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Furan Analysis
Mohd Taufiq Bin Ishak
Degree of Polymerization
(DP)
The
solid
insulation
(paper,
pressboard,
transformer-board) used in transformers is a
sheet of material made from vegetable cellulose.
The main source of cellulose fibre is wood. In a
dry condition, wood contains 40 to 50%
cellulose, 20 to 30% lignin and 10 to 30%
hemicellulose
and polysaccharides.
DP
DP
The good mechanical properties of cellulose and its derivatives,
on which their utility depends, are due to their polymeric and
fibrous nature.
The number of monomer units in the polymer is known as
degree of polymerisation (DP).
Very often, the quality of the cellulose is measured in terms of
its degree of polymerisation by the average viscometric method.
The length of the cellulose chain thus measured by the average
degree of polymerisation based on viscosity method will be
denoted by DPV.
DP
The measurement of the degree of polymerization is intended
to determine the condition of the paper winding insulation.
Paper samples are taken from the transformer and the degree
of polymerization is determined by measuring the tensile
strength of the samples.
A drawback of this method is that, in order to take a paper
sample, the transformer tank must be opened.
Furthermore, there is no guarantee that the sample taken from
a certain location of the paper winding is representative of the
complete winding
DP
New Kraft paper has an average chain length of 1000 to
1500.
After a long period of service at high temperature with high
content of water and oxygen, the paper becomes brittle,
changes colour to dark brown and DPV falls to 200 to 250.
Sometimes cotton is used as an insulating material. Cotton
fibre lengths are greater than those of unbleached soft
wood sulphate cellulose, but their diameter is smaller.
The average degree of polymerisation for new cotton is
higher than Kraft paper.
DP
DP
DP
For Kraft paper with a DPV of 150 to 200 the mechanical strength of
paper can be reduced to 20% of its initial strength and this point is
regarded as the end of life criterion for transformer insulation.
At DPV from 900 to 500, the strength of the paper is virtually constant
but, in the range 500 to 200, it decreases in direct proportion to DPV.
Comprehensive literature is now available based on accelerated ageing
of oil -paper insulation.
Most of these papers take the paper end of life criterion as 50% of its
original tensile strength or 200-250 as its degree of polymerisation value.
Then a thermal endurance curve is plotted to predict the remaining life of
paper insulation
DP
Pahlavanpour presents some experimental investigation of the thermal
ageing of Kraft paper and suggests that DPV of paper starts decreasing at
120C.
The decrease of DPV is faster with increases of temperature, reaching the
corresponding end of life DPV at a temperature of 180C.
McNutt describes the importance of insulation end of life criterion in his
paper. He pointed out that different investigators tend to choose different
end point DPV levels.
Bozzini suggested 100-150, Lampe used 200, Fabre and Pichon proposed
100-200. The author also highlights that many in-service transformers
have continued to operate with insulation DPV levels below 100.
McNutt suggested that his own end point DPV would be 200.
DP
DP
They related the slope of the kinetic plot (that is the reaction
rate constant k) to temperature by the Arrhenius relationship,
plotting log(k) against reciprocal absolute temperature.
They also showed that the slopes of the plots and hence the
activation energy of the reaction remained constant under a
wide variety of experimental conditions.
Substituting values of initial and final DPV of 1000 and 200
respectively and combining with equation (2), they have given
the equation for transformer remaining life as in equation (3)
DP
DP
DP
DP
DP
Furan Analysis
When cellulose degrades by the breaking of its long molecules, the fragments
produced are molecules of water, oxides of carbon and a variety of
carbohydrates, mostly short-lived, which result from the opening of the
hexagonal glucose ring.
Furans are major degradation products of cellulose insulation paper and are
found in the insulation oils of operational transformers.
The concentration of individual furans in transformer oil can be separately
measured by high performance liquid chromatography (HPLC).
Furan analysis offers a more convenient method of analysis than direct
measurement on insulation paper.
The method is now standardized (IEC 1198), but requires time-consuming preextraction of the furans. A direct-injection HPLC process has been proposed
which allows a fivefold reduction in technician time.
Furan Analysis
Furan Analysis
A family of cellulose degradation products known as
furanic compounds indicated in Figure 1 finds value in
diagnosing cellulose overheating and in the indirect
estimation of DP.
These are five-membered heterocyclic molecules (with
oxygen in the ring), and usually 2-furfural (2-FAL) is the
most commonly measured furanic compound in oil for
diagnostic purposes.
High furanic content of the oil would indicate overheating
of the cellulose.
Furan Analysis
The concentration of five furanic compounds:
2-furaldehyde (2FAL)
5-methyl-2-furaldehyde (5M2F)
5-hydroxylmethyl-2-furaldehyde (5H2F)
2-acetyl furan (2ACF)
2-furfuryl alcohol (2FOL)
Furan Analysis
Figure 1
Furan Analysis
Causes of specific furan compounds:
2-furaldehyde (2FAL)-General overheating, normal
ageing
5-methyl-2-furaldehyde (5M2F)- high temperatures
5-hydroxylmethyl-2-furaldehyde (5H2F)-oxidation
2-acetyl furan (2ACF)-rare, causes not fully defined
2-furfuryl alcohol (2FOL)-high moisture
Furan Analysis
Correlation charts and formulas have been developed
from field sample testing to relate furanic content to DP.
Figure 2 shows DP versus 2-FAL correlation plots
constructed from the field sample. The lab data used for
construction of these plots show some scatter so there
is uncertainty regarding the DP estimation.
The DPs estimated or measured need not represent the
most aged part of the insulation because representative
samples are difficult to be retrieved.
Furan Analysis
Figure 2
Furan Analysis
Furan Analysis
Shroff and Stannett reported on the formation of 2-furfuraldehyde
from the degradation of cellulosic insulation papers in accelerated
ageing experiments and found that an approximately logarithmic
relationship existed between the concentration of 2-furfuraldehyde
in the oil and the degree of polymerisation of the cellulose in the
paper.
Burton made an extensive study and measured the rate of furan
formation of several furan products over a wide range of
temperatures (120-350C).
They also found an approximately logarithmic relationship between
the concentration of 2-furfuraldehyde and the DPV of the paper.
Furan Analysis
Unsworth and Mitchell used HPLC technique to monitor the formation of furan
components during ageing of cellulose insulation paper at 20, 80 and 110C.
They correlated their results for the tensile strength of the paper with the
concentration of 2-furfuraldehyde and observed that the decrease in the tensile
strength of the paper corresponded to an increase in the concentration of the furans
in the oil.
Hill developed a kinetic model and found that the concentration of furans in the
transformer oil should increase in a parabolic form with degradation time as shown in
equation (4).
where Nc is the number of cellulose chains present per kilogram of paper at time t,
A is proportionality constant and k is the rate constant. Also b = A(Nc)0 and c=
( Ak)/2.
Furan Analysis
The authors determined the values of c/b experimentally and compared
those predicted from the model using the values of k and (Nc)0 obtained
from a molecular weight study.
They also reported that 5-hydroxymethyl hydroxymethyl-2furfuraldehyde (HMF and 2-furfuraldehyde(F) are present in the oil at
significantly greater concentrations than any other furan components.
Furfuraldehyde is the furan present in greatest amounts. This study also
found that the rate of HMF formation is faster with an increase in
temperature than the rate of F formation.
Emsley reported that production of 2-furfuraldehyde always outweighed
that of the other three furans and the main production occurred when
the DPV dropped below about 400.