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A STUDY ON THE RELATIONSHIP BETWEEN PASSIVATOR AND GAS FORMATION By: Annalie Lombard Eskom Enterprises Division and

John Osborne Osborne Analytical

Corrosive sulphur problems in insulating oil have been experienced internationally and a number of failures have been well documented. Passivation of the oil was offered as a quick solution for this problem at a time when panic struck the electrical industry. The addition of passivator was proposed based on limited experience with insulating oil, but based more on the experience with lubricating oils.

The bulk of electrical insulating oil used in Southern Africa is mineral oil mixtures of hydrocarbon compounds originating as crude oil from different geographical areas around the world. As a result oils currently in use comprise of slightly different chemical structures, most with higher amounts of Naphthenic compounds than Paraffinic compounds, but also containing low amounts of Polyaromatic hydrocarbons (PAH) as well as aromatic compounds. Paraffinic refers to carbon atoms bonded to one another in straight chains or branched structures, whereas carbon atoms bonded to one another to form 5, 6 or 7 carbon rings are referred to as Naphthenic. The primary functions of transformer or insulating oil are to insulate the primary windings from the secondary windings and ground, as well as to function as a heat transfer medium to transfer the heat from the windings to external cooling equipment [1]. It is thus important that the oil posses good insulation and dielectric properties. This will include, but are not limited to low moisture content, high dielectric breakdown voltage and good anti-ageing properties thus a low tendency to form oxidation breakdown products such as acids and sludge. The full detail regarding the required characteristics will normally be specified by the equipment manufacturer as well as the end-user. These requirements from the power industry as well as environmental legislation placed refiners under pressure to control the refining process and deliver a non-corrosive Naphthenic oil at an economically viable price. The end product conforming to corrosive sulphur, with negative gassing characteristics and other requirements are defined by the crude oil chemistry that is obtainable as well as the refining process utilized by a specific refiner. As a result only some refiners are capable of

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The South African transformer oil or insulating oil market has been dominated by the usage of uninhibited Naphthenic oil for several decades. This however is rapidly changing and may have catastrophic consequences for uninformed users, regenerators and recyclers of transformer oil.

1. BACKGROUND

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This paper discusses the laboratory observations as well as passivator related experience with transformers in the field.

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The distinct relationship of increased hydrogen with increased Irgamet 39 was observed. If a limited amount of oxygen is available more hydrogen is produced. If oxygen is eliminated, very little of any gas is produced. The copper was found to enhance or catalyse gas production.

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Laboratory studies sought to establish any clear relationship between dissolved gas and passivator content under conditions of temperature and exposure to copper (the metal passivated). Tests were performed in ambient air as well as in sealed containers.

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Immediately following the addition of passivator increased dissolved gas concentrations, particularly hydrogen, have been observed in some transformer oils which were dosed with 100 ppm passivator.

producing uninhibited (class U) products whilst others can produce only inhibited (class I) and others class U and I. [1] Uninhibited oil must contain natural inhibitors, which are semi reactive and probably sulphur containing. However, the identification of such unique compounds present in the oil are yet to be achieved as the composition of oil, which comprises in excess of thousand different hydrocarbon structures are currently not possible. Corrosive sulphur testing have become more stringent resulting in the removal of natural inhibitors during more demanding refining processes to achieve stable oil. This has reduced the supply of available uninhibited class U transformer oil in the marketplace.

1.1

CORROSIVE SULPHUR AND PASSIVATION A number of processes are employed during refining following crude fractionation. Processes such as solvent extraction, hydrotreating and hydrocracking are specifically employed during transformer oil production, each resulting in an end product with different chemical characteristics. The amount of sulphur present in oil and thus possibly the corrosiveness of transformer oil can be controlled by a refiners process. If the requirement is to eliminate or greatly reduce the risk of corrosive sulphur then the user should look for severely refined transformer oil which has corrosive sulphur compounds stabilised. It must be noted however that the more sulphur is stabilised within the oil the less likely it will make a totally uninhibited class U oil, this implies that inhibitors will be added resulting in class I products. The natural inhibiting process of uninhibited oil depends on the remaining sulphur compounds or the natural inhibitors in the oil during refining. If the oil choice is to use totally uninhibited oil then it is advised to choose oil that has been fully certified as free of corrosive sulphur by specific methods. The chemistry to support totally uninhibited oil is diminishing in the Naphthenic crude supply, resulting in limited availability of class U oils. The primary crude sources that have traditionally been rich in the natural inhibitors to make uninhibited class U oil have become very hard to find. The process of refining to produce an inhibited class I transformer oil lends itself to ensuring that the corrosive sulphur is stabilised. This also allows a refiner to pull from a wider variety of Naphthenic crudes to keep up with demand. As a result of the above gassing tendency, inhibitor and passivator content as well as corrosive sulphur amongst other important properties needs to be specified during oil purchases. With oil having a highly positive gassing tendency, the application of the oil needs to be carefully considered as mentioned above. When oil contains passivators and inhibitors, these need to be monitored during the life of the equipment to ensure that the levels of depletion do not drop to less than 25% of the original added value. Whilst the residual values of these products need to be monitored following purification and regeneration. Certain in-line processing units are also known to remove these chemicals. Corrosive sulphur problems in insulating oil have been experienced internationally and a number of failures have been well documented. Passivation of the oil was offered as a quick solution of this problem at a time when panic struck the electrical industry. The addition of passivator was proposed based on limited experience with insulating oil, but based more on the experience with lubricating oils. Immediately following the addition of passivator increased dissolved gas concentrations, particularly hydrogen, have been observed in some transformer oils which were dosed with 100 ppm passivator. Irgamet 39 is the trade name of N-Bis (2-ethylhexyl)-aminomethyl-tolutriazole, and is manufactured by the CIBA company. Its function in a mineral oil is as a metal deactivator or passivator. The recommended concentration in oil is 100 ppm (mg.kg-1). The chemical composition is C24H43N4 which translates to 74.4% carbon, 11.1% hydrogen and 14.5% nitrogen.

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Irgamet 39 has a high viscosity (80 mm /sec), low melting point (-30 C) and solubility of 5% in oil and esters, and 0.01% in water and a density of 0.95 g/ml. The boiling point and decomposition temperature is not documented. The chemical structure is given below.
CH3 CH2

CH3 CH2

C4H9-CH-CH2- N -CH2-CH-C4H9

N N

CH3

CH3

2. OBJECTIVES

The distinct relationship of increased hydrogen with increased Irgamet 39 had to be observed. The effect of oxygen on the reaction needed to be monitored and the absence of oxygen versus the amount of gas produced had to be observed. The effect of the copper on the whole reaction had to be established in order to see if copper reacts as a catalyst to the production of gas. A few key questions had to be considered, these are: What effect do various conditions have on the production of gas? How much hydrogen is produced by this process? Is there a difference between new and regenerated oil with respect to types and rate of gas production? Which other gases are produced following passivation? Will in-line processes such as Dry-Keep drying remove the passivator?

3. PROCEDURES FOLLOWED AND OBSERVATIONS New uninhibited oil was obtained courtesy of Engen, of type Poweroil TO 1020 (60U) - uninhibited. Irgamet 39 was obtained from Ciba (but with no certificate of purity). The purity was accepted to be -1 approximately 95%. A stock solution of 100 g of oil containing 1% Irgamet (10g.l ) was prepared. Further dilutions of this stock in the new oil were used in the experiments.

Laboratory studies sought to establish any clear relationship between dissolved gas and passivator content under conditions of temperature and exposure to copper (the metal passivated). Tests were performed in ambient air, elevated temperatures as well as in sealed containers, with argon and air respectively.

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At high levels of hydrogen in a transformer oil sample, partial discharges are indicated. If significant concentrations of hydrogen are introduced through the addition of excess passivator, electrical faults will be falsely diagnosed, and a unit may be taken out of service for a repair which turns out not to be necessary. If a distinct correlation between dissolved hydrogen gas and Irgamet 39 concentration can be found, a maximum dose of the passivator must be enforced. By performing tests with increasing concentrations of Irgamet 39 under different conditions, any trends should indicate levels at which unacceptable hydrogen concentrations are produced.

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Oil samples have been received from transformers which have exhibited high levels of dissolved hydrogen when a high concentration of passivator Irgamet 39 has been dosed. Although the recommended dose is 100 mg.kg-1, concentrations up to 2000 mg.kg-1 have been present in some Southern African oils. The hydrogen introduced with the Irgamet 39 is covalently bound, as it is with the mineral oil component. Hydrogen gas is released in a transformer when there is a certain fault (i.e. an electrical discharge). Hydrogen is released by the breaking of hydrogen-carbon bonds in the hydrocarbon material of the oil. If increased hydrogen is present due to excess passivator, this probably indicates that hydrogen is more easily released from the Irgamet 39 molecule than from the oil material.

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Each concentration was prepared by mass in the open laboratory (i.e. no measures were taken to eliminate the elements of air). The main focus of the experiment was to determine any relationship between the release of hydrogen and concentration of the passivator, under the test conditions. The influence of dissolved ambient air on this experiment was expected to be negligible, but may play a role in sealed transformers. Any variations in other gases (methane, carbon monoxide, ethane, ethylene and acetylene) would be indicated by the dissolved gas analysis (DGA). All samples were prepared on the same day. 11 ml of the prepared oil was measured into a headspace vial. After the exposure/reaction period, samples were analysed for dissolved gases by headspace capillary Gas Chromatography (GC) and for residual passivator (Irgamet 39) concentration by High Performance Liquid Chromatography (HPLC). 3.1 Experiment 1 - Dissolved Gas Production versus Passivator Concentration with New Oil.

3.2

Experiment 2 Dissolved Gas Production Rate with 100 mg.l-1 Passivator with New Oil. Samples of oil containing 100 mg.l of Irgamet 39 was prepared and placed in an oven at 100C, 20 samples were left at ambient temperature. At intervals of 24 hours, one vial with a copper strip and one without were removed from the oven and cooled. Together with one vial with a labeled, these four were submitted for DGA and Irgamet 39 determination. This test was continued for 1 week. An extra set was removed after 2 weeks for another data point.
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3.3

Experiment 3 - Dissolved Gas Production rate in Argon with New Oil. After the first few samples were analysed, it was apparent that only about 70-80% of the air had been eliminated by flushing. The flushing method was therefore only partially effective or air was able to return to the vial before sealing. The vial of oil (and a cap) and the argon outlet were enclosed in a light plastic bag. This was allowed to fill during a flush, then squeezed out whilst the argon flowed. This was repeated several times during the (approx. 2 minute) flush after which the cap (inside the bag) was crimped on (with the crimping tool outside the bag). This latter action punctured the bag, so a new bag was used for each test sample. In this way >99.5% of air was eliminated. This experiment was conducted for heated samples only, since gas concentrations were very low for ambient tests in all previous experiments, and were not expected to reveal new information in this experiment. The data produced in this experiment gave some interesting observations. Firstly the hydrogen produced in the atmosphere of less than 0.5% air was in concentrations between 100 and 200 vpm, about one tenth of that produced in the reduced (25%) air experiments. Also the concentrations did not increase with time.

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For each concentration, two vials containing the oil only and two with oil plus a copper strip were prepared, one of each was placed in the oven, and the other was kept at ambient temperature (22 C 2C) for 1 week (168 Hours). After this the DGA was performed and the remaining sample was analysed for Irgamet 39 content by HPLC. An empty sealed vial was heated for a week to establish whether there was any contribution from vial, cap or seal.

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The stock (1% Irgamet 39) oil was diluted in the pure oil to produce 6 different concentrations of the passivator between 100 ppm (the recommended dose) and 2000 ppm (the maximum encountered). A blank oil (0 ppm added Irgamet 39) was also used.

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During this experiment new oil was passivated and heated in an oven at 100C. The rate and type of gas was monitored.

The oxygen was depleted within the first 24 hours of the experiment and the hydrogen appeared within a few hours (the first sample was removed after 3 hours). After that time the measurements fluctuated but showed no distinct trend. (The fluctuations are suspected to be due to small amounts of air leaking past the seals on some of the vials.) 3.4 Experiment 4 Dissolved Gas Production versus Concentration in Ambient Air with Regenerated Oil. This was a repeat of Experiment 1, however during this experiment uninhibited regenerated oil was used to conduct the experiments. 3.5 Experiment 5 Dissolved Gas Production versus Passivator Concentration in Argon with Regenerated Oil. Over 99% of the air was eliminated in most of these tests, by means of the Argon flush procedure explained in Experiment 3.

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500g of oil containing 100 mg.l of Irgamet 39 was prepared from the stock (1% oil) and pure oil. 11 ml of this was accurately measured into each of 40 headspace vials. Into each of 20 of these was placed a single standard copper strip. All vials were sealed (with aluminium liners). 20 of these vials (10 with copper strip and 10 without) were placed in an oven at 100 C, and the remaining 20 were left at ambient temperature. At intervals of approximately 24 hours one vial with copper strip and one without were removed from the oven and cooled. Together with one vial with copper strip and one without which had been at ambient, adequately labeled, these four were submitted for DGA and Irgamet 39 determination. This test was continued for 8 days.

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3.6.

Experiment 6 - Dissolved Gas Production Rate with 100 mg.l Passivator in Ambient Air with Regenerated Oil.

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The sample preparation was the same as experiment 6, except that the vials were thoroughly argon-flushed before sealing.

3.8

Experiment 8 - Passivator removal by Molecular Sieve In order to observe the possible removal of passivator by Molecular Sieve used in on-line drying systems such as Dry-Keep an experiment was set up to establish if removal occurs. A mass (approx. 100 g) of molecular sieve granules was placed in a dry extraction column. Approx 200 g of the new oil containing Irgamet 39 was added to the top of the Molecular Sieve. This was allowed to drain through under gravity (approx. 3 ml/min at first) until it stopped dripping (about 2 hours). The oil collected was stirred for 10 minutes (magnetic stirrer), then sampled for Irgamet 39 determination.

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Hydrogen production of up to 200 vpm with copper, and about 120 vpm without was measured in the heated tests. After an initial increase, the concentrations did not increase with time. This contrasted with the new oil in which hydrogen concentrations increased to around 2000 vpm in the same time (with heating and with or without copper). The oxygen was depleted within the first 48 hours of the heated experiments (slower than with new oil which was totally consumed by 24 hours). There was only a slight deterioration in the Irgamet 39 concentration with time.

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3.7

Experiment 7 - Dissolved Gas Production Rate with 100 mg.l with Regenerated oil.

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Passivator in Argon

Concentration (mg/kg)

104.97

1052.1

Before

100.9

940.58

Mass Irgamet 39 (mg)

20.11 100.01

188.79 100.018

Mass of molsieve (g)

Mass of oil (g)

199.28

200.714

Concentration I39 (mg/l)

87.93

876.03

% Removal

12.85

6.86

Mass Irgamet 39 removed (mg)

2.58

12.96

3.9

Eskom Transformer Data Passivator addition versus Gas produced

4. DISCUSSIONS 4.1. Experiment 1 and 2

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There is a distinct correlation between passivator (Irgamet 39) concentration and hydrogen generation in transformer oil, particularly at the elevated temperatures at which transformers may operate. The relationship is proportional. Copper seems to reduce the hydrogen production rate slightly. Hydrogen generation coincides with reduction in Irgamet 39 concentration indicating that it originates from the passivator and not from the oil. When the passivator concentration had depleted, so did the hydrogen production. It may have been consumed during normal oxidation reactions. Pahlavanpour et al reports that the Irgamet 39 does not decompose at elevated temperatures (in sealed transformers), except when the oil is oxidised [2]. That report also reports the observation that the passivator remains irreversibly bound to the copper surface, so that maintaining an excessive dose has no advantage. Production of alkane gases (ethane and methane) seemed to be stimulated by the presence of passivator, but was not proportional to its concentration. This suggests a mild catalytic reaction, (i.e. Irgamet 39 participates in but is not consumed by this reaction). Carbon monoxide was initially consumed in the presence of Irgamet 39, but then increased gradually with Irgamet 39 concentration increase. In the time progression, the carbon monoxide steadily increased when copper was present, even when the Irgamet 39 had depleted, whereas when copper was absent, carbon monoxide depleted after the Irgamet 39 had been used up. This suggests the copper has a reducing effect, preventing the conversion of carbon monoxide to carbon dioxide, which probably happened in the absence of copper. For the 100 mg.kg Irgamet 39 test, the passivator concentration depleted by 95% within one week at the elevated temperatures, both with and without copper. This raises questions of its lasting applicability, particularly in transformers that are not sealed and in which circulation is slow. Regular (maintenance) dosing may be necessary, although this will be coupled with unwanted gas production. However, once initially applied, the adhesion of the passivation layer is permanent [2] thus only an initial excess of the Irgamet 39 is necessary, after which no additions will be required. In the event of refurbishment of a transformer, a fresh dose of Irgamet 39 may be appropriate to passivate any copper surface that may be new or physically affected.
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Amount of transformers No gas produced Hydrogen produced Methane produced CO/CO2 produced Ethane produced Ethylene produced Acetylene produced

% for SEALED (COSERVATOR BAGS) 29 3 97 61 64 45 45 6

% for NOT SEALED 26 15 85 39 62 27 27 15

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These experiments were prepared at ambient conditions i.e. without any preliminary degassing or exclusion of the elements of air (particularly oxygen and carbon dioxide). The tests were performed on new oil of one type from one manufacturer. It is possible that other oils may have different effects when Irgamet 39 is used. The effects reported may also involve a factor of incomplete mixing. If the circulation of insulating fluid in the transformer is slow, it will take some time before the distribution of the additive is relatively even throughout the oil volume. There may be localised hydrogen production, which may show up depending on how close it is to the sample point. With forced circulation, the time will be relatively short, and the existence of localised dissolved hydrogen pockets will be less evident. Also if the passivator has not circulated well, parts of the copper windings may not be passivated before the Irgamet deteriorated (particularly for free breathing units). This aspect may also deserve study.

4.2.2

Hydrocarbon Gases

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The overall concentrations of hydrogen varied differently at the different air levels. When air was limited the concentrations of hydrogen were highest and the hydrogen concentration was less when no air limitation was attempted. This observation indicates that the reactions involving hydrogen depend strongly on the air (oxygen) present. There appears to be two types of reaction, those generating hydrogen and those consuming it. When air is absent, no significant hydrogen is produced. With limited air, hydrogen is produced more effectively but consumed slowly. When ample air is present, hydrogen is probably produced at an optimal rate, but also consumed, (probably by some reaction during oxidation or perhaps producing moisture with the oxygen). In all cases, the passivator has a role in accelerating hydrogen production.

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4.2.1

Hydrogen

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Average concentrations after one week exposure with 100 mg.l presence of Irgamet 39 are given in Table 4.1.1. (Not included is the enhanced ethylene production observed at reduced air levels at ambient temperature, 60 vpm with copper present and 25 vpm without). Acetylene was present in detection limit amounts or less. Table 4.1 Hydrocarbon gas production for heated tests at different air levels
Argon flush Nil Partial Full Air concentration 100% 25% <0.5% Methane concentration (vpm) Heated with copper Heated only 500 200 150 50 15 15 Ethylene concentration (vpm) Heated with copper Heated only 9 6 12 2 8 2 Ethane concentration (vpm) Heated with copper Heated only 300 250 350 150 14 10

Argon flush Nil Partial Full

Argon flush Nil Partial Full

Clearly lower concentrations of air present (oxygen) resulted in lower levels of hydrocarbon formation, and hydrocarbons were formed irrespective of the quantity of passivator present, but were enhanced by the metal (copper windings). Ethylene formed rapidly and reacted rapidly with full oxygen, i.e. it is intermediate in the formation of something else (ethane). Formation was found to be faster than consumption when oxygen was limited.

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Air concentration 100% 25% <0.5%

Air concentration 100% 25% <0.5%

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4.2

Comparative Observations Experiments 1-3

4.2.3

Oxides of Carbon Carbon oxide (both CO and CO2) production is affected by Irgamet 39 concentration, and is limited by the amount of oxygen available. Trends are similar for both gases and the table 4.1.2 shows the 1-week gas concentrations at 100 mg.l-1 concentration of the passivator at different air levels. At ambient temperatures in full air the carbon dioxide was steady around 600 vpm and carbon monoxide <10 vpm for all tests. In reduced air the ambient concentrations were CO2 150 vpm and CO <1 vpm, and with full flush: 10 vpm and <1 vpm respectively. Table 4.1.2 Hydrocarbon gas production for heated tests at different air levels
Argon flush Nil Partial Full Air concentration 100% 25% <0.5% Carbon Monoxide concentration (vpm) Heated with copper Heated only 1500 1500 350 350 40 40 Carbon Dioxide concentration (vpm) Heated with copper Heated only 3600 1400 2500 800 150 150

4.3 Comparative Observations Experiments 4-7

4.3.2

Passivator Behaviour The passivator deteriorated from 100 mg.l to below 20 mg.l only with the new oil in the presence of air. In other series minimal deterioration was observed over the week i.e when air is (almost) absent and in either case with regenerated oil. This was supported by comparing different concentrations of passivator, the new oilin-air tests showed most Irgamet 39 deterioration than the others (though the higher range of concentrations made the effect look less distinct).
-1 -1

4.3.3

Hydrocarbon Gases The production of hydrocarbon gases are best depicted by methane as the others (ethane, ethylene and acetylene) were generally produced in minimal concentrations. This is not related to the Irgamet 39 concentration. In new oil more methane is produced in air than when air is limited, however in the regenerated oil slightly more is produced in the absence of air. Methane was produced increasingly with time and it was observed that the production in new oil was the fastest. The production was significantly reduced in an argon atmosphere, thus the reaction involves components in the new oil and oxygen. Ethane was produced in concentrations of up to 500 vpm in new oil with air, and not related to passivator concentration. Low concentrations were observed in argon atmosphere, and

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There was a distinct correlation between Irgamet 39 concentration and hydrogen production in experiments with both the new and the used oil. The presence of copper had little influence on the hydrogen concentration. It is obvious that this reaction occurred far more readily in the new oil.

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4.3.1

Hydrogen

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Unless otherwise stated, the comparisons were made using data from the heated tests with copper present. These tests provided higher gas concentrations and enabled better trending than the other tests.

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The relationship between copper and the monoxide concentrations is clear when air is available.

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Argon flush Nil Partial Full

Air concentration 100% 25% <0.5%

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ethylene concentrations always low, acetylene barely detectable. Small concentrations of ethane were produced in the regenerated oil with argon atmosphere only, and not related to passivator concentration. Traces of ethylene were produced, with acetylene barely detectable. 4.3.4 Oxides of Carbon In contrast to the trends observed in the new oil, the carbon monoxide production does not appear to be significantly influenced by the passivator concentrations for regenerated oil. In the new oil, more CO was produced in air, whereas in regenerated oil the concentrations in argon atmosphere are larger than in air. The production of carbon monoxide increases with time, and is far faster in the new oil than in the regenerated oil.

4.2.5

Gas Formation Following Passivation

5. CONCLUSIONS AND RECOMMENDATIONS 5.1 Experimental Data

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The observations of the first investigations (where air was not 100% eliminated) were confirmed but additional tests showed that chemical behaviour in sealed conditions was different in many ways. There is a distinct correlation between passivator (Irgamet 39) concentration and hydrogen generation in transformer oil, particularly at the elevated temperatures at which transformers may operate, and even with reduced air levels. Production of hydrogen is affected by the presence of oxygen (since nitrogen was not detectably depleted in all experiments, but oxygen was totally consumed rapidly in the sealed test vessels). For hydrogen, concentrations were higher compared to where the air was reduced to 25%, but significantly reduced when <0.5% air was present. Air is initially involved in generation of hydrogen, then reacts to consume hydrogen (in reactions to oxidise oil, or addition reactions to saturate ethylene to ethane, or simply to combine to produce moisture). Irgamet 39 passivator is consumed significantly over time and with heat when oxygen is present. When oxygen is completely eliminated, very little decomposition was observed. It is the free or excess passivator in the oil phase that is oxidised, since the passivator bond on the copper surface remains intact. The decomposition and hydrogen production will be minimised by effective sealing of the transformer. Further protection can be made by supplying a constant positive low pressure of nitrogen (or inert gas) to the unit, so that inert gas exiting any leaking seal will prevent air (and thus oxygen) ingress. Employing the latter may however assist in partially flushing dissolved gases out of the oil, which factor will need to be considered for diagnostic interpretation of DGA.

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From actual transformer data extracted from the Eskom transformer oil analysis database it was evident that some degree of hydrogen and hydrocarbon formation did take place following passivation. In nearly all the cases there was an increase in the ethylene gas content as well.

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Molecular Sieve has an effect of removing Irgamet 39 from the regenerated transformer oil. Under the conditions used, the removal has a low efficiency. The removal rate is dependent on concentration of Irgamet 39 in the oil. It is suspected that removal efficiency depends on flow rate and probably temperature. The capacity for removal needs to be determined by an experiment designed differently (e.g. extended soaking of Molecular Sieve in an oil of excess Irgamet 39 concentration.)

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4.2.4

Experiment 8 Passivator Removal by Molecular Sieve

As previously observed, production of alkane gases (ethane and methane) seemed to be stimulated by the presence of passivator but not related to passivator concentration. In reduced air, ethylene production was significant at ambient temperature, but not at 100C. It is suspected that the ethylene is saturated to ethane more rapidly at higher temperature and with copper present (i.e. ethylene concentration at any time is negligible in hot tests). This reaction consumes hydrogen. Any acetylene initially formed will quickly be converted to ethylene then ethane by the same process. Similar reactions may be expected in unsaturated (carbon-carbon double or triple bond containing) compounds in the oil. For all hydrocarbon gases the production/presence was minimal when air was 95.5% eliminated. There is a definite correlation between passivator concentration and the generation of carbon oxides. For this air is required, correlation was only observed in the presence of -1 sufficient air. In limited air, the correlation for CO was clear up to 600 mg.kg of passivator. Above this the correlation was less clear, probably due to the reduced amount of oxygen available. The CO concentrations in full and limited air were also higher when copper was present, again suggesting catalytic action in its formation. The conversion of CO to CO2 is affected less than CO production.

The optimal passivation philosophy is probably to insure the correct dose in the oil when it is initially added, and add small amounts after any maintenance has been performed. The event of passivator addition should be flagged on the oil sample, so the analyst is alert to a possible excursion in the dissolved gas trends, and will factor this in to any recommendations made. The comparison of the tests performed in Experiments 4-7 on the used transformer oil gave different results than the new oil previously investigated. Trends were similar but gas production of all gases was far less, and the deterioration of the passivator (Irgamet 39) was minimal, in extreme contrast to the new oil. It appears that new oil contains components that are readily oxidisable (and generally reactive). After these components have reacted, remaining components are more stable, i.e. less reactive in oxygen and less reactive toward the passivator. Thus it appears that the initial passivator is consumed (in new oil) by initial reaction with these reactive components, and not necessarily with passivation of the copper. Generation of hydrogen again correlated with Irgamet 39 concentration, and significantly reduced in the absence of air (in this respect the same as for the new oil), but the striking effect was that the concentrations were one tenth of that in the new oil. Methane concentrations were higher in minimal oxygen conditions, indicating carbon from the oil is more amenable to reaction with hydrogen. Neither in the presence or (almost) absence of oxygen is there any correlation with Irgamet 39 concentration, but a gradual increase with time. Significant ethylene production was only observed in the argon-flushed tests, gradually increasing with time but not relating to Irgamet 39 concentration. The data for ethylene and acetylene were in too low a concentration to derive any meaningful conclusions. The Irgamet 39 cannot therefore be related to the production of hydrocarbon gases.

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increases gas generation disturbs diagnostic trends increases oxidation rate of the oil excess Irgamet 39 itself is decomposed in a relatively short time (longer for sealed systems).

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This investigation indicates that the addition of Irgamet 39 in excess of its recommended -1 level (100 mg. l ) has no benefit whatever, but has several detrimental effects:

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The trends in carbon dioxide and carbon monoxide production were erratic, but no distinct correlation with passivator concentration. There were more carbon oxides in air as would be expected. The monoxide reached 300-350 vpm in air (compared to 1500 with the new oil). In both air and its (almost) absence when heated, carbon monoxide increased with time then leveled off at about 100-120 hours. With lack of air it actually decreased after 120 hours. Carbon dioxide did the same in air, but kept increasing over the 200 hours without air, suggesting that the carbon monoxide was slowly converted to the dioxide. In inert atmosphere, concentrations reached 70 vpm for carbon monoxide and 700 vpm for the dioxide, compared to 40 vpm and 300 vpm respectively for new oil. When new oil is used the initial reaction between reactive components in the oil and passivator produces hydrogen and reduces the passivator concentration. Analysis after a determined time will indicate the more stable state of the oil. Any way of removing gas (inert gas purging or vacuum treatment on the oil) after this period will remove initial hydrogen and render the data from ongoing dissolved gas analysis more reliable. Also adjustment to the passivator content should be made after the first period, when the initial deterioration is complete. This first period will probably depend on the oil type and the operating temperature (i.e. the reactive components present and the reaction rate). It is expected to be in the range of 1 to 6 months (but this will need to be established by experiment or experience).

5.2

Real Transformer Data

6 1

The data from live plant supported all the laboratory findings. There were a higher percentage of free breathing transformers that produced hydrogen (15% vs 3%). There was a definite relationship between increased gas production and the addition of passivator. The passivator is consumed over time with heat that is produced by the energized transformers. More sealed units produced hydrocarbon gas, but it can be concluded that sealed and non-sealed units produced hydrocarbon gas following passivation. REFERENCES

Jimmy M. Rasco; Petroleum refining production of Naphthenic transformer oil control of corrosive sulphur. 2007, Doble Engineering Company - 74th Annual International Doble Client Conference. Mineral Insulating Oil Passivation Effectiveness of Passivation to Stop Copper Deposition. Pahlavanpour, B (Prof.), Sundkvist, K. Nynas Naphthenics Ltd.

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It is not suspected that the difference is derived from regeneration, but from the initial reaction of new oil. This needs to be confirmed by testing oil before and after regeneration.

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The production of other gases (hydrocarbons and oxides of carbon) appears to have little or no correlation with passivator concentration, but is significantly greater during the tests with new oil rather than the regenerated oil.

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