Agilent Solutions for the Analysis of Ethanol- Based Fuels Derived From Biomass. James D. McCurry, Ph.D. Senior Scientist

Agilent Solutions for the Analysis of Ethanol- Based Fuels Derived From Biomass James D. McCurry, Ph.D. Senior Scientist

Agilent Solutions for the Analysis of Ethanol-Based Fuels Derived From Biomass Presented by Presented by James D. McCurry, Ph.D. Senior Scientist

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 3

Motor Fuels Containing Ethanol 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% gasoline hydrocarbons High ethanol content encourages production using green, renewable sources Requires special spark ignition engines Reformulated gasoline (RFG) Contain up to 12 wt% ethanol Additive used to reduce smog emitted from motor vehicles Replaces methyl-tert-butyl ether (MtBE) and other oxygenated additives in many countries Used in standard d spark-ignition iti engines

ASTM Ethanol Fuel Standards Citing GC Methods ASTM D4806 - Denatured Fuel Ethanol for Blending with Gasoline Property Specification ASTM Test Method Minimum ethanol content 92.1 vol % D5501 Maximum methanol content 05vol% 0.5 D5501 ASTM D5798 Standard Specification for Fuel Ethanol (E75-E85) E85) Property Specification ASTM Test Method Minimum ethanol content 70 79 vol % D5501 Maximum methanol content 0.5 vol% None

ASTM Method D5501 Agilent 7890A GC Instrument Conditions Method Scope 93 to 98 wt% ethanol 0.01 to 0.6 wt% methanol Column and Oven Temperature Column DB-1, 150 m x 0.25mm x 0.5 um Carrier gas Helium at 2.0 ml/min Initial Oven Temp 60 o C Initial Hold Time 15 min. Oven Ramp Rate 30 o C/min Final Temp 250 o C Final Hold Time 23 min. Split/Spltless Inlet Mode Split Mode Split ratio 200:1 Temp 300 o C Injection Size 0.5 ul Flame Ionization Detector Temp 300 o C

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% 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) RRF 1.95 2.15E-03 1.00 0.05 6.06E-03 2.82 92 4.28E-03 1.99 2.9 2.14E-03 1.00 0.1 6.05E-03 2.82 93 4.24E-03 1.98 3.8 2.14E-03 1.00 0.2 5.86E-03 2.74 94 4.23E-03 1.98 4.7 3.55E-03 1.00 0.3 1.22E-02 3.43 95 4.13E-03 1.16 5.6 2.12E-03 1.00 0.4 7.66E-03 3.61 96 4.26E-03 2.01 6.5 2.14E-03 1.00 0.5 6.22E-03 2.90 97 4.25E-03 1.98 7.4 2.15E-03 1.00 0.6 6.43E-03 2.99 98 4.24E-03 1.97 Avg 1.00 3.04 1.87

ASTM Method D5501 Commercial Denatured Fuel Ethanol Sample ethanol 12.89 min methanol 11.54 min 45 minute run time 15 20 25 30 35 40 min.

D5501 Interference of Methanol on 150-m Column Peak integration not optimized methanol isobutane & 1-butene 11.4 11.6 11.8 12.0 12.2 min. Peak integration optimized methanol isobutane & 1-butene 11.4 11.6 11.8 12.0 12.2 min.

ASTM D5501 - Agilent 7890A GC Analysis Precision Commercially available denatured fuel ethanol sample Run methanol ethanol heptane 1 0.038 98.006 0.049 2 0.038 97.993 0.053 3 0.038 97.983 0.050 4 0.040 97.992 0.049 5 0.040 97.985 0.049 6 0.038 98.036 0.049 7 0.036 97.998 0.054 8 0.038 98.004 0.052 9 0.038 98.016 0.049 10 0.038 98.022 0.049 Avg 0.038 98.004 0.050 STDDEV 0.001 0.017 0.002 RSD 2.972% 0.017% 3.870%

Extended D5501 A New ASTM Ethanol Fuel Method Needed for motor fuels containing > 10 vol% ethanol Identical GC configuration and conditions as existing D5501 Method Scope 10 to 100 wt% ethanol 0.01 to 0.6 wt% methanol Method uses linear regression calibration instead of average RRF

Extended D5501 Methanol and Ethanol Calibrations 120 25000 methano ol peak area 100 80 60 40 20 0 0.78 wt% 0.46 wt% 0.28 wt% 0.20 wt% y = 139.17x 0.02 0.04 wt% R² = 0.9989 0 0.2 0.4 0.6 0.8 1 peak area ethanol 20000 15000 10000 5000 0 19.8 wt% 49.7 wt% 75.1 wt% 98.9 wt% 90.3 wt% y = 205.45x 0.42 R² = 0.9997 0 20 40 60 80 100 120 wt% methanol wt% ethanol Meets ASTM Calibration Specification: R 2 = 0.99 099 y-int < 5

Extended D5501 Analysis of Three Fuels pa 5000 4000 Denatured fuel ethanol 3000 2000 1000 0 5000 4000 3000 2000 E85 1000 0 1600 1200 800 E25 400 0 10 15 20 25 30 35 40 min

Extended D5501 Agilent 7890A Precision Denatured Fuel Ethanol E85 Run methanol ethanol 1 0.040 96.620 2 0.045 95.651 3 0.045 96.287 4 0.046 97.478 5 0.043 97.818 Avg 0.044 96.771 STDDEV 0.002 0.881 RSD 5.451% 0.911% Run methanol ethanol 1 0.400 84.293 2 0.390 83.193 3 0.390 82.120 4 0.370 83.478 5 0.380 82.337 Avg 0.386 83.084 STDDEV 0.011 0.883 RSD 2.954% 1.062% E25 Run methanol ethanol 1 0.490 23.800 2 0.480 23.882 3 0.483 23.969 4 0.473 24.154 5 0.473 24.130 Avg 0.480 23.987 STDDEV 0.007 0.154 RSD 1.499% 0.641% Results are precise but E85 and E25 has methanol errors Reported amounts too high Large isobutane interference in sample

Improving Speed and Resolution for Ethanol Fuel Analysis D5501 and D5501 Extended methods run time > 50 minutes 150-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% ethanol) Accurate result requires fine tuning of column flow and peak integration High hydrocarbon content fuel (E85 and E25) has higher isobutane content

D5501 Interference of Methanol on 150-m Column Peak integration not optimized methanol isobutane 11.4 11.6 11.8 12.0 12.2 min. Peak integration optimized methanol isobutane 11.4 11.6 11.8 12.0 12.2 min.

Extended D5501 Agilent 7890A Precision Denatured Fuel Ethanol E85 Run methanol ethanol 1 0.040 96.620 2 0.045 95.651 3 0.045 96.287 4 0.046 97.478 5 0.043 97.818 Avg 0.044 96.771 STDDEV 0.002 0.881 RSD 5.451% 0.911% Run methanol ethanol 1 0.400 84.293 2 0.390 83.193 3 0.390 82.120 4 0.370 83.478 5 0.380 82.337 Avg 0.386 83.084 STDDEV 0.011 0.883 RSD 2.954% 1.062% E25 Run methanol ethanol 1 0.490 23.800 2 0.480 23.882 3 0.483 23.969 4 0.473 24.154 5 0.473 24.130 Avg 0.480 23.987 STDDEV 0.007 0.154 RSD 1.499% 0.641% Results are precise but E85 and E25 has methanol errors Reported amounts too high Large isobutane interference in sample

Improving Speed and Resolution for Ethanol Fuel 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

Deans Switch Configuration for Fuel Ethanol Analysis FID 1 restrictor 0.38m x 0.1 mm UDFS S/S Inlet PCM column1 - HP-1 15m x 0.25 mm x 0.25um FID 2 column2 - Innowax 15m x 0.25 mm x 0.25um Capillary Flow Technology Deans Switch

Heart-Cutting 2-D GC Ethanol Fuel Analysis Agilent 7890A GC Instrument Conditions Column and Oven Temperature 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 Column 2 flow Helium at 2.0 ml/min Oven Temp 45 o C isothermal Backflush on 3 min. Backflush off 3.5 min. Split/Spltless Inlet Mode Split Mode Split ratio 200:1 Temp 300 o C Injection Size 0.5 ul Flame Ionization Detector Temp 300 o C

Heart-Cutting 2-D GC Ethanol Fuel Analysis Denatured Fuel Ethanol Sample Unresolved ethanol, methanol and hydrocarbons Column 1 no heart cut, no backflush Cut time 1.2 1.6 min. 2 4 6 8 10 12 14 Backflush @ 3 min. Column 1 after heart cut plus backflush 2 4 6 8 10 12 14 Ethanol and methanol resolved from hydrocarbons Column 2 after heart cut plus backflush 2 4 6 8 10 12 14 min min min

Heart-Cutting 2-D GC Ethanol Fuel Analysis Methanol and Ethanol Calibrations 35 6000 methano ol peak area 30 25 20 15 10 5 0.28 wt% 0.20 wt% 0.46 wt% 078wt% 0.78 y = 38.517x - 0.3841 R² = 0.9989 peak area ethanol 5000 4000 3000 2000 1000 19.85 wt% 49.70 wt% 98.9292 wt% 90.26 wt% 75.09 wt% y = 51.717x -1.315 R² = 0.9984 0 004 0.04 wt% 0 0 0.2 0.4 0.6 0.8 1 0 50 100 150 methanol wt% ethanol wt% Meets ASTM Calibration Specification: R 2 = 0.99 y-int < 5

Heart-Cutting 2-D GC Ethanol Fuel Analysis Denatured Fuel Ethanol Sample Ethanol 2.552 min Methanol 2.305 min 1.6 1.8 2 2.2 2.4 2.6 2.8 Min.

Heart-Cutting 2-D GC Ethanol Fuel Analysis Denatured Fuel Ethanol Sample Precision Heart-Cutting 2-D GC D5501 (150m column) Run methanol ethanol Run methanol ethanol 1 0.021 97.882 1 0.019 98.006 2 0.021 97.883 2 0.019 97.993 3 0.021 97.877 3 0.019 97.983 4 0.021021 97.878 4 0.020020 97.992992 5 0.021 97.868 5 0.020 97.985 6 0.021 97.883 6 0.019 98.036 7 0.021 97.878 7 0.018 97.998 8 0.020020 97.894 8 0.019019 98.004 9 0.021 97.863 9 0.019 98.016 10 0.020 97.877 10 0.019 98.022 Avg 0.021 97.878 Avg 0.019 98.004 STDDEV 0.000 0.008 RSD 2.027% 0.009% STDDEV 0.001 0.017 RSD 2.972% 0.017%

Heart-Cutting 2-D GC Ethanol Fuel Analysis Check Sample Results Deans Switch methanol ethanol heptane ref 0.3 95.0 4.7 1 0.3 95.1 4.6 2 0.3 95.1 4.6 3 0.3 95.1 4.5 4 0.3 95.1 4.6 5 0.3 95.1 4.6 Avg 03 0.3 95.1 4.6

Heart-Cutting 2-D GC Ethanol Fuel Analysis E85 Fuel Sample E85 Run methanol ethanol 1 0.000 82.347 2 0.000 81.660 3 0.000 81.400 4 0.000 82.802 5 0.000 83.115 Avg 0.000 82.265 STDDEV 0.000000 0.730 RSD 0.887% Ethanol 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 min.

Heart-Cutting 2-D GC Ethanol Fuel Analysis E25 Fuel Sample E25 Run methanol ethanol 1 0.000 23.481 2 0.000 24.185 3 0.000000 23.411 4 0.000 25.306 5 0.000 25.212 Avg 0.000 24.319 STDDEV 0.000000 0.911 RSD 3.744% Ethanol 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 min

Expanding Analysis to Include Benzene and Toluene in a Single Run ethanol cut 1.2 1.6 min. benzene cut 2.07 2.13 min. toluene cut 3.38 3.58 HP-1 Primary Column Backflush 6.0 to 7.0 min 1 2 3 4 5 Min. ethanol HP-Innowax Secondary Column benzene toluene 1 2 3 4 5 Min.

Expanding Analysis to Include Benzene and Toluene in a Single Run Denatured Fuel Ethanol methanol ethanol benzene toluene avg wt% 0.021 97.881 0.006 0.016 RSD 2.794% 0.003% 3.892% 3.677% E85 Flex Fuel methanol ethanol benzene toluene avg wt% <0.010 81.802 0.049 0.246 RSD 0.598% 3.876% 4.016% E25 Fuel methanol ethanol benzene toluene avg wt% < 0.010 23.692 0.330 2.740 RSD 1.807% 2.020% 3.469% 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

Wrap-up e-seminar Questions Thank you for attending today s Agilent e-seminar. Our e-seminar schedule is expanding regularly. Please check our web site frequently at: www.agilent.com/chem/eseminars Or register for Stay current with e-notes to receive regular updates. Slide 31