Agilent Solutions for the Analysis of Ethanol-Based Fuels Derived From Biomass

James D. McCurry, Ph.D. Senior Scientist

September 14 2010September 14, 2010

Agilent Solutions for the Analysis of g yEthanol-Based Fuels Derived From

BiomassBiomass

Presented byPresented byJames D. McCurry, Ph.D. Senior ScientistSeptember 14, 2010

Outline

• Overview of ethanol containing motor fuels

• Current ASTM fuel ethanol standards and methods

• New developments in ASTM for ethanol based fuel methods

• Agilent 7890A GC Analysis Using ASTM Method D5501

• Agilent 7890A GC Analysis Using New ASTM Method

• Improving Productivity and Resolution

September 14, 2010

3

Motor Fuels Containing EthanolD t d f l th l• Denatured fuel ethanol

• Anhydrous ethanol denatured with natural gasoline (natural gas condensates)

• Used as a blending stock for oxygenated motor fuels (E85 and RFG)

• Produced from renewable resources: sugars or biomass

• Fuel ethanol (E75-E85) “Flex Fuel”

• A new fuel containing 75 to 85 vol% denatured fuel ethanol and 25 to 15 vol%A new fuel containing 75 to 85 vol% denatured fuel ethanol and 25 to 15 vol% gasoline hydrocarbons

• High ethanol content encourages production using green, renewable sources

• Requires special spark ignition enginesRequires special spark ignition engines

• Reformulated gasoline (RFG)

• Contain up to 12 wt% ethanol

Additi d t d “ ” itt d f t hi l• Additive used to reduce “smog” emitted from motor vehicles

• Replaces methyl-tert-butyl ether (MtBE) and other oxygenated additives in many countries

U d i t d d k i iti i• Used in standard spark-ignition engines

September 14, 2010

ASTM Ethanol Fuel Standards Citing GC MethodsMethods

ASTM D4806 - Denatured Fuel Ethanol for Blending with Gasoline

Property Specification ASTM Test MethodMinimum ethanol content 92.1 vol % D5501

Maximum methanol content 0 5 vol% D5501Maximum methanol content 0.5 vol% D5501

ASTM D5798 Standard Specification for Fuel Ethanol (E75 E85)ASTM D5798 Standard Specification for Fuel Ethanol (E75-E85)

Property Specification ASTM Test MethodMinimum ethanol content 70 – 79 vol % D5501

Maximum methanol content 0.5 vol% None

September 14, 2010

ASTM Method D5501Agilent 7890A GC Instrument ConditionsAgilent 7890A GC Instrument Conditions

• Method Scope

• 93 to 98 wt% ethanol• 93 to 98 wt% ethanol

• 0.01 to 0.6 wt% methanol

Column and Oven Temperature Split/Spltless InletColumn and Oven Temperature

Column DB-1, 150 m x 0.25mm x 0.5 um

Carrier gas Helium at 2.0 mL/min

Split/Spltless Inlet

Mode Split Mode

Split ratio 200:1

Initial Oven Temp 60 oC

Initial Hold Time 15 min.

Oven Ramp Rate 30 oC/min

Temp 300 oC

Injection Size 0.5 uL

Final Temp 250 oC

Final Hold Time 23 min.

Flame Ionization Detector

Temp 300 oC

September 14, 2010

ASTM D5501 - Agilent 7890A GC Calibration• 7 Levels of calibration

• Heptane range: 1.95 to 7.4 wt%

• Methanol range: 0.05 to 0.6 wt%g

• Ethanol range: 92 to 98 wt%

• Use average RRF for sample quantification

n-heptane methanol ethanol

wt% RF (wt%/area) RRF wt% RF (wt%/area) RRF wt% RF (wt%/area) RRF1.95 2.15E-03 1.00 0.05 6.06E-03 2.82 92 4.28E-03 1.992.9 2.14E-03 1.00 0.1 6.05E-03 2.82 93 4.24E-03 1.983.8 2.14E-03 1.00 0.2 5.86E-03 2.74 94 4.23E-03 1.984.7 3.55E-03 1.00 0.3 1.22E-02 3.43 95 4.13E-03 1.165.6 2.12E-03 1.00 0.4 7.66E-03 3.61 96 4.26E-03 2.016.5 2.14E-03 1.00 0.5 6.22E-03 2.90 97 4.25E-03 1.987.4 2.15E-03 1.00 0.6 6.43E-03 2.99 98 4.24E-03 1.97

September 14, 2010

Avg 1.00 3.04 1.87

ASTM Method D5501 – Commercial Denatured Fuel Ethanol SampleFuel Ethanol Sample

ethanol12.89 min

methanol 45 minute run time

15 20 25 30 35 40 min

11.54 min

September 14, 2010

15 20 25 30 35 40 min.

D5501 – Interference of Methanol on 150-m ColumnColumn

Peak integration not optimized

methanol isobutane& 1-butene

11.4 11.6 11.8 12.0 12.2 min.

methanol isobutane

Peak integration optimized

methanol isobutane& 1-butene

September 14, 2010

11.4 11.6 11.8 12.0 12.2 min.

ASTM D5501 - Agilent 7890A GC Analysis PrecisionPrecisionCommercially available denatured fuel ethanol sample

Run methanol ethanol heptaneRun methanol ethanol heptane1 0.038 98.006 0.0492 0.038 97.993 0.0533 0.038 97.983 0.0503 0.038 97.983 0.0504 0.040 97.992 0.0495 0.040 97.985 0.0496 0.038 98.036 0.0497 0.036 97.998 0.0548 0.038 98.004 0.0529 0.038 98.016 0.049

10 0.038 98.022 0.049Avg 0.038 98.004 0.050

STDDEV 0.001 0.017 0.002

September 14, 2010

RSD 2.972% 0.017% 3.870%

Extended D5501 – A New ASTM Ethanol Fuel MethodMethod

• Needed for motor fuels containing > 10 vol% ethanol

• Identical GC configuration and conditions as existing D5501• Identical GC configuration and conditions as existing D5501

• Method Scope

• 10 to 100 wt% ethanol10 to 100 wt% ethanol

• 0.01 to 0.6 wt% methanol

• Method uses linear regression calibration instead of average RRFMethod uses linear regression calibration instead of average RRF

September 14, 2010

Extended D5501 – Methanol and Ethanol CalibrationsCalibrations

0.78 wt%100

120 25000

0.46 wt%60

80

100

ol p

eak

area

75.1 wt%

90.3 wt%98.9 wt%

15000

20000

peak

are

a

0.20 wt%0.28 wt%

y = 139.17x – 0.02R² 0 9989

20

40

met

hano

19.8 wt%

49.7 wt%

y = 205.45x – 0.42R² 0 9997

5000

10000

etha

nol

0.04 wt% R² = 0.99890

0 0.2 0.4 0.6 0.8 1

wt% methanol

R² = 0.99970

0 20 40 60 80 100 120

wt% ethanol

Meets ASTM Calibration Specification:

R2 = 0.99

September 14, 2010

0 99y-int < 5

Extended D5501 – Analysis of Three Fuels

pA

4000

5000

Denatured fuel ethanol

0

1000

2000

3000 Denatured fuel ethanol

2000

3000

4000

5000

E85

0

1000

1600

0

400

800

1200 E25

September 14, 2010

min10 15 20 25 30 35 400

Extended D5501 – Agilent 7890A PrecisionD t d F l Eth l E8Denatured Fuel Ethanol

Run methanol ethanol1 0.040 96.6202 0.045 95.651

E85Run methanol ethanol

1 0.400 84.2932 0.390 83.193

3 0.045 96.2874 0.046 97.4785 0.043 97.818

Avg 0.044 96.771

3 0.390 82.1204 0.370 83.4785 0.380 82.337

Avg 0.386 83.084STDDEV 0.002 0.881

RSD 5.451% 0.911%

gSTDDEV 0.011 0.883

RSD 2.954% 1.062%

E25Run methanol ethanol

1 0.490 23.8002 0.480 23.8823 0.483 23.969

Results are precise but…

E85 and E25 has methanol errors

Reported amounts too high4 0.473 24.1545 0.473 24.130

Avg 0.480 23.987STDDEV 0.007 0.154

• Reported amounts too high

• Large isobutane interference in sample

September 14, 2010

STDDEV 0.007 0.154RSD 1.499% 0.641%

Improving Speed and Resolution for Ethanol Fuel AnalysisFuel Analysis

• D5501 and D5501 Extended methods run time > 50 minutes

• 150-meter column needed to resolve alcohols from hydrocarbons150 meter column needed to resolve alcohols from hydrocarbons

• Shorter column are faster, but have insufficient resolution

• Higher selectivity columns (GS-OxyPLOT) have insufficient capacity

• Long oven temperature program

• Extra time needed to cool down between runs

• Poor methanol/isobutane resolution

• Resolution only marginal with denatured fuel ethanol (92 – 99 wt% th l)ethanol)

• Accurate result requires fine tuning of column flow and peak integration

• High hydrocarbon content fuel (E85 and E25) has higher isobutane

September 14, 2010

g y ( ) gcontent

D5501 – Interference of Methanol on 150-m ColumnColumn

Peak integration not optimized

methanol isobutane

11.4 11.6 11.8 12.0 12.2 min.

methanol isobutane

Peak integration optimized

methanol isobutane

September 14, 2010

11.4 11.6 11.8 12.0 12.2 min.

Extended D5501 – Agilent 7890A PrecisionD t d F l Eth l E8Denatured Fuel Ethanol

Run methanol ethanol1 0.040 96.6202 0.045 95.651

E85Run methanol ethanol

1 0.400 84.2932 0.390 83.193

3 0.045 96.2874 0.046 97.4785 0.043 97.818

Avg 0.044 96.771

3 0.390 82.1204 0.370 83.4785 0.380 82.337

Avg 0.386 83.084STDDEV 0.002 0.881

RSD 5.451% 0.911%

gSTDDEV 0.011 0.883

RSD 2.954% 1.062%

E25Run methanol ethanol

1 0.490 23.8002 0.480 23.8823 0.483 23.969

Results are precise but…

E85 and E25 has methanol errors

Reported amounts too high4 0.473 24.1545 0.473 24.130

Avg 0.480 23.987STDDEV 0.007 0.154

• Reported amounts too high

• Large isobutane interference in sample

September 14, 2010

STDDEV 0.007 0.154RSD 1.499% 0.641%

Improving Speed and Resolution for Ethanol Fuel AnalysisFuel Analysis

• 2-D GC can improve both speed and resolution

• Using shorter columns improves speed

• Combining different column types improves resolution

• Use other techniques to improve speed

• GC backflush can quickly remove unwanted peaks

• Isothermal analysis have zero cycle time between runs

September 14, 2010

Deans Switch Configuration for Fuel Ethanol AnalysisAnalysis

FID 1

S/S Inlet PCM

restrictor0.38m x 0.1 mm UDFS

S/S Inlet PCM

column1 - HP-115m x 0 25 mm x 0 25um

FID 2

15m x 0.25 mm x 0.25um

column2 - Innowax15m x 0.25 mm x 0.25um

Capillary Flow TechnologyDeans Switch

Heart-Cutting 2-D GC Ethanol Fuel AnalysisAgilent 7890A GC Instrument ConditionsAgilent 7890A GC Instrument Conditions

Column and Oven Temperature Split/Spltless Inlet

Column 1 HP-1, 15m x 0.25mm x 0.25 um

Column 1 flow Helium at 1.0 mL/min

Column 2 HP-Innowax, 15m x 0.25mm x 0.25um

Mode Split Mode

Split ratio 200:1

Temp 300 oCColumn 2 HP Innowax, 15m x 0.25mm x 0.25um

Column 2 flow Helium at 2.0 mL/min

Oven Temp 45 oC isothermal

Temp 300 C

Injection Size 0.5 uL

Backflush on 3 min.

Backflush off 3.5 min.

Flame Ionization Detector

Temp 300 oC

September 14, 2010

Heart-Cutting 2-D GC Ethanol Fuel AnalysisDenatured Fuel Ethanol SampleDenatured Fuel Ethanol Sample

Unresolved ethanol, methanol and hydrocarbons

min2 4 6 8 10 12 14

Column 1 – no heart cut,no backflush

and hydrocarbons

min2 4 6 8 10 12 14

Column 1 – after heart cut

Cut time1.2 – 1.6 min.

Backflush @ 3 min.

min2 4 6 8 10 12 14

plus backflush

Ethanol and methanol resolved

min2 4 6 8 10 12 14

Column 2 – after heart cutplus backflush

methanol resolved from hydrocarbons

min2 4 6 8 10 12 14

Heart-Cutting 2-D GC Ethanol Fuel Analysis Methanol and Ethanol CalibrationsMethanol and Ethanol Calibrations

0 78 wt%30

35

98 92 wt%5000

6000

0.46 wt%

0.78 wt%

20

25

30

ol p

eak

area

49 70 t%

75.09 wt%90.26 wt%

98.92 wt%

3000

4000

5000

peak

are

a

0 04 t%

0.20 wt%

0.28 wt%

y = 38.517x - 0.3841R² = 0.99895

10

15

met

hano

19.85 wt%

49.70 wt%

y = 51.717x -1.315R² = 0.99841000

2000

etha

nol

0.04 wt%00 0.2 0.4 0.6 0.8 1

methanol wt%

00 50 100 150

ethanol wt%

Meets ASTM Calibration Specification:R2 = 0.99y-int < 5

September 14, 2010

Heart-Cutting 2-D GC Ethanol Fuel AnalysisDenatured Fuel Ethanol SampleDenatured Fuel Ethanol Sample

Ethanol2.552 min

Methanol2.305 min

1.6 1.8 2 2.2 2.4 2.6 2.8 Min.

September 14, 2010

Heart-Cutting 2-D GC Ethanol Fuel AnalysisDenatured Fuel Ethanol Sample PrecisionDenatured Fuel Ethanol Sample Precision

D5501 (150m column)Run methanol ethanol

Heart-Cutting 2-D GCRun methanol ethanol Run methanol ethanol

1 0.019 98.0062 0.019 97.9933 0.019 97.9834 0 020 97 992

Run methanol ethanol1 0.021 97.8822 0.021 97.8833 0.021 97.8774 0 021 97 878 4 0.020 97.992

5 0.020 97.9856 0.019 98.0367 0.018 97.9988 0 019 98 004

4 0.021 97.8785 0.021 97.8686 0.021 97.8837 0.021 97.8788 0 020 97 894 8 0.019 98.004

9 0.019 98.01610 0.019 98.022

Avg 0.019 98.004

8 0.020 97.8949 0.021 97.86310 0.020 97.877

Avg 0.021 97.878STDDEV 0.001 0.017

RSD 2.972% 0.017%STDDEV 0.000 0.008

RSD 2.027% 0.009%

September 14, 2010

Heart-Cutting 2-D GC Ethanol Fuel AnalysisCheck Sample ResultsCheck Sample Results

Deans SwitchDeans Switchmethanol ethanol heptane

ref 0.3 95.0 4.71 0.3 95.1 4.62 0.3 95.1 4.63 0.3 95.1 4.53 0.3 95.1 4.54 0.3 95.1 4.65 0.3 95.1 4.6

0 3 9 1 6Avg 0.3 95.1 4.6

September 14, 2010

Heart-Cutting 2-D GC Ethanol Fuel AnalysisE85 Fuel SampleE85 Fuel Sample

EthanolE85Run methanol ethanol

1 0.000 82.3472 0.000 81.6603 0.000 81.4004 0.000 82.8025 0.000 83.115

Avg 0.000 82.265STDDEV 0 000 0 730STDDEV 0.000 0.730

RSD 0.887%

1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 min.

September 14, 2010

Heart-Cutting 2-D GC Ethanol Fuel AnalysisE25 Fuel SampleE25 Fuel Sample

E25 EthanolE25Run methanol ethanol

1 0.000 23.4812 0.000 24.1853 0 000 23 411

Ethanol

3 0.000 23.4114 0.000 25.3065 0.000 25.212

Avg 0.000 24.319STDDEV 0 000 0 911STDDEV 0.000 0.911

RSD 3.744%

min1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8

September 14, 2010

Expanding Analysis to Include Benzene and Toluene in a Single RunToluene in a Single Run

ethanol cut1.2 – 1.6 min.

benzene cut2.07 – 2.13 min.

toluene cut3.38 – 3.58

HP-1 Primary Column

Backflush

1 2 3 4 5 Min.

Backflush6.0 to 7.0 min

ethanol HP-Innowax Secondary Column

1 2 3 4 5 Min

benzene toluene

September 14, 2010

Min.

Expanding Analysis to Include Benzene and Toluene in a Single RunToluene in a Single Run

Denatured Fuel Ethanolmethanol ethanol benzene toluenemethanol ethanol benzene toluene

avg wt% 0.021 97.881 0.006 0.016RSD 2.794% 0.003% 3.892% 3.677%

E85 Flex Fuelmethanol ethanol benzene toluene

avg wt% <0.010 81.802 0.049 0.246RSD 0 598% 3 876% 4 016%RSD 0.598% 3.876% 4.016%

E25 Fuelmethanol ethanol benzene toluene

avg wt% < 0.010 23.692 0.330 2.740RSD 1.807% 2.020% 3.469%

September 14, 2010

Statistics calculated for 3 consecutive runs for each sample

Summary• Improving Speed and Accuracy of Ethanol Fuel Analysis with 2-D GC

– Initially developed by Agilent in 2003, now update for the 7890A GC– Greater Productivity

– 7890A backflush capabilities to reduce run time to 3 minutes– Can be used to obtain same results as D5501 and the Extended D5501

methods– Higher resolution improves methanol accuracy – Easily expanded to include benzene and toluene analysis in ethanol fuels

September 14, 2010

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