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 100µm • Liquids only • Quantitative analysis – 50 ppm to 5 % • Reproducible and easy to use

4

October 12, 2012

Single Transmission Cell Operation

1. Place Sample on Lower Window

5

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

Confidentiality Label 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

8

Confidentiality Label 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.  Agilent’s 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

3

2

1 0 0

14

1

2 3 Actual Gasoline Concentration (vol%)

4

5 Confidentiality Label 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

Confidentiality Label October 12, 2012

Multi-reflection Sampling Crystal – 5500a ASTM D7371-07 Biodiesel in Diesel (1-100%)

18

Confidentiality Label October 12, 2012

Agilent 5500 DialPath EN 14078 : 2009 Biodiesel in Diesel (0.5-25%)

19

Confidentiality Label October 12, 2012

DialPath Accessory –Closed EN 14078 – 2009 (0.5-25%)

20

Confidentiality Label 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) R²=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) R²=1.000

21 7

% Biodiesel = 5.595(x) - 0.074 6

Concentration

5

20 6

4

3 19 5

2

18 4

1 3 17

0

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

Confidentiality Label 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

Confidentiality Label 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

Confidentiality Label October 12, 2012

100

Quant Validation Plot for ETOH R²=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

0

1

2

3 Peak Area

4

5

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 Beer’s Law calibration plot.

31

Confidentiality Label October 12, 2012

MicroLab FTIR Software: Fuel – Ethanol in Gasoline 0-100% 100um Final result using a 30 second measurement.

32

Confidentiality Label 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 (R² = 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 (R² = 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