improved performance of the analysis of aromatics in gasoline … · 2016. 9. 4. · get standards...
TRANSCRIPT
![Page 1: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/1.jpg)
Improved Performance of the Analysis of Aromatics in Gasoline by ASTM Method D5769 Using the Agilent 5977B GC/MS with the InertPlus Source
Agilent technologies, Inc.
June 2016
Fred Feyerherm
![Page 2: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/2.jpg)
Reformulated Gasoline from epa.gov website
![Page 3: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/3.jpg)
Reformulated Gasoline - background:
US Congress Clean Air Act of 1973
Amended 1990
Directed EPA to clean up urban air
EPA method 80.46 (f) (from 40 CFR)
ASTM subsequently developed D5769
High accuracy and precision using GCMS
Impacted 180 refineries in US and anyone
shipping gasoline to US
![Page 4: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/4.jpg)
Reformulated Gasoline - background:
Parameters Regulated:
Total Aromatics (GCMS) limited to <25 vol%
Benzene (GC)
Oxygenates (GC-OFID)
Olefins (D1319 FIA)
Sulphur (X-ray)
Reid Vapor Pressure
Why GCMS for Aromatics?
EPA wanted to identify unknowns from possible dumping
EPA has a lab in Ann Arbor Michigan
![Page 5: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/5.jpg)
What is Gasoline…chemically?
Saturates
Olefins
Napthenes (e.g. cyclohexane)
Aromatics
Oxygenates
Traces of other compounds
![Page 6: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/6.jpg)
GCMS Chromatogram of Gasoline
![Page 7: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/7.jpg)
Use Mass Spec to identify peaks
![Page 8: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/8.jpg)
ASTM Method D5769 for Total Aromatics in Gasoline
![Page 9: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/9.jpg)
Use Extracted ion to find targeted compoundsExtracted Ion Chromatogram EIC m/z 78
![Page 10: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/10.jpg)
Quantitation by GCMS
Get a standard for each compound
Use extracted ion chromatogram to get peak and integrate
Use an Internal Standard (e.g. Benzene-d6)
But you can’t readily get standards for every possible aromatic
Get standards for all C6 – C9 and selected C10 Aromatics
Create Uncalibrated Compound Groups as directed in D5769
![Page 11: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/11.jpg)
D5769 Uncalibrated C10-benzenes
![Page 12: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/12.jpg)
C7 (Toluene m/z 91) and C8 Aromatics
![Page 13: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/13.jpg)
C9 Aromatics m/z 120
![Page 14: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/14.jpg)
C10 Aromatics m/z 134
![Page 15: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/15.jpg)
C11 Aromatics m/z 148
![Page 16: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/16.jpg)
C12 Aromatics m/z 162
![Page 17: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/17.jpg)
Additional Aromatics: Indane and alkylated Indanes m/z 117
![Page 18: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/18.jpg)
Additional Aromatics: Naphthalenes
![Page 19: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/19.jpg)
Quantitation Compound List for D5769
![Page 20: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/20.jpg)
D5769 differences from normal GCMS type analysisSpecial Software
Gravimetric calibration
• Raw weights
• Multiple gravimetric ISTDs
• Update from disc (Accustandard)
Quantitate Uncalibrated aromatics using RF from
calibrated cpnd
Report both Wt % and Vol %
![Page 21: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/21.jpg)
![Page 22: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/22.jpg)
Keys for SuccessExcellent Linearity for all analytes on 5977B GCMS
![Page 23: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/23.jpg)
Regulatory Compliance
EPA has contracted Southwest Research Institute (SWRI) for
compliance monitoring
SWRI Lab in San Antonio does most monitoring samples
EPA Ann Arbor also does some
![Page 24: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/24.jpg)
Regulatory Compliance
My Opinion: Everyone needs to get the same answer, not necessarily the best answer for total aromatics in gasoline.
As SWRI
Same STDs
Same column
Same method
![Page 25: Improved Performance of the Analysis of Aromatics in Gasoline … · 2016. 9. 4. · Get standards for all C6 –C9 and selected C10 Aromatics Create Uncalibrated Compound Groups](https://reader035.vdocument.in/reader035/viewer/2022071507/6127c3a5b5dc9a19b4301ec5/html5/thumbnails/25.jpg)
Thank you Let’s Continue the Conversation