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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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