and 8) equipped with
standard-Kraft paper. For unit #2, the carbon oxides are char-
acterized by a high value compared to the levels found for the
other markers; this behavior can be explained by the fact that
these oxides could also be produced from oil oxidation (acidity
of 0.1 mg KOH/g of oil). For the unit in service in 1967 (unit #4),
which shows marginal amounts of both CH OH and carbon ox-
ides, the use of TU-paper cannot be confirmed. But the fact that
2-FAL is not detected indicates that this unit probably contains
TU-paper. The other apparatus equipped with TU-paper shows
IEEE TRANSACTIONS ON POWER DELIVERY, VOL. 27, NO. 2, APRIL 2012
Fig. 3. Comparison of the three markers on substation transformers.
Fig. 4. Whisker plot key parameters.
a certain amount of methanol and carbon oxides with only one
in which a very small amount of 2-FAL is quantified. In the latter
case, the involvement of board aging has to be considered.
B. Survey of Power Plant Transformers
Contrary to the previous case, power plant transformers op-
erate at close to 100% of their rated load. This characteristic
allows for a direct comparison of the concentration measured in
the oil samples of the units.
A thorough comparison using the three chemical markers
(CO CO , 2-FAL, and CH OH) was established for the 290
transformers currently in operation in EDF’s nuclear power
plants. One-hundred sixty-nine step-up transformers operating
under an cover are among these units.
Each apparatus with a given configuration (shell or core type)
is considered to exhibit almost the same characteristics as the
others. However, there is a significant difference between the
two types of configurations in terms of the amount of insulating
materials involved (paper, board, and oil). The main characteris-
tics of the transformers under investigation are given in Table II.
The labels correspond to the type of configuration (S for shell
and C for core) and the average effective service time . Due
to the narrow age distribution of the apparatus, a statistical ap-
proach is used to compare the transformers. A Whisker plot
graphical representation illustrates the key values of the sum-
mary statistics, with these values being defined in Fig. 4 [16]. In
JALBERT et al.: METHANOL: A NOVEL APPROACH TO POWER TRANSFORMER ASSET MANAGEMENT
TABLE II
CHARACTERISTICS OF THE TRANSFORMERS INVESTIGATED
this study, the units are consider outliers when they are outside
the 5th and 95th percentile.
To facilitate the comparison between the two types of trans-
former configurations, based on the total amount of oil and cel-
lulose (paper board) for each type, the amount of marker mea-
sured was then standardized per weight of total cellulose (i.e.,
milligrams of marker per kilogram of total cellulose).
Moreover, in order to take into account the solubility in this
paper of each marker at the operating temperature, the data were
normalized as follows:
In the case of carbon oxides, the normalization was obtained
by applying equations taken from [2] for the solubility of the
species with the temperature
(2)
(3)
where oil temperature in C, ppm of CO
in the sample at 80 C, of CO in the sample at T,
ppm of CO in the sample at 80 C and of CO in
the sample at T.
In the case of 2-FAL, it is stated in the previously cited [2]
that there is no significant temperature effect on the solubility
between 55 C–100 C and then, the total amount of 2-FAL
generated by the cellulose could be estimated as 6.7 times its
value measured in the oil. This factor takes into account the
partition of 2-FAL between the oil and the paper.
Finally, the amount of methanol lost by the paper due to its
partition in the oil was evaluated in our laboratory using the fol-
lowing procedure. A total of 81 20-mL ampoules was prepared
by inserting a piece of 0.5 g of paper and 8-mL solution of 1 ppm
(w/w) of CH OH in oil. These ampoules were sealed under air
and distributed in equally in three forced-air ovens operating at
40 C, 60 C, and 80 C. Three ampoules were removed from
the ovens after varied lengths of equilibration time and then sta-
bilized for 3 h at 20 C to equilibrate all of the systems at a given
temperature. After the seal was broken, an aliquot portion of oil
was transferred into a 10-mL headspace vial for the determina-
tion of the CH OH. Fig. 5 shows the equilibrium reached for
the three temperatures investigated (each data point corresponds
to the average of three analyses). Under these experimental con-
ditions, the methanol equilibrates very rapidly (24 h) compared
to 2-FAL (30 days) [2]. The amount of methanol at equilibrium
is 4.3 times less than what it was initially in the oil (100/23.3%)
and, as observed for 2-FAL, is independent of the temperature
investigated. This latter value was used to further normalize all
of the CH OH data.
The Whisker plots of the normalized data obtained for the
configurations listed in Table II are reproduced in Fig. 6. First,
517
Fig. 5. Equilibrium of methanol versus temperature.
in the case of the carbon oxides, no major discrepancy in the
data was noted for transformers with an average of 13 7 to
25 3 years. However, the comparison of the distributed data
points for each configuration (shell versus core) is very sim-
ilar: the shell type displays a normal distribution of data com-
pared to the core type, where two groups of data can be noted.
Notwithstanding the difference in the operating temperature and
, this marker seems to indicate that the paper degradation of
these transformers is almost of the same extent regardless of the
configuration (shell versus core).
Second, compared to the carbon oxides, the 2-FAL data anal-
ysis shows a very different trend. As expected, the data obtained
for the transformers isolated with 100% TU paper (S13) showed
the lowest level of markers, and the data are on a narrow range,
which suggests that these transformers did not age significantly.
However, a survey conducted on a decommissioned unit of this
family showed that contrary to the indication received from the
2-FAL, paper and board have been aged with the degree of poly-
merization (DP ) values as low as 525 and 875, respectively.
On the other hand, based on data collected from our laboratory
tests on this type of paper [10], these results suggest that 2-FAL
mainly originates from insulation board aging.
If we compare the other 2-FAL data distributions for a compa-
rable (22 4 versus 25 3 years), the paper insulation of the
shell-type transformers operating at 360 MVA seems to degrade
to a lesser extent than the core type; given that the operating
temperature of the shell-type transformers is higher, this result
is surprising unless the absorption of the 2-FAL compounds by
the boards results in apparent lower concentrations. This is taken
into account. Moreover, even if there is a significant difference
in the between core-type transformers operating at 360 and
550 MVA ( versus 16 3 years), the distributions are sim-
ilar, except for the outliers.
Finally, a comparison of the methanol concentrations with the
different transformer configurations showed a mix of what was
observed with the carbon oxides and the 2-FAL data analysis.
Knowing that TU- and standard-Kraft paper generate methanol,
it is not surprising to note a lower average concentration for
518 IEEE TRANSACTIONS ON POWER DELIVERY, VOL. 27, NO. 2, APRIL 2012

TABLE III
OUTLIERS IDENTIFIED WITH A WHISKER
>
COEFFICIENT OF 0.5 ( 90 PERCENTILE)

On the other hand, lower concentrations were surprisingly

noted with methanol for the 360-MVA core-type transformers
( 24.7 3.2 years) compared to the 550-MVA equivalent
design ( 16 3 years). This suggests that the materials
are more thermally involved in the 550-MVA transformers com-
pared to the 360-MVA units. Note that the same behavior is also
observed for the carbon oxides.
These results illustrate the need to compare pieces of equip-
ment of the same configuration (i.e., core data should not be
compared directly with shell data) as mentioned previously [17].
For a better comparison, it is also important to obtain the amount
of materials involved (paper/board/oil) in order to standardize
the data. Finally, an empirical model based on the methanol con-
centrations with average transformer DP could be developed
by taking the paper and board DP distributions into account.

C. Outlier Comparison
After the characterization of the entire transformer families,
it is important to determine the units needing special attention.
This could be approached by identifying the units from each
family distribution that correspond to the higher concentrations
for the three markers studied. Using this approach and a Whisker
coefficient of 0.5, it is possible to pinpoint transformers that
need particular attention. Table III summarizes the statistics for
the transformers studied.
Based on this table, methanol exhibits the maximum number
of outliers, particularly for the shell type. The units of this
configuration are known to be used to a greater extent. It is
interesting to note that this trend is confirmed only by methanol,
Fig. 6. Comparison of the cellulose marker statistics on EDF’s power plant which is most likely due to the high sensitivity of this marker
transformers. to the cellulose-chain scissions. In particular, if one compares
the transformer outliers identified by each marker, only I1TP0
is common for the three different markers in the case of the
550-570-MVA shell-type transformers ( years) 550–570-MVA shell-type transformers (100% TU Kraft).
compared to 360-MVA shell-type transformers. However, for For 360-MVA shell-type transformers (100% std Kraft), five
approximately the same ( versus years), the transformers are common for three different markers (K1TP4,
average concentration of the shell-type transformer (square dot K2TP8, L2TP0, L2TP4, and L2TP8) from which those from
on the Whisker graph) is higher than what is observed with the site L are known to be overloaded. For the two core-type trans-
core type, probably due to the highest operating temperature formers (10% TU Kraft: 90% std Kraft), no common outliers
attributed to this configuration. are found for the three markers.
JALBERT et al.: METHANOL: A NOVEL APPROACH TO POWER TRANSFORMER ASSET MANAGEMENT 519

TABLE IV ACKNOWLEDGMENT
RECOVERY OF MARKERS AFTER OIL PROCESSING
The authors would like to thank L. Brossard for his revision
and helpful contribution in the drafting of this paper as well as
P. Tétreault, B. Morin, and S. Duchesne from IREQ for their
technical assistance.

IV. OIL REGENERATION
One important parameter is the marker’s capability, after
oil regeneration, to rapidly re-equilibrate with the oil in order
to diagnose the degree of paper insulation degradation. The
“memory” of the paper degradation is only possible with
2-FAL and CH OH due to the high concentrations remaining
in the paper insulation. This parameter was investigated for
methanol and 2-FAL on three core-type transformers where oil
regeneration with degassing was applied. The concentrations in
the oil of these markers after varied lengths of time following
regeneration are summarized in Table IV. This table demon-
strates the capability of the regeneration process to remove
more than 90% of the 2-FAL and 80% of the CH OH from
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V. CONCLUSION
These practical examples from in-service transformers
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cule over 2-FAL is its ability to be generated in the presence
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2010.
Jocelyn Jalbert (SM’09) was born in Canada in 1967. He received the B.Sc.
degree in chemistry and the M.Sc. degree in analytical chemistry from Univer-
sité de Montréal, Montréal, QC, Canada, in 1990 and 1992, respectively, and the
Ph.D. degree in energy and materials from the Institut National de la Recherche
Scientifique—Énergie et Matériaux, Varennes, QC, Canada, in 2009.
He joined Hydro-Québec’s Research Institute, Varennes, in 1992, where his
main contributions were taking part in the development and normalization of
a headspace method for dissolved gas analysis, and the assessment of trace
amounts of moisture in transformer oil. More recently, he headed a major project
on insulating paper degradation.
Dr. Jalber is a member of the ASTM D27 Committee.
520
Roland Gilbert was born in Canada in 1946. He received the M.Sc. and Ph.D.
degrees in physical chemistry from Université de Montréal, Montréal, QC,
Canada, in 1971 and 1974, respectively.
He joined Hydro-Québec’s Research Institute (IREQ), Varennes, QC Canada,
in 1973 under an industrial postdoctoral scholarship from the Natural Sciences
and Engineering Research Council of Canada. In 1977–1978, he was assigned
to Chalk River Nuclear Laboratories (CRNL), Chalk River, ON, Canada, where
he was involved in nuclear power plant decontamination and steam generator
chemical cleaning. During his career at IREQ, he was responsible for the sci-
entific aspects of a wide range of research activities: chemical analysis and
physico-chemical phenomena related to nuclear power plant operation, chem-
ical treatment of distribution wood poles, and chemistry of transformer insu-
lating materials. He has authored and co-authored more than 100 papers and
patents in these different fields of expertise.
Yves Denos was born in France in 1966. He received the M.Sc. and Ph.D. de-
grees in energy and materials from the Institut National de la Recherche Sci-
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IEEE TRANSACTIONS ON POWER DELIVERY, VOL. 27, NO. 2, APRIL 2012
entifique—Énergie et Matériaux, Varennes, QC, Canada, in 1991 and 1994, re-
spectively.
He was with Hydro-Québec. Varennes, QC, Canada, from 1990 to 1996,
working on fuel-cell material characterization, followed by Gaz de France
(1996–2004), France, and Electricité de France, France (since 2004) in the field
of power generation and material aging.
Pierre Gervais was born in Canada in 1949. He received the B.Sc. and M.Sc.
degrees in physical chemistry from Université de Montréal, Montréal, QC,
Canada.
He was with Hydro-Québec’s, Varennes, QC Canada, substation maintenance
division from 1978 to 1985, then from 1985 to 1992, followed by Hydro-Québec
TransÉnergie, Montreal, as a Specialist in the diagnosis of transformer insula-
tion materials.