Gasoline and Diesel

Fuel Quality
Confirmation and
Composition by FTIR

Gulf Coast Conference 2012

Agilent Mobile Spectroscopy
5500/4500 FTIR

Frank Higgins
Applications Development Scientist
October 2012
1

October 12, 2012

Product Portfolio In Lab Systems

Physical Attributes
8 lbs
8 x 8 x 4.5
External Computer
USB connection
External Power
Full spectral analysis

4500 Series FTIR

Physical Attributes
15 lbs
8 x 11.5 x 7.5
Integrated PDA computer
Optional PC
Internal battery
Dedicated sample interface
Designed for field use

5500/4500 Series FTIR Sampling Interfaces

5500t FTIR
Single Transmission Cell
Fixed path length liquid transmission cell
Standard 100m
Liquids only
Quantitative analysis
50 ppm to 5 %
Reproducible and easy to use

October 12, 2012

Single Transmission Cell Operation

1. Place Sample
on Lower Window

2. Rotate into
place

3. Once
in place analyze
the sample

4. Cleaning is
easy!

October 12, 2012

Gasoline in Diesel Fuel

Gasoline fuel contamination in diesel fuel causes engine
failures
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

Gasoline can wash varnish deposits into the engine

Lowers the diesel cetane value or energy content
Manufacturers want proof of no gasoline in diesel for
warranty engine repairs
6

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October 12, 2012

Gasoline in Diesel Fuel

5.0

Gasoline, 87 Oct
Diesel

4.5

Light
Aromatics

Ethanol

4.0
3.5

Absorbance

3.0
2.5
2.0
1.5
1.0
0.5
0.0

3800

3600

3400

3200

3000

2800

2600

2400
2200
Wavenumber

2000

1800

1600

1400

1200

1000

800

Gasoline in Diesel Fuel

Aromatic IR bands from gasoline are best to quantitate the
amount of contamination
Ethanol bands are strong with less interference with diesel
but are less suitable for quantitative analysis.
Pipeline gasoline contamination might not have ethanol
Amount used in gasoline varies
Some gasolines can use MTBE or ETBE as oxygenates with little or
no EtOH

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October 12, 2012

Gasoline in Diesel Fuel

Mono/meta phenyl,
ring pucker

Meta phenyl, 3 adj H wag

1350

1300

1100

1050

1000

950

900

850

800

Meta Xylene
Para Xylene

1091

881

1496

1171

1273

0.5
0.0
1700

1650

1600

1550

1500

1450

1400

700

Toluene

Ethanol
1750

750

Ortho Xylene

1340

1.0

1516

1.5

Aromatic Ring
semicircle stretch
Total Aromatic,
Aromatic Ring
Quadrant stretch
1607

Absorbance

2.0

1150

1379

Petrol_Gasoline, Danbury CT
2.5

1250 1200
Wavenumber

1350

1300

1250 1200
Wavenumber

1150

1100

1050

1000

695

1400

676

1450

729

1500

742

1550

768

1600

806
795

1650

967

1700

1051

1750
3.0

950

Benzene/meta xylene

0.0

699

Lone H wag, Meta

phenyl &mono naphthyl

848
833

0.5

CH2 Rock,
Long chain

Para 2 adj. H wag

1307

1.0

Mono phenyl
(5 adj. H wag);
& 4 adj. H wag

1505
1493

1.5

Aromatic Ring
semicircle stretch
Total Aromatic,
Aromatic Ring
Quadrant stretch
1606

Absorbance

2.0

876

2.5

806

1378

Diesel, Danbury CT

780
766
751
741
723

3.0

900

850

800

750

700

Gasoline in Diesel Fuel

Diesel Aromatics
0.60
0.55
0.50
0.45

0.0% Gasoline
0.5% Gasoline
1.5% Gasoline
3.0% Gasoline
5.0% Gasoline

0.40

Absorbance

0.35

Ethanol, Gasoline

0.30
0.25
0.20
0.15

Toluene,
Gasoline

0.10
0.05
0.00

Benzene, Gasoline

-0.05
1150

1100

1050

1000

950

900

Wavenumber

850

800

750

700

4331.5

Gasoline in Diesel Fuel

0.0% Gasoline
0.5% Gasoline
1.5% Gasoline
3.0% Gasoline
5.0% Gasoline

Diesel Hydrocarbons
4258.9

0.20

0.18

4167.5

0.12

Ethanol, Gasoline

0.10

3347.7

0.06

3602.2

0.08
3633.3

Absorbance

0.14

4069.1

0.16

0.04

0.02

0.00
4600

4500

4400

4300

4200

4100

4000

3900

3800

Wavenumber

3700

3600

3500

3400

3300

3200

3100

Gasoline in Diesel Fuel

Winter diesel has more aromatics relative to summer diesel.

This causes some interference with the measurement of the
gasoline aromatics.
Chemometrics or partial least squares (PLS) calibration models help
reduce the interference from these seasonal variations.
PLS models are trained with gasoline in diesel standards
prepared from both winter, summer, and 50/50 mixed diesel.
PLS calibrations allow the use of multiple regions of the spectra.
Agilents Microlab software includes conditional reporting
Determines which calibration model is best for the current
sample spectrum
Chooses winter, summer, or mixed diesel calibrations.
These capabilities allow for more robust and reproducible gasoline
in diesel measurements by FTIR.

Gasoline in Diesel Fuel

IR spectra of pure summer diesel (blue) and pure winter diesel (purple).
The light aromatics from gasoline absorb in this region as well, but have
frequencies that are shifted relative to the diesel aromatics.
0.70

pure winter diesel test1_2011-08-12t11-15-49(1)

0.65
0.60
0.55
0.50
0.45

Absorbance

0.40
0.35
0.30
0.25
804.626 0.210

0.20
0.15
0.10
0.05

pct gasoline(691.497 -0.003)

0.00
-0.05
-0.10
2100

2000

1900

1800

1700

1600

1500

1400
Wavenumber

1300

1200

1100

1000

900

800

700

Gasoline in Diesel Fuel

Predicted Gasoline Concentration (vol%)

Final gasoline in diesel PLS calibration model (vol% Gasoline): SECV= 0.100, R2=
0.9957, 6 factors, LOQ=0.225

5
4

1
0
0

14

2
3
Actual Gasoline Concentration (vol%)

5
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October 12, 2012

Cetane Booster in Diesel Fuel

1.0

diesel fuel audi vin wa1am7419d035555_2010-05-28t11-49-15(1)

0.9

0.7

Petrol toluene(728.7 0.001)

Alkyl Nitrate,
Cetane booster

0.8

0.5

0.3

0.2

(676 2 0 012)

1277.7

805.8 2.507

0.4

1638.0

0.1

0.0

P t lb

Absorbance

0.6

Aromatics

-0.1
1900

1800

1700

1600

1500

1400

1300

1200

1100

1000

900

800

700

Biodiesel Analysis
Increased use of Biodiesel.
Many countries allow or require biodiesel in regular diesel
Some states allow up to 3% biodiesel in diesel without disclosure

Biodiesel is not appropriate for all fuel uses

Can clog filters, reduce cold weather performance, or cause problems with
storage.

Need exists to measure biodiesel for 2 different goals

1. Monitor % biodiesel for blending
B5, B10, B50
Regulatory and compliance

2. Monitor low levels of biodiesel as a contaminant

0.025% to 20%

Regulatory methods specify FTIR

EN 14078 : 2009 Transmission Liquid Cell
ASTM D7371-07 Mulitple Reflection ATR

Agilent 5500a Multibounce FTIR

ASTM D7371-07 Biodiesel in Diesel (1-100%)

17

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October 12, 2012

Multi-reflection Sampling Crystal 5500a

ASTM D7371-07 Biodiesel in Diesel (1-100%)

18

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October 12, 2012

Agilent 5500 DialPath

EN 14078 : 2009 Biodiesel in Diesel (0.5-25%)

19

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October 12, 2012

DialPath Accessory Closed

EN 14078 2009 (0.5-25%)

20

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October 12, 2012

Biodiesel Analysis- Range A Biodiesel in

Diesel Calibration Plot
2.5

19
5

Biodiesel Concentration %(v/v)

Quant Validation Plot for EN 14078:2009 Range A Biodiesel % (V/V)

R=1.000
2.0

% Biodiesel = 5.567(x) 0.069

1.5

18
4

1.0

3
17

0.5
16
2

0.0

115

34
30

29
33

0.05

0.10

0.15

0.20

0.25

Peak Height Absorbance

0.30

0.35

0.40

0.50

Biodiesel in Diesel EN 14078:2009 Range A

0.45
0.40
0.35

Biodiesel % (V/V)(1747.2)

Biodiesel Analysis- Range A Biodiesel in

Diesel Spectral Overlay

Absorbance

0.30
0.25
0.20
0.15
0.10
0.05
0.00
-0.05
-0.10

1820

1810

1800

1790

1780

1770

1760

1750
1740
1730
Wavenumber

1720

1710

1700

1690

1680

1670

1660

Biodiesel Analysis- Range B Biodiesel in

Diesel Calibration Plot
7

Quant Validation Plot for En 14078:2009 Range B Biodiesel % (V/V)

R=1.000

21
7

% Biodiesel = 5.595(x) - 0.074

6

Concentration

20
6

3
19
5

18
4

1
3
17

115

0.0

0.1

0.2

0.3

0.4

0.5

0.6
0.7
Peak Height

0.8

0.9

1.0

1.1

1.2

1.3

Biodiesel Analysis- Range B Biodiesel in

Diesel Calibration Plot
Biodiesel in Diesel EN 14078:2009 Range B
Biodiesel % (V/V)(1747.1)

1.4

1.2

1.0

Absorbance

0.8

0.6

0.4

0.2

0.0

-0.2
1820

1810

1800

1790

1780

1770

1760

1750 1740 1730

Wavenumber

1720

1710

1700

1690

1680

1670

1660

Biodiesel Methods
Method Name
Fuel - Biodiesel % in Diesel Version4.a2m
*requires 5500t/4500t or DialPath

Components
Biodiesel 0.025% 1%
Biodiesel 1% - 10%
Biodiesel 10% - 20%
Interference water vapor
Interference diesel oxidation

Fuel - Biodiesel ASTM D7371-07 Version3.a2m

Biodiesel 1% - 10%
*requires 5500/4500a w/ Multi-reflection ATR Biodiesel 10% - 30%
Biodiesel 30% - 100%
Fuel - Biodiesel EN 14078 2009 Version4.a2m
*requires 5500/4500 DialPath

Biodiesel 0.5% -20%

Peak area @ 1745 cm-1

Fuel - Water in Diesel Version4.a2m

*requires 5500t/4500t or DialPath
*requires Water in Oil Surfactant Kit

Water in diesel 100 ppm 900 ppm

Water in diesel 900 ppm 3000 ppm
Diesel oxidation

Petrochemical - Fuel Methods

In addition to Biodiesel contamination, the 5500/4500 can be

used to determine fuel quality parameters.
Water Contamination
Gasoline
Diesel

Gasoline contamination in diesel

Gasoline performance characteristics
Oxygenates, RON, MON, Aromatics

Petrochemical - Fuel Methods

Method Name

Fuel Type

Sample Interface

Fuel - Gasoline Analysis PAL

Gasoline

TumblIR

Fuel - Gasoline Water Analysis

Fuel - Water in Diesel Stabilized

Fuel - Water in Gasoline (0-80%)

Stabilized
Fuel - Gasoline in Diesel Version5

Gasoline
Diesel

Gasoline
Diesel

Components

Range

MTBE
ETBE
Ethanol
Total Aromatics
Total Olefins
Benzene
Toluene
RON
MON
Water

0.25-16.5 vol%
0.25-16.5 vol%
0.1-16.5 vol%
0.5-45 vol%
2-12 vol%
0.2-2.5 vol%
0.5-25 vol%
85-97
80-86
Relative

Water

150-6000ppm

Water
Oxidation

100-4000ppm
Relative

Water

0 - 80 vol%

Gasoline
Oxidation
Antioxidant

2000-10000ppm
Relative
150-10000ppm

TumblIR
TumblIR

TumblIR
TumblIR

Ethanol in Gasoline High Concentrations

Typical standard US gasoline contains 7-10% ethanol (EtOH).
New flexfuel engines allow the use of E85 gasoline
E85 has less exhaust emissions
High volatility increases octane level and horsepower
Lower combustion and exhaust temperatures
Renewable
Can be produced locally
E85 has some draw backs
30% less energy per gallon compared to normal gasoline with 10% EtOH
On a mileage basis it may be more expensive than normal gasoline
Ethanol is hydroscopic and water build up is a potential problem if fuel sits for
a long period of time
Inconsistency can cause engine tuning/performance problems

28

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October 12, 2012

Ethanol in Gasoline High Concentrations

Inconsistency Problem
85% EtOH is the maximum spec in E85 gasoline
E85 can be in spec with as little as 51% EtOH
Gasoline is added to meet volatility requirements
Seasonal variations in temp require different formulations
Actual EtOH concentrations in E85 can vary widely from pump to pump
Auto manufacturers need a fast and easy onsite EtOH in gasoline measurement
Aides in diagnosing engine problems or failures
Warranty issues

29

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October 12, 2012

.4

100v pct etoh, 100um dp6 630 64scns_2012-07-03t16-28-24(1)

.2

.0

ETOH(1924.1)

0.8

0.6

0.4

0.2

0.0

2700

2600

2500

2400

2300

2200
2100
Wavenumber

2000

1900

1800

1700

Ethanol in Gasoline 0-100%

The overlaid IR spectra of ethanol in gasoline calibration standards
measured at 100um with the DialPath accessory.

30

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October 12, 2012

100

Quant Validation Plot for ETOH

R=0.999

39

90

34

80
35

Concentration

70
60
36

50

37

40
30
38

20
16
13
32
33
43

10
0

2312
17

3
Peak Area

High concentration ethanol in gasoline

calibration
Nine calibration standards are prepared volumetrically in the 0-100%
ethanol range. The peak area at 1924cm-1 is used for this Beers
Law calibration plot.

31

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October 12, 2012

MicroLab FTIR Software:

Fuel Ethanol in Gasoline 0-100% 100um
Final result using a 30 second measurement.

32

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October 12, 2012

Water in oil

Low PPM Water quantification by FTIR

Turbine
Gear
Hydraulic
Bunker fuel
Crude Oil
Biodiesel
Diesel
Gasoline
Water/glycol mix

PLS Method with Surfactant:

Water in Turbine Oil
Addition of surfactant oil stabilizer to the turbine oil
Creates a stable emulsion
Maximum IR water absorbance achieved at 3% surfactant
Two different non-ionic PEO based surfactants used

Three fold increase in water absorbance

Less IR scattered light, more absorbed
Smaller water particle (micelle) sizes, with a narrower distribution

Water measurements are very reproducible

Variability in the non-surfactant method has been eliminated

Preliminary PLS Analysis: Water in Turbine Oil

Without Surfactant
turbine oil water.tdf,105 (R = 0.859309544)

268

161
265

1400
240
242

145
146
147

158
160

267

159

266

Predicted Concentration ( F11 C1 )

279
135

188

800
306

106

500ppm
Span
214
211
213
212

200

199
200
201

185
186
187

254
253172
133
136
256
134
174
255

308

173
175

202
297 118
296
121

225

294
295

224
227
103
120
119

307

238
239
277
280
278148
281

300ppm span

107
226
104
105

92
93

122

94

91

-400
-100

200

500

800

Actual Concentration ( C1 )

1100

1400

1700

0.022
0.020
0.018

Water OH stretch

3410.8

FT-IR subtraction spectra without surfactant:

1200ppm standard minus 20ppm spectra on four
Instruments Water absorbance is weak and
inconsistent

Water hindered
Rotation

0.016

Absorbance

0.014
0.012

Water HOH
Deformation/ Scissors

0.010
0.008
0.006
0.004
0.002
0.000
-0.002
4600 4400 4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000
Wavenumber

800

600

3454.3

FT-IR subtraction spectra with surfactant: 1300ppm

spectra minus 5ppm spectra on four Instruments
(3x more abs.)

0.045
0.040
0.035

0.025
0.020
0.015
1127.5 0.3136

Absorbance

0.030

0.010
0.005
0.000

4200

4000

3800

3600

3400

3200

3000

2800

2600 2400
Wavenumber

2200

2000

1800

1600

1400

1200

1000

800

600

IR spectral overlay of turbine oil (Mobil DTE)

calibration standards 5-4300ppm, with surfactant
stabilizer
0.22
0.20
0.18
0.16
0.14
0.12

Absorbance

0.10
0.08
0.06
0.04
0.02
0.00
-0.02
-0.04
-0.06
-0.08

3950

3900

3850

3800

3750

3700

3650

3600

3550
3500
Wavenumber

3450

3400

3350

3300

3250

3200

3150

3100

3050

PLS Actual vs. Predicted Quant

Plot: Water in Turbine, w/
Surfactant Stabilizers (55500ppm)
5500t Predictions: Water in
Turbine Oil w/ Surfactant
Stabilizers
turbine water surfactant.tdf ,25 (R = 0.998029969)

5500

32
31
29

Predict ed Conc ent ration ( F 4 C 1 )

4000

60
58
59
57

28
26
27
25

54
56
55
22
21
24
23

2500

50
52
49
51

20

64
63
61

Difference
PAL (ppm) KF (ppm (ppm)
525
504
21
1052
965
87
2027
2002
25
2914
2838
76
4835
4753
82

% Error
4.2
9.0
1.2
2.7
1.7

Fuel Analysis - Conclusions

The 4500t/5500t or DialPath can be used for multiple fuel analysis applications
Gasoline in Diesel
0.2-10% gasoline range
Works in summer, winter, or mixed season diesel
Biodiesel concentration in diesel fuel
Both mixing and contamination levels
Ethanol in Gasoline
Covers the high concentration range for E85 gasoline
Uses the same 100um DialPath or TumblIR used for other oil and fuel methods
Calibrations are pre-defined in the Microlab software
Water in turbine oil surfactant technology applies to diesel, gasoline, and crude oil
Makes FTIR water measurements consistent
Calibrated to Coulometric Karl Fischer water
Easy to use step by step method