gasoline and diesel fuel quality confirmation and … · gasoline and diesel fuel quality...

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

October 12, 2012 1

Product Portfolio – In Lab Systems

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

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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

Single Transmission Cell

• Fixed path length liquid transmission cell – Standard 100µm

• Liquids only • Quantitative analysis

– 50 ppm to 5 % • Reproducible and easy to use

October 12, 2012 4

5500t FTIR

Single Transmission Cell Operation

October 12, 2012 5

1. Place Sample on Lower Window

3. Once in place analyze

the sample

2. Rotate into place

4. Cleaning is easy!

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

October 12, 2012 Confidentiality Label

6

Gasoline, 87 Oct Diesel


Wavenumber 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800

5.0

4.5

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0

Abso

rban

ce

Ethanol Light

Aromatics

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


1606

1505

14

93

1378

1307

876

848

833

806

780 76

6 75

1 741

723

699

Diesel, Danbury CT

1750 1700 1650 1600 1550 1500 1450 1400 1350 1300 1250 1200 1150 1100 1050 1000 950 900 850 800 750 700

3.0

2.5

2.0

1.5

1.0

0.5

0.0

Wavenumber

Abs

orba

nce

729

1607

1516

14

96

1379

1340

1273

1171

1091

1051

967

881

806

795

768 74

2

695

676

Petrol_Gasoline, Danbury CT

1750 1700 1650 1600 1550 1500 1450 1400 1350 1300 1250 1200 1150 1100 1050 1000 950 900 850 800 750 700

3.0

2.5

2.0

1.5

1.0

0.5

0.0

Wavenumber

Abs

orba

nce

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

CH2 Rock, Long chain

Mono/meta phenyl, ring pucker

Meta phenyl, 3 adj H wag

Para 2 adj. H wag Lone H wag, Meta phenyl &mono naphthyl

Toluene

Ben

zene

/met

a xy

lene

Meta Xylene Para Xylene

Ortho Xylene

Ethanol

Total Aromatic, Aromatic Ring Quadrant stretch

Aromatic Ring semicircle stretch

Total Aromatic, Aromatic Ring Quadrant stretch

Aromatic Ring semicircle stretch


1150 1100 1050 1000 950 900 850 800 750 700

0.60

0.55

0.50

0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.00

-0.05

Wavenumber

Abs

orba

nce

Ethanol, Gasoline

Diesel Aromatics

Toluene, Gasoline

Benzene, Gasoline

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


4331

.5

4258

.9

4167

.5

4069

.1

3633

.3

3602

.2

3347

.7

4600 4500 4400 4300 4200 4100 4000 3900 3800 3700 3600 3500 3400 3300 3200 3100

0.20

0.18

0.16

0.14

0.12

0.10

0.08

0.06

0.04

0.02

0.00

Wavenumber

Abs

orba

nce Ethanol, Gasoline

Diesel Hydrocarbons 0.0% Gasoline 0.5% Gasoline 1.5% Gasoline 3.0% Gasoline 5.0% Gasoline


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.


804.626 0.210

pct gasoline(691.497 -0.003)

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

2100 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700

0.70

0.65

0.60

0.55

0.50

0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.00

-0.05

-0.10

Wavenumber

Abs

orba

nce

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.



14

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

5

2

4

3

1

0

Actual Gasoline Concentration (vol%)

Pre

dict

ed G

asol

ine

Con

cent

ratio

n (v

ol%

)

5 2 4 3 1 0

805.

8 2

.507

Petro

l tol

uene

(728

.7 0

.001

)

Pt

l b(6

762

001

2)

1638

.0

1277

.7

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

1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700

1.0

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0.0

-0.1

Abs

orba

nce

Alkyl Nitrate, Cetane booster

Aromatics

Cetane Booster in Diesel Fuel

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

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


18

Agilent 5500 DialPath

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


19

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


20

1

2

3

4

5

15

16

17

18

19

29 30 33 34

Quant Validation Plot for EN 14078:2009 Range A Biodiesel % (V/V) R²=1.000

0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40

2.5

2.0

1.5

1.0

0.5

0.0

Peak Height Absorbance

Bio

dies

el C

once

ntra

tion

%(v

/v) % Biodiesel = 5.567(x) – 0.069

Biodiesel Analysis- Range A Biodiesel in Diesel Calibration Plot

Bio

dies

el %

(V/V

)(17

47.2

) Biodiesel in Diesel EN 14078:2009 Range A

1820 1810 1800 1790 1780 1770 1760 1750 1740 1730 1720 1710 1700 1690 1680 1670 1660

0.45

0.40

0.35

0.30

0.25

0.20

0.15

0.10

0.05

0.00

-0.05

-0.10 Wavenumber

Abso

rban

ce

0.50

Biodiesel Analysis- Range A Biodiesel in Diesel Spectral Overlay

1

3

4

5

6

7

15

17

18

19

20

21 Quant Validation Plot for En 14078:2009 Range B Biodiesel % (V/V) R²=1.000

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3

7

6

5

4

3

2

1

0

Peak Height

Con

cent

ratio

n

% Biodiesel = 5.595(x) - 0.074

Biodiesel Analysis- Range B Biodiesel in Diesel Calibration Plot

Bio

dies

el %

(V/V

)(17

47.1

)

Biodiesel in Diesel EN 14078:2009 Range B

1820 1810 1800 1790 1780 1770 1760 1750 1740 1730 1720 1710 1700 1690 1680 1670 1660

1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0

-0.2

Wavenumber

Abso

rban

ce

Biodiesel Analysis- Range B Biodiesel in Diesel Calibration Plot

Biodiesel Methods

Method Name Components Fuel - Biodiesel % in Diesel Version4.a2m Biodiesel 0.025% – 1% *requires 5500t/4500t or DialPath 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 Biodiesel 0.5% -20% *requires 5500/4500 DialPath Peak area @ 1745 cm-1 Fuel - Water in Diesel Version4.a2m Water in diesel 100 ppm – 900 ppm *requires 5500t/4500t or DialPath Water in diesel 900 ppm –3000 ppm *requires Water in Oil Surfactant Kit 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

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 Version5 Diesel TumblIR

Gasoline 2000-10000ppm Oxidation Relative

Antioxidant 150-10000ppm

Petrochemical - Fuel Methods


28

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


29

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

Ethanol in Gasoline 0-100% The overlaid IR spectra of ethanol in gasoline calibration standards measured at 100um with the DialPath accessory.


30

ETO

H(1

924.

1)

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

2700 2600 2500 2400 2300 2200 2100 2000 1900 1800 1700

.4

.2

.0

0.8

0.6

0.4

0.2

0.0

Wavenumber

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

12

1316

1723

3233

34

35

36

37

38

39

43

Quant Validation Plot for ETOHR²=0.999

0 1 2 3 4 5

100

90

80

70

60

50

40

30

20

10

0

Peak Area

Con

cent

ratio

n

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


32

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)turbine oil water.tdf,105 (R² = 0.859309544)

Actual Concentration ( C1 )Actual Concentration ( C1 )

Pred

icte

d C

once

ntra

tion

( F11

C1

)Pr

edic

ted

Con

cent

ratio

n ( F

11 C

1 )

-400

200

800

1400

-100 200 500 800 1100 1400 1700

-400

200

800

1400

-100 200 500 800 1100 1400 1700

91

92

93

94

103

104105

106

107

118

119

120

121

122

133

134

135

136

145

146147

148

158

159

160

161

172

173

174

175

185186187

188

199200201202

211212213214

224

225

226

227

238239

240242

253254

255

256

265

266

267

268

277

278

279

280281

294295

296297

306

307

308

-400

200

800

1400

-100 200 500 800 1100 1400 1700

300ppm span 500ppm Span

FT-IR subtraction spectra without surfactant: 1200ppm standard minus 20ppm spectra on four Instruments – Water absorbance is weak and inconsistent

3410

.8

4600 4400 4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600

0.022

0.020

0.018

0.016

0.014

0.012

0.010

0.008

0.006

0.004

0.002

0.000

-0.002

Wavenumber

Abso

rban

ce

Water OH stretch

Water HOH Deformation/ Scissors

Water hindered Rotation

1127

.5 0

.313

6

3454

.3

4200 4000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600

0.045

0.040

0.035

0.030

0.025

0.020

0.015

0.010

0.005

0.000

Wavenumber

Abso

rban

ce

FT-IR subtraction spectra with surfactant: 1300ppm spectra minus 5ppm spectra on four Instruments (3x more abs.)

IR spectral overlay of turbine oil (Mobil DTE) calibration standards 5-4300ppm, with surfactant stabilizer

3950 3900 3850 3800 3750 3700 3650 3600 3550 3500 3450 3400 3350 3300 3250 3200 3150 3100 3050

0.22

0.20

0.18

0.16

0.14

0.12

0.10

0.08

0.06

0.04

0.02

0.00

-0.02

-0.04

-0.06

-0.08

Wavenumber

Abs

orba

nce

turbine water surf actant.tdf ,25 (R² = 0.998029969)turbine water surf actant.tdf ,25 (R² = 0.998029969)

Pre

dic

ted C

onc

entr

atio

n (

F4 C

1 )

Pre

dic

ted C

onc

entr

atio

n (

F4 C

1 )

2500

4000

5500

2500

4000

5500

20

21222324

252627

28

2931

32

49505152

545556

57585960

616364

2500

4000

5500

PLS Actual vs. Predicted Quant Plot: Water in Turbine, w/ Surfactant Stabilizers (5-5500ppm)

5500t Predictions: Water in Turbine Oil w/ Surfactant

Stabilizers

PAL (ppm) KF (ppmDifference

(ppm) % Error525 504 21 4.2

1052 965 87 9.02027 2002 25 1.22914 2838 76 2.74835 4753 82 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

gasoline and diesel fuel quality confirmation and … · gasoline and diesel fuel quality...

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