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Methanol: A Novel Approach to Power Transformer Asset Management

Article  in  IEEE Transactions on Power Delivery · April 2012


DOI: 10.1109/TPWRD.2012.2185957

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Jocelyn Jalbert Yves Denos


Hydro-Québec Électricité de France (EDF)
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514 IEEE TRANSACTIONS ON POWER DELIVERY, VOL. 27, NO. 2, APRIL 2012

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 in the oil [2] prevents marker re-equilibration in the oil, after
the residual life of their in-service power transformers. Given the which its correlation with the insulation paper degradation be-
difficulties experienced with the use of first and second generations comes meaningless. Since a transformer most likely experiences
of markers (carbon oxides and 2-furfuraldehyde), several organi-
zations are now considering the use of methanol for this purpose. some maintenance work during its useful life and some leaks
Hydro-Québec, which discovered this approach, uses this molecule may be observed in sealed transformers, the use of the CO/CO
on a regular basis to evaluate the state of the cellulose insulation content to detect or predict the end of useful life becomes highly
of in-service power transformers and applies it to Électricité de questionable.
France’s nuclear power plant transformers. In this paper, some An alternative approach consists in considering a family of
examples of the application of methanol in the field are presented
furan compounds, especially 2-furfuraldehyde (2-FAL), more
against the information received from the early marker genera-
tions. specifically linked to paper insulation breakdown [3], though
many drawbacks have to be taken into account. In particular,
Index Terms—Asset management, carbon oxides, cellulose the presence of a very small amount of 2-FAL for thermally up-
degradation, insulating paper, methanol, 2-furfuraldehyde,
residual life.
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
I. INTRODUCTION 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
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
the remaining life of cellulose insulation is under scrutiny by the
scientific community.
Recently, the use of methanol (CH OH) has been reported
insulation, the first efforts focused on the use of CO and CO ,
for the first time in the literature by Jalbert et al. [8] for es-
quantified by dissolved gas analysis (DGA) analysis, for the de-
timating the degree of cellulose insulation degradation. Labo-
tection of faults occurring in the paper or oil components. How-
ratory tests showed that methanol is mainly produced during
ever, the situation is more complex with respect to useful life
the aging of oil-impregnated paper insulation at 60 C–120 C
due to the potentially long aging time an apparatus may experi-
(inhibited naphthenic oil under air), regardless of whether the
ence ( 20 years). For example, in open breathing transformers,
specimens are thermally upgraded. This work revealed the exis-
the presence of a sufficient amount of oxygen is favorable to the
tence of a direct relationship between CH OH production and
generation of CO/CO from the oil and the paper degradation
the scission of 1,4-ß-glycosidic bonds (bonds that link the cel-
processes, with the paper moisture being a parameter of prime
lulose glucose units). Moreover, methanol was detected in the
importance [1].
aging tests in the early scissions of the bonds even at temper-
Moreover, in open-breathing transformers, the carbon oxides
atures as low as 60 C. More recently, a kinetics study car-
can escape from the systems and completely disappear during
ried out by the same research group on standard-Kraft paper
operations, such as oil degassing or regeneration; the low sol-
(std) [9] and on TU-Kraft paper [10] showed that depolymer-
ubility of CO/CO in the insulation paper compared to the one
ization and methanol production required an activation energy
of about 104 kJmol , thus confirming the link between
Manuscript received July 07, 2010; revised February 10, 2011, April 13, the two processes. Moreover, the production of methanol and
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 broken cellulose chains showed about the same value for the
was supported in part by Hydro-Québec TransEnergie and in part by Electricité exponential factors of the Arrhenius expression, which in-
de France. Paper no. TPWRD-00515-2010. troduces the possibility that the rate of production of CH OH
J. Jalbert is with the Institut de recherche d’Hydro-Québec (IREQ), Varennes,
QC J3X ISI Canada (e-mail: Jalbert.jocelyn@ireq.ca).
from chopped chains is much higher than the rate of depolymer-
R. Gilbert, retired, was with the Institut de recherche d’Hydro-Québec, ization, so that the latter becomes the rate determining step of
Varennes, QC J3X ISI Canada. the overall reaction. This means that contrary to the 2-FAL, the
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
methanol is instantaneously produced after the opening of the
77818, France (e-mail: denos.yves@edf.fr). 1,4-ß-glycosidic bonds and, consequently, detected early in the
P. Gervais, retired, was with Hydro-Québec TransEnergie, Montreal, QC oil. These authors also demonstrated the role played by oxygen
H5B 1H7 Canada.
Color versions of one or more of the figures in this paper are available online
and moisture on the exponential factors as obtained from the
at http://ieeexplore.ieee.org. application of different degradation models: pseudozero Eken-
Digital Object Identifier 10.1109/TPWRD.2012.2185957 stam’s rate constants [11], first-order time-dependent decrease
0885-8977/$31.00 © 2012 IEEE
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 IEEE TRANSACTIONS ON POWER DELIVERY, VOL. 27, NO. 2, APRIL 2012

Fig. 3. Comparison of the three markers on substation transformers.

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 Fig. 4. Whisker plot key parameters.
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
a certain amount of methanol and carbon oxides with only one
for CTs compared to those for the power transformers, and
in which a very small amount of 2-FAL is quantified. In the latter
no particular trends may be conducted for these systems. The
case, the involvement of board aging has to be considered.
only cases showing a significantly higher content for methanol
are those where a corona discharge or a hot spot is present,
B. Survey of Power Plant Transformers
suggesting that paper damage occurred in these CTs (see
Fig. 2). These examples show the applicability of methanol for Contrary to the previous case, power plant transformers op-
detecting paper aging in different pieces of equipment. erate at close to 100% of their rated load. This characteristic
Finally, Fig. 3 presents a comparison of the relative concen- allows for a direct comparison of the concentration measured in
trations of the three markers under consideration as obtained the oil samples of the units.
from the units of a given substation. (Each unit’s in-service year A thorough comparison using the three chemical markers
is given at the top of the respective bar graph.) The concen- (CO CO , 2-FAL, and CH OH) was established for the 290
trations were normalized by adjusting the maximum concen- transformers currently in operation in EDF’s nuclear power
tration to 100%. These core-open-breathing transformers were plants. One-hundred sixty-nine step-up transformers operating
from different manufacturers, with some units equipped with under an cover are among these units.
TU-Kraft paper (units #1, 3, and 9). As expected, all of the Each apparatus with a given configuration (shell or core type)
markers show a quantitative response for the apparatus in op- is considered to exhibit almost the same characteristics as the
eration from 1961 to 1962 (units #2, 5, 7, and 8) equipped with others. However, there is a significant difference between the
standard-Kraft paper. For unit #2, the carbon oxides are char- two types of configurations in terms of the amount of insulating
acterized by a high value compared to the levels found for the materials involved (paper, board, and oil). The main characteris-
other markers; this behavior can be explained by the fact that tics of the transformers under investigation are given in Table II.
these oxides could also be produced from oil oxidation (acidity The labels correspond to the type of configuration (S for shell
of 0.1 mg KOH/g of oil). For the unit in service in 1967 (unit #4), and C for core) and the average effective service time . Due
which shows marginal amounts of both CH OH and carbon ox- to the narrow age distribution of the apparatus, a statistical ap-
ides, the use of TU-paper cannot be confirmed. But the fact that proach is used to compare the transformers. A Whisker plot
2-FAL is not detected indicates that this unit probably contains graphical representation illustrates the key values of the sum-
TU-paper. The other apparatus equipped with TU-paper shows mary statistics, with these values being defined in Fig. 4 [16]. In
JALBERT et al.: METHANOL: A NOVEL APPROACH TO POWER TRANSFORMER ASSET MANAGEMENT 517

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 Fig. 5. Equilibrium of methanol versus temperature.
normalized as follows:
In the case of carbon oxides, the normalization was obtained
by applying equations taken from [2] for the solubility of the in the case of the carbon oxides, no major discrepancy in the
species with the temperature data was noted for transformers with an average of 13 7 to
25 3 years. However, the comparison of the distributed data
(2) points for each configuration (shell versus core) is very sim-
(3) ilar: the shell type displays a normal distribution of data com-
pared to the core type, where two groups of data can be noted.
where oil temperature in C, ppm of CO Notwithstanding the difference in the operating temperature and
in the sample at 80 C, of CO in the sample at T, , this marker seems to indicate that the paper degradation of
ppm of CO in the sample at 80 C and of CO in these transformers is almost of the same extent regardless of the
the sample at T. configuration (shell versus core).
In the case of 2-FAL, it is stated in the previously cited [2] Second, compared to the carbon oxides, the 2-FAL data anal-
that there is no significant temperature effect on the solubility ysis shows a very different trend. As expected, the data obtained
between 55 C–100 C and then, the total amount of 2-FAL for the transformers isolated with 100% TU paper (S13) showed
generated by the cellulose could be estimated as 6.7 times its the lowest level of markers, and the data are on a narrow range,
value measured in the oil. This factor takes into account the which suggests that these transformers did not age significantly.
partition of 2-FAL between the oil and the paper. However, a survey conducted on a decommissioned unit of this
Finally, the amount of methanol lost by the paper due to its family showed that contrary to the indication received from the
partition in the oil was evaluated in our laboratory using the fol- 2-FAL, paper and board have been aged with the degree of poly-
lowing procedure. A total of 81 20-mL ampoules was prepared merization (DP ) values as low as 525 and 875, respectively.
by inserting a piece of 0.5 g of paper and 8-mL solution of 1 ppm On the other hand, based on data collected from our laboratory
(w/w) of CH OH in oil. These ampoules were sealed under air tests on this type of paper [10], these results suggest that 2-FAL
and distributed in equally in three forced-air ovens operating at mainly originates from insulation board aging.
40 C, 60 C, and 80 C. Three ampoules were removed from If we compare the other 2-FAL data distributions for a compa-
the ovens after varied lengths of equilibration time and then sta- rable (22 4 versus 25 3 years), the paper insulation of the
bilized for 3 h at 20 C to equilibrate all of the systems at a given shell-type transformers operating at 360 MVA seems to degrade
temperature. After the seal was broken, an aliquot portion of oil to a lesser extent than the core type; given that the operating
was transferred into a 10-mL headspace vial for the determina- temperature of the shell-type transformers is higher, this result
tion of the CH OH. Fig. 5 shows the equilibrium reached for is surprising unless the absorption of the 2-FAL compounds by
the three temperatures investigated (each data point corresponds the boards results in apparent lower concentrations. This is taken
to the average of three analyses). Under these experimental con- into account. Moreover, even if there is a significant difference
ditions, the methanol equilibrates very rapidly (24 h) compared in the between core-type transformers operating at 360 and
to 2-FAL (30 days) [2]. The amount of methanol at equilibrium 550 MVA ( versus 16 3 years), the distributions are sim-
is 4.3 times less than what it was initially in the oil (100/23.3%) ilar, except for the outliers.
and, as observed for 2-FAL, is independent of the temperature Finally, a comparison of the methanol concentrations with the
investigated. This latter value was used to further normalize all different transformer configurations showed a mix of what was
of the CH OH data. observed with the carbon oxides and the 2-FAL data analysis.
The Whisker plots of the normalized data obtained for the Knowing that TU- and standard-Kraft paper generate methanol,
configurations listed in Table II are reproduced in Fig. 6. First, 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.

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is then restored in the oil phase. Finally, after approximately six [9] R. Gilbert, J. Jalbert, P. Tétreault, B. Morin, and Y. Denos, “Kinetics
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methanol formation during ageing of paper/oil systems. Part 1: Stan-
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of more than 100% are tentatively attributed to the high aging [10] R. Gilbert, J. Jalbert, P. Tétreault, B. Morin, and Y. Denos, “Kinetics
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showed the universal application of methanol as a marker for [16] OriginLab Corporation. Northampton, MA, Origin Pro.
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“Ageing diagnosis by chemical markers: Influence of core-type and
cule over 2-FAL is its ability to be generated in the presence shell-type technology,” presented at the CIGRE, Paris, France, Aug.
of TU paper regardless of the temperature and the moisture 2010.
present in the insulation. It could readily be used to sort out the
Jocelyn Jalbert (SM’09) was born in Canada in 1967. He received the B.Sc.
problematic units of a given family and technology. In addition, degree in chemistry and the M.Sc. degree in analytical chemistry from Univer-
contrary to carbon oxides, because of its high affinity for the sité de Montréal, Montréal, QC, Canada, in 1990 and 1992, respectively, and the
paper, methanol will tend to re-equilibrate in the oil after the Ph.D. degree in energy and materials from the Institut National de la Recherche
Scientifique—Énergie et Matériaux, Varennes, QC, Canada, in 2009.
latter has been regenerated. This is a major step for electrical He joined Hydro-Québec’s Research Institute, Varennes, in 1992, where his
utilities seeking, namely, to determine whether a given unit main contributions were taking part in the development and normalization of
should be refurbished or replaced. This research project allowed 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
Hydro-Québec and Électricité de France to begin using the on insulating paper degradation.
methanol marker for managing their fleet of transformers. Dr. Jalber is a member of the ASTM D27 Committee.
520 IEEE TRANSACTIONS ON POWER DELIVERY, VOL. 27, NO. 2, APRIL 2012

Roland Gilbert was born in Canada in 1946. He received the M.Sc. and Ph.D. entifique—Énergie et Matériaux, Varennes, QC, Canada, in 1991 and 1994, re-
degrees in physical chemistry from Université de Montréal, Montréal, QC, spectively.
Canada, in 1971 and 1974, respectively. He was with Hydro-Québec. Varennes, QC, Canada, from 1990 to 1996,
He joined Hydro-Québec’s Research Institute (IREQ), Varennes, QC Canada, working on fuel-cell material characterization, followed by Gaz de France
in 1973 under an industrial postdoctoral scholarship from the Natural Sciences (1996–2004), France, and Electricité de France, France (since 2004) in the field
and Engineering Research Council of Canada. In 1977–1978, he was assigned of power generation and material aging.
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 Pierre Gervais was born in Canada in 1949. He received the B.Sc. and M.Sc.
physico-chemical phenomena related to nuclear power plant operation, chem- degrees in physical chemistry from Université de Montréal, Montréal, QC,
ical treatment of distribution wood poles, and chemistry of transformer insu- Canada.
lating materials. He has authored and co-authored more than 100 papers and He was with Hydro-Québec’s, Varennes, QC Canada, substation maintenance
patents in these different fields of expertise. 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.

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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