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Bring The Power of Mobile Measurement To The Energy and Power Generation Industry
Bring The Power of Mobile Measurement To The Energy and Power Generation Industry
Bring The Power of Mobile Measurement To The Energy and Power Generation Industry
FT-IR Spectroscopy
in the Power
Generation Industry
Jim Fitzpatrick
Mobile FT-IR Product Specialist
Agilent Technologies, Inc.
July 16, 2013
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Spectroscopy
“Spectroscopy” is the study of how electromagnetic radiation interacts with the atoms
and molecules that compose matter
Infrared Infrared
(heat) Detector
Source
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Hexane
H H H H H H
| | | | | |
H–C–C–C–C–C–C–H
| | | | | |
H H H H H H
C – H stretch
Absorbance
H – C – H bend
Wavenumber (cm-1)
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Hexanol
H H H H H H
| | | | | |
H–C–C–C–C–C–C–O–H
| | | | | |
H H H H H H
Absorbance
C – O stretch
O – H stretch
Wavenumber (cm-1)
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What role can FT-IR play in the
Power Generation Industry?
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FT-IR
Relegated to laboratories
due to
• Its large size
• Complexity of use
• Expensive
• Generates data and not
actionable answers.due
to
• Its large size
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Mobile FT-IR
•Agilent has pioneered the
introduction of portable
spectrometers
•Comparable results to
laboratory spectrometers
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Analysis of Lubricants
- Lubricants protects parts, inherent part of a machine (without it, the machine does not function
properly) and prevent premature system/ machine failure
- Lubricants have a finite life (determined by certain specifications) beyond which they do not perform
their role.
- Without a proper lubrication management program, lubricated machines and engines see their
operating costs and maintenance costs skyrocket
- FT-IR spectroscopy can easily determine if an oil is fit for function or not
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Causes of oil failure
• Heat
• Extreme Pressures
• High sheer conditions
• Water
– Accelerates oxidation by forming peroxides
– Can cause wash out of antioxidants and other additives
• Metal wear particles
– Acts as a catalysts that accelerate oxidation
• Electrostatic sparking
– Introduces nitrates
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Oxidation
• Oxidation is a chemical change within the lubricating oil that significantly lowers it
lubricity and shortens remaining useful life.
• It is critical to extend the life of the lubricating oil and to minimize oxidation. This is
done with the use of anti-oxidants
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Infrared Spectrum of Oil
1.6
1.4
1.2
1.0 Demulsifying
Agents, Rust
0.8
Various Oxidation/ Inhibitors, Foam
Phenolic Suppressants,
0.6 Nitration Products,
Antioxidant Water/ And Antioxidants
0.4
and Additives
Amine
0.2 Antioxidant
0.0
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600
Wavenumber
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Measuring Anti Oxidants in Turbine Oil
di-tertiary-butyl
paracresol
N
H
Absorbance
Absorbance
3680 3675 3670 3665 3660 3655 3650 3645 3640 3635 3630 3625 3620 3615 3610 3460 3455 3450 3445 3440 3435 3430 3425 3420 3415 3410 3405
340 3400 3395
Wavenumber
5
Wavenumber
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Phenolic/Aminic Antioxidants in Turbine Oil
9000
8000 4
7000
19
6000
Concentration
5000
25
4000
3000
10
2000
Absorbance
7
1000
28
13
22
1
0
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Typical Oil Monitoring Graph (applicable to all
sorts of Oil)
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Water – The tribologists nemesis
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Water in oil – A difficult measurement
• Lack of Homogeneity
– Water forms micelles in oil
– Water adheres to container walls
– Separates out quickly (demulsifiers present)
– Forms layers
– Water droplets are attracted to each other
and air bubbles
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Problems with Water Measurement
Scatter
Detector I Detector I
R R
Large droplets => IR scattered Small droplets => IR absorbed
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Water Measurement Comparison
Conventional Method Stabilization Method
turbine oil water.tdf ,105 (R² = 0.859309544) turbine water surf actant.tdf ,25 (R ² = 0.998029969)
5500
268 67
66
68
161
265
1400
64
63
240
242 158 267
145 160 32 61
31
29
146
147 159
266 4000 60
58
59
57
279
135
Predicted Concentration ( F11 C1 )
188 238
Predicted Concentration ( F4 C1 )
239 28
277
26
27
25
254172
253 280
278148
185 133
136 281
800 186
306 187 256 54
56
134
500ppm
55
174
199 255 2500 22
21
24
23
106 200
201 308 173
175
202
297 307
296 118 225 50
52
121 51
49
200
span
214
211
213
212
294
295
120
119
224
227
103
107
226
104
105 300ppm span 1000
46
48
47
45
20
18
19
17
92
93 122 15
16
14
13
41
43
44
42
94
38
3910
37
4011
9
12
35
36
33 6
7
5
8
34
2
3
1
4
91
-500
-400
-500 1000 2500 4000 5500
-100 200 500 800 1100 1400 1700
Actual Concentration ( C1 )
Actual Concentration ( C1 )
Water OH
stretch
Absorbance
Absorbance
1127.5 0.3136
4000 2600 1600
4000 3400 2600 1600
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PAL Predictions: Water in Turbine Oil w/
Surfactant Stabilizers
Difference
PAL (ppm) KF (ppm (ppm) % Error
525 504 21 4.2
1052 965 87 9.0
2027 2002 25 1.2
2914 2838 76 2.7
4835 4753 82 1.7
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Usefulness of FT-IR for oil analysis
FT-IR provides an early warning on oil failure based on chemical changes within the oil
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FT-IR Spectroscopy - Operation
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Single Transmission Cell Operation
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Easy-to-understand results
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Petrochemical - Oil Methods
Gear
ASTM 2412 EP Fluid Mineral Hydraulic
DTE PM 220 Mineral ASTM 2412 Polyol Ester Synthetic/ Polyol Ester
EP 460 Mineral Calpar 150 Mineral
Spartan EP 220 Mineral Mobile DTE (24, 25, 26) Mineral
Terrestic 220 Mineral EHC (Fyrquel) Phosphate Ester
Duolec LE 1606 Iso 320 Mineral Exxon Nuto 68 Mineral
Duolec LE 1607 ISO 460 Mineral Hitachi HN 46 Mineral
Mobile 600 XP ISO 460 Mineral/Synthetic Cheveron H46 Mineral
Mobile SHC 220 Mineral/Synthetic HyGuard Mineral
Mobile SHC 636 ISO 680 Mineral/Synthetic Quinplex White LE 4010 H1 ISO 46 Mineral
Mobile SHC 636 ISO 68 Mineral/Synthetic Quinplex White L4030 H1 ISO 100 Mineral
Royal Purple Synfilm 220 Mineral/Synthetic Monolec LE 61110 ISO 46 Mineral
SL 150 Mineral Royal Purple Synfilm GT 100 Synthetic/ Mineral
SL 220 Mineral Quintolub 822-300 Synthetic Polyol Ester
SL 320 Mineral Quintolub 888-68 Synthetic Polyol Ester
SL 460 Mineral
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Petrochemical - Oil Methods (cont.)
Turbine Transformer
Busch Mineral ASTM D2668 - Antioxidants
Monolec LE 6404 ISO 100 Mineral
Synthetic/ Compressor
Royal Purple Syndraulic ISO 32 Mineral
Monolec LE6403 ISO 68
Exxon Terrestic GT 32 Mineral
Turbine Oil Mineral
Crude
Chevron GST Mineral
Water in Crude Oil (0 - 1%)
Water in Crude Oil (0 - 80%)
Engine
ASTM 2412 Crankcase Mineral
Crankcase Oil (A2 Method) Mineral Other
Military Oil Mineral Antifreeze in water
Rotella T 15w40 Mineral
Mobile 1 Synthetic Water in ethanol
Oil in water (0 - 30 ppm)
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Contaminant Detection By FT-IR
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Environment – Oil in Water
High solids in water requires solvent extraction
•Process waters from offshore oil drilling
•Accidental oil spills
•Harbor water cleanup
•Waste water regulation
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Environment –
Oil in Water by Extraction
•Oil in water a key environmental measurement
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Environment – Oil in Water by Cyclohexane
Extraction (ASTM D7678)
• These ASTM D7678 based FT-IR results will correlate to other methods
- ASTM D3921, D7066, ISO 9377-2, EPA 413.2, and 418.1 methods
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Environment – Oil in Water by Cyclohexane
Extraction (ASTM D7678) Simplified Procedure
Simple 5 step process –
1. Add Cyclohexane
Add 20mL of cyclohexane to 900mL of process water and vigorously
shake for 2 minutes.
2. Remove Top Layer
Allow layers to separate, and remove the top layer for analysis
3. Add Cleaning Agents
Add 2g drying agent (sodium sulfate) and 2g Florisil™ to the cyclohexane
extract, shake vigorously, and allow to settle for 2minutes.
4. Filter Cyclohexane Extract
Filter the “cleaned” cyclohexane with a 0.45um nylon syringe filter (17mm).
5. Measure FTIR Spectrum
Add the cyclohexane to the Dialpath™ or TumblIR™ cell and initiate the FTIR
scanning. The result will be displayed after 30seconds of scanning.
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The automatically obtained data results from the MicroLab software for the
4500series and 5500series FTIR spectrometers.
This result is from a validation standard of 9.3mg/L mineral oil and 5mg/L
vegetable oil in fresh water, then extracted with 20mL cyclohexane and filtered.
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The mineral oil in cyclohexane calibration plot of actual (x-axis) vs. predicted
(y-axis) values. The values displayed are the final concentrations of oil in water
based on the ASTM D7678 parameters (900mL water, 20mL cyclohexane).
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Fuel Analysis By FT-IR
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Petrochemical - Fuel Methods
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Petrochemical - Fuel Methods
Method Name Fuel Type Sample Interface Components Range
Fuel - Gasoline Analysis PAL Gasoline TumblIR
MTBE 0.25-16.5 vol%
ETBE 0.25-16.5 vol%
Ethanol 0.1-16.5 vol%
Total Aromatics 0.5-45 vol%
Total Olefins 2-12 vol%
Benzene 0.2-2.5 vol%
Toluene 0.5-25 vol%
RON 85-97
MON 80-86
Water Relative
Fuel - Gasoline Water Analysis Gasoline TumblIR
Water 150-6000ppm
Fuel - Water in Diesel Stabilized Diesel TumblIR
Water 100-4000ppm
Oxidation Relative
Fuel - Water in Gasoline (0-80%)
Stabilized Gasoline TumblIR
Water 0 - 80 vol%
Fuel - Gasoline in Diesel Version3 Diesel TumblIR
Gasoline 1000-20000ppm
Oxidation Relative
Antioxidant 150-10000ppm
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Gasoline in Diesel Fuel
-- Causes coke formation on fuel injectors, and excessive wear on fuel contact
parts
-- Problem is worse in Ultra low sulfur diesel (ULSD) engines
Much less lubricity than off-road, agricultural or older diesel formulations
Sulfonated hydrocarbons are removed in ULSD
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Gasoline in Diesel Fuel
5.0
Gasoline, 87 Oct Light
4.5
Diesel Ethanol Aromatics
4.0
3.5
3.0
Absorbance
2.5
2.0
1.5
1.0
0.5
0.0
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800
Wavenumber
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Gasoline in Diesel Fuel
Diesel Aromatics
0.60 0.0% Gasoline
0.55
0.5% Gasoline
1.5% Gasoline
0.50
3.0% Gasoline
0.45
5.0% Gasoline
0.40
0.35
Absorbance
0.30
Ethanol, Gasoline
0.25
0.20
0.15
0.10
Toluene,
Gasoline
0.05
0.00
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Biodiesel Analysis
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Petrochemical - Biodiesel Methods
Method Name Components
Fuel - Biodiesel % in Diesel Version4.a2m Biodiesel 0.025% – 1%
*requires 5500t/4500t Biodiesel 1% - 10%
Biodiesel 10% - 20%
Interference – water vapor
Interference – diesel oxidation
Fuel - Water in Diesel Version4.a2m Water in diesel 100 ppm – 900 ppm
*requires 5500t/4500t Water in diesel 900 ppm –3000 ppm
*requires Water in Oil Surfactant Kit Diesel oxidation
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Agilent 5500a Multibounce FT-IR
ASTM D7371-07 Biodiesel in Diesel (1-100%)
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Material Verification /Degradation
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Hand Held FTIR Material Identification
Germanium ATR
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Hand Held FT-IR Material Identification
O-ring and Seal Identification
Demonstration
15 samples provided by Material Research Society
Exoscan correctly identified all samples
Only one sample had a close second match
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Cable Degradation Analysis
The protective jacket made from XLPE, EPR, Hypalon, EPDM etc are losing their
original properties
Insulating power,
Mechanical properties.
Hand-held FT-IR provides a means for non-destructive cable analysis in the field.
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Degradation at elevated temperatures over time
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Thank you for attending!
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