Understanding Dissolved Gas Analysis of Ester Liquids
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1 Understanding Dissolved Gas Analysis of Ester Liquids an Updated Review of Gas Generated in Ester Liquid by Stray Gassing, Thermal Decomposition and Electrical Discharge Initially presented at the 216 IEEE ELETRIAL INSULATIN NFERENE (EI)
2 Mineral il hemical Structure arbon ydrogen = ydrocarbon
3 Mineral il hemical Structure Aromatic Paraffinic Naphthenic arbon ydrogen = ydrocarbon
4 Ester hemical Structure R 2 R 1 R 1, R 2 = arbon Based ompound
5 Natural Ester hemical Structure 2 2 R R R Fatty Acid Fatty Acid Fatty Acid Glycerol
6 Natural Ester hemical Structure R R 2 R R 2 R R Ester
7 Natural Ester hemical Structure For R = and R, R, R = long hydrocarbon chain R 2 R R Fatty Acid Fatty Acid R R Fatty Acid R 2
8 Natural Ester hemical Structure R 2 2 R R Glycerol + Fatty Acid = Glyceride
9 Natural Ester hemical Structure R 2 2 R R Glycerol + 3 * Fatty Acid = Triglyceride
10 R, R, R = Fatty Acid
11 Fatty Acid omposition (%) of Some Natural Ester Liquids Unsaturated = Grape Seed Palmitic 16: 8 Stearic 18: 4 leic 18: Linoleic 18: Linolenic 18:3 3 <1 Sum % 1 Peanut <1 93 Sunflower <1 1 Walnut Soybean anola Flax Seed
12 Differences of Natural Ester il from Mineral il Mineral il
13 Differences of Natural Ester il from Mineral il 2 2 Ester il
14 Differences of Natural Ester il from Mineral il 2 2 Numerous arbon Double Bonds
15 Differences of Natural Ester il from Mineral il 2 2 Numerous Bonds
16 Differences of Natural Ester il from Mineral il 2 2 Large amount of xygen
17 Differences of Natural Ester il from Mineral il 2 2 Large Molecule
18 Mineral il Natural Ester Different composition Different structure Different properties Different reactions?
19 il Degradation Moderate temperature might produce gas Excessive temperature (ot Spot) will produce gas Arcing will produce gas PD will produce gas It occur in both mineral and ester oil
20 il Degradation Fortunately the gases produced are the same: 2 hydrogen 4 methane 2 6 ethane 2 4 ethylene 2 2 acetylene carbon monoxide 2 carbon dioxide Just not in the same proportion
21 il Degradation There is several way to degrade a molecule Autoxidation (Free Radical) xydation ( 2 ) Pyrolysis (eat) Ionisation (harge transfer) Each way has several possible mechanisms
22 Natural Ester Degradation: Stray Gassing In normal service, no gas production is expected owever, Ethane has been reported for normal operation This phenomena is called Stray Gassing It is also observed with some Mineral il But Mineral il produce mostly 2, not 26 Why?
23 Degradation by Autoxidation (Free Radical) R R + R + R R + 2 RR R R + R R + R + 2
24 1 + (From a nearby R) Ethane ( 2 6 ) 1 mega-3 Stray Gassing: Formation of Ethane from Linolenic Acid (xidation)
25 Stray Gassing: Formation of Ethane from Linolenic Acid is unstable 3 2 is the normal form of xygen So where 1 2 come from?
26 S n S 2 е - Generation of 1 2 Electronic states Singlet (S,S 1,S 2,S n ) Triplet (T 1,T 2 ) Vibrational states S 1 Photon absorption γ S е - е - Electronic Ground State Photosensitive Molecule Photon xygen apture
27 S n S 2 S 1 е - е - Generation of 1 2 Electronic states Singlet (S,S 1,S 2,S n ) Triplet (T 1,T 2 ) Vibrational states Internal conversion (I), heat transfer γ Fluorescent emission S е - е - Electronic Ground State Photosensitive Molecule Fluorescence
28 Generation of 1 2 S n S 2 е - е - S 1 T 2 Electronic states Singlet (S,S 1,S 2,S n ) Triplet (T 1,T 2 ) Vibrational states Internal conversion (I), heat transfer Intersystem crossing (IS) е - T 1 S е - Electronic Ground State Photosensitive Molecule IS
29 Generation of 1 2 S n S 2 Electronic states Singlet (S,S 1,S 2,S n ) Triplet (T 1,T 2 ) Vibrational states е - S 1 T 2 е - T 1 S γ Phosphorescent emission е - Electronic Ground State Photosensitive Molecule Phosphorescence
30 Generation of 1 2 S n S 2 Electronic states Singlet (S,S 1,S 2,S n ) Triplet (T 1,T 2 ) Vibrational states S 1 T 2 xygen е - T 1 е - е S е - е - Electronic Ground State Spin inversion е - е Photosensitive Molecule Spin Inversion
31 Stray Gassing Photoreaction is compound dependant It is also dependant of light energy Is photoreaction also occurring in natural ester? The short answer is YES
32 Stray Gassing Natural ester fluid showing phosphorescence from photo activity (left) and after this activity had subsided (right).
33 Stray Gassing in Natural Ester ould be initiated by Free radical reaction ould be initiated by Photoreaction Exposure to light (UV and Sunlight) create gas Exposure to Light also increase gas generation at moderate temperature. Mostly 2, 2 6, and production related to oil composition
34 Stray Gassing in Natural Ester Importance of storing il properly New Stored New ASTM 715 Stored ASTM Impact of 3 years exposure of soybean oil to sunlight in Polyethylene tank (ASTM D715 at 12 )
35 Stray Gassing in Natural Ester Importance of storing il properly New Stored As Received New ASTM 715 Stored ASTM 715
36 Stray Gassing in Natural Ester Importance of storing il properly New Stored New ASTM 715 Stored ASTM After Stray Gassing Test
37 Stray Gassing in Natural Ester Importance of storing sample properly Impact of one week sample exposure to light (ASTM D3612 method at 7 )
38 Stray Gassing Do not store oil sample under the sun Do not store outside in translucent container Expect some Ethane
39 Thermal Studies ontrolled thermal stress zone Studies from 25 to 7 at 5 degree intervals ontrolled fluid flow Thermal relaxation zone Fluid reservoir and headspace Managed system pressure Nitrogen environment Low oxygen content Fixed study time Ensemble of studies optimized at 8 hours. Liquid and gas sample collection
40 Thermal Studies Gas ollector Pump Sampling N 2 il 1.5 L 8 ours eater 25 7
41 Thermal Studies
42 Total gas volume 8 ours Total Gas Generation Volume (liters) Soybean Sunflower Mineral Temperature
43 Gas Produced in Soybean il Soybean il Amount of Gas (ppm) 1,, 8, 6, 4, 2, Temperature
44 Gas Produced in Sunflower il Sunflower il Amount of Gas (ppm) 1,, 8, 6, 4, 2, Temperature
45 Gas Produced in Mineral il 1,, Mineral il Amount of Gas (ppm) 8, 6, 4, 2, Temperature
46 Duval Triangle Mineral il Duval 1 PD 1 T1 4 T2 24 D1 D2 DT T
47 Duval Triangle Mineral + Soybean il Duval 1 PD 1 T1 4 T2 24 D1 D2 DT T
48 Duval Triangle Mineral + Soybean + Sunflower il Duval 1 PD 1 T1 4 T2 24 D1 D2 DT T
49 Modified Duval Triangles Duval 3 b 1 PD Duval 3 d 1 PD T1 T T2 D1 D1 T2 D2 DT T3 D2 DT 1 T
50 Acidity Thermal Degradation of Natural Ester generate also high level of Acidity Acid Number Temperature Soybean il >1 >1 >1 >1 >1 Sunflower il >1 >1 >1 >1 Mineral il
51 Electrical Discharges in Ester il In Arcing and PD, oil degradation occur in gas phase Plasma is involved Large difference of energy level
52 Partial Discharges Studies 1. il 2. Salt Bath 3. Gas Phase 4. Electrode 5. Tesla oil
53 Partial Discharges Studies
54 Partial Discharges In Air Mineral il Soybean il igh leic Sunflower il Rape seed il A Rape seed il B Synthetic Ester il In Nitrogen Mineral il Soybean il igh leic Sunflower il Rape seed il A Rape seed il B Synthetic Ester il
55 D1 Study 1 Mineral il Soybean il igh leic Sunflower il Rape seed il Synthetic Ester il Study 2 Mineral il Soybean il igh leic Sunflower il
56 Duval 1 for D1 studies Duval 1 PD 1 T1 4 T2 24 D1 D2 DT T
57 Statistical Study 9 Percentile 9 Percentile Ester Liquids Mineral il Percentile 95 Percentile Ester Liquids Mineral il
58 Reference
59 Thank You Questions? orresponding laude Beauchemin
60 Understanding Dissolved Gas Analysis of Ester Liquids an Updated Review of Gas Generated in Ester Liquid by Stray Gassing, Thermal Decomposition and Electrical Discharge Initially presented at the 216 IEEE ELETRIAL INSULATIN NFERENE (EI)
61 Mineral il hemical Structure arbon ydrogen = ydrocarbon
62 Mineral il hemical Structure Aromatic Paraffinic Naphthenic arbon ydrogen = ydrocarbon
63 Natural Ester hemical Structure For R = and R, R, R = long hydrocarbon chain R 2 R R R Fatty Acid Fatty Acid R Fatty Acid R 2 Glycerol + Triglyceride Fatty Glycerol Ester Acid = Glyceride
64 R, R, R = Fatty Acid
65 Fatty Acid omposition (%) of Some Natural Ester Liquids Unsaturated = Grape Seed Palmitic 16: 8 Stearic 18: 4 leic 18: Linoleic 18: Linolenic 18:3 3 <1 Sum % 1 Peanut <1 93 Sunflower <1 1 Walnut Soybean anola Flax Seed
66 Differences of Natural Ester il from Mineral il 2 2 Numerous arbon Double Bonds Numerous Bonds Large amount of xygen Large Molecule
67 Mineral il Natural Ester Different composition Different structure Different properties Different reactions?
68 il Degradation Moderate temperature might produce gas Excessive temperature (ot Spot) will produce gas Arcing will produce gas PD will produce gas It occur in both mineral and ester oil
69 il Degradation Fortunately the gases produced are the same: 2 hydrogen 4 methane 2 6 ethane 2 4 ethylene 2 2 acetylene carbon monoxide 2 carbon dioxide Just not in the same proportion
70 Natural Ester Degradation: Stray Gassing In normal service, no gas production is expected owever, Ethane has been reported for normal operation This phenomena is called Stray Gassing It is also observed with some Mineral il But Mineral il produce mostly 2, not 26 Why?
71 1 + (From a nearby R) Ethane ( 2 6 ) 1 mega-3 Stray Gassing: Formation of Ethane from Linolenic Acid (xidation)
72 Stray Gassing: Formation of Ethane from Linolenic Acid is unstable 3 2 is the normal form of xygen So where 1 2 come from? That is Torun contribution to the science of DGA!!
73 Jablonski Diagram: Generation of 1 2 S n S 2 е - е - е - S 1 T 2 Electronic states Singlet (S,S 1,S 2,S n ) Triplet (T 1,T 2 ) Vibrational states Internal conversion (I), heat transfer Intersystem crossing (IS) γ Photon absorption γ S е - Fluorescent emission γ Phosphorescent emission е - Electronic Ground State T 1 Spin inversion е - е - е е - е - е Photosensitive Molecule Energy xygen Levels
74 Stray Gassing Photoreaction is compound dependant It is also dependant of light energy Is photoreaction also occurring in natural ester?
75 Stray Gassing The short answer is YES Natural ester fluid showing phosphorescence from photo activity (left) and after this activity had subsided (right).
76 Stray Gassing in Natural Ester ould be initiated by Free radical reaction ould be initiated by Photoreaction Exposure to light (UV and Sunlight) create gas Exposure to Light also increase gas generation at moderate temperature. Mostly 2, 2 6, and production related to oil composition
77 Stray Gassing in Natural Ester Importance of storing il properly New Stored New ASTM 715 Stored ASTM Impact of 3 years exposure of soybean oil to sunlight in Polyethylene As tank Received (ASTM D715 at 12 ) After Stray Gassing Test
78 Stray Gassing in Natural Ester Importance of storing sample properly Impact of one week sample exposure to light (ASTM D3612 method at 7 )
79 Stray Gassing Do not store oil sample under the sun Do not store outside in translucent container Expect some Ethane
80 Thermal Studies ontrolled thermal stress zone Studies from 25 to 7 at 5 degree intervals ontrolled fluid flow Thermal relaxation zone Fluid reservoir and headspace Managed system pressure Nitrogen environment Low oxygen content Fixed study time Ensemble of studies optimized at 8 hours. Liquid and gas sample collection
81 Thermal Studies Gas ollector Pump 8 ours Sampling N 2 il 1.5 L eater 25 7
82 Thermal Studies
83 Total gas volume 8 ours Total Gas Generation Volume (liters) Soybean Sunflower Mineral Temperature
84 Gas Produced in Soybean il Soybean il Amount of Gas (ppm) 1,, 8, 6, 4, 2, Temperature
85 Gas Produced in Sunflower il Sunflower il Amount of Gas (ppm) 1,, 8, 6, 4, 2, Temperature
86 Gas Produced in Mineral il 1,, Mineral il Amount of Gas (ppm) 8, 6, 4, 2, Temperature
87 Duval Triangle Mineral il Duval 1 PD 1 T1 4 T2 24 D1 D2 DT T
88 Duval Triangle Mineral + Soybean il Duval 1 PD 1 T1 4 T2 24 D1 D2 DT T
89 Duval Triangle Mineral + Soybean + Sunflower il Duval 1 PD 1 T1 4 T2 24 D1 D2 DT T
90 Modified Duval Triangles Duval 3 b 1 PD Duval 3 d PD 1 T1 T T2 D1 D1 T2 D2 DT T3 D2 DT 1 T
91 Acidity Thermal Degradation of Natural Ester generate also high level of Acidity Acid Number Temperature Soybean il >1 >1 >1 >1 >1 Sunflower il >1 >1 >1 >1 Mineral il
92 Electrical Discharges in Ester il In Arcing and PD, oil degradation occur in gas phase Plasma is involved Large difference of energy level
93 Partial Discharges Studies 1. il 2. Salt Bath 3. Gas Phase 4. Electrode 5. Tesla oil
94 Partial Discharges In Air Mineral il Soybean il igh leic Sunflower il Rape seed il A Rape seed il B Synthetic Ester il In Nitrogen Mineral il Soybean il igh leic Sunflower il Rape seed il A Rape seed il B Synthetic Ester il
95 D1 Study 1 Mineral il Soybean il igh leic Sunflower il Rape seed il Synthetic Ester il Study 2 Mineral il Soybean il igh leic Sunflower il
96 Duval 1 for D1 studies Duval 1 PD 1 T1 4 T2 24 D1 D2 DT T
97 Statistical Study 9 Percentile 9 Percentile Ester Liquids Mineral il Percentile 95 Percentile Ester Liquids Mineral il
98 Reference
99 Thank You Questions? orresponding laude Beauchemin
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