RAPID FUEL STREAM HYDROCARBON CHARACTERIZATION ACHIEVED THROUGH GAS - - PowerPoint PPT Presentation

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RAPID FUEL STREAM HYDROCARBON CHARACTERIZATION ACHIEVED THROUGH GAS - - PowerPoint PPT Presentation

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RAPID FUEL STREAM HYDROCARBON CHARACTERIZATION ACHIEVED THROUGH GAS CHROMATOGRAPHY- VACUUM ULTRAVIOLET SPECTROSCOPY Ryan Schonert, James Diekmann, Jack Cochran Just because something works doesnt mean it cant be improved.

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RAPID FUEL STREAM HYDROCARBON CHARACTERIZATION ACHIEVED THROUGH GAS CHROMATOGRAPHY- VACUUM ULTRAVIOLET SPECTROSCOPY

Ryan Schonert, James Diekmann, Jack Cochran

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SLIDE 2

“Just because something works doesn’t mean it can’t be improved.” – Princess Shuri, Black Panther (2018)

Image: https://www.popsugar.com/entertainment/Shuri-What-Those-Joke-Black-Panther-44597679

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GASOLINE ANALYSIS

ASTM D6730 DHA:

  • PIONA
  • Oxygenates
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GASOLINE ANALYSIS

  • Required for quality control

and regulation

  • Can be accomplished using

Detailed Hydrocarbon Analysis (DHA)

  • ASTM Method D6730, for

example

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SLIDE 5

DETAILED HYDROCARBON ANALYSIS

FID

Flame Ionization Detector

ASTM D6730-01(2016), Standard Test Method for Determination of Individual Components in Spark Ignition Engine Fuels by 100–Metre Capillary (with Precolumn) High-Resolution Gas Chromatography, ASTM International, West Conshohocken, PA, 2016, www.astm.org.
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SLIDE 6

DETAILED HYDROCARBON ANALYSIS

✓Well-known method ✓Approved for quality control ✓Used for decades X Identification by retention time only X 2+ hour run time, plus data analysis time X Not equipped to analyze novel compounds

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SLIDE 7

DETAILED HYDROCARBON ANALYSIS

✓Well-known method ✓Approved for quality control ✓Used for decades X Identification by retention time only X 2+ hour run time, plus data analysis time X Not equipped to analyze novel compounds

Our goal: create an alternative to DHA using GC-VUV

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SLIDE 8

VACUUM ULTRAVIOLET SPECTROSCOPY (VUV)

VUV Analytics VGA-100 125 to 240nm 1 to 75 spectra/sec

43 cm 8

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SLIDE 9

VACUUM ULTRAVIOLET SPECTROSCOPY (VUV)

9

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Hexane 1-Hexene Benzene 2-Hexanone

10

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SLIDE 12

12

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SLIDE 13

13

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SLIDE 14

14

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ASTM D8071 – PIONA ANALYSIS WITH GC-VUV

  • Identification by retention

time and absorption spectra

  • Spectral deconvolution
  • Easily add new compounds

to spectral library

  • Run time: ~33.6 min
ASTM D8071-17, Standard Test Method for Determination of Hydrocarbon Group Types and Select Hydrocarbon and Oxygenate Compounds in Automotive Spark-Ignition Engine Fuel Using Gas Chromatography with Vacuum Ultraviolet Absorption Spectroscopy Detection (GC-VUV), ASTM International, West Conshohocken, PA, 2017, www.astm.org.
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SLIDE 16

VUV Verified Hydrocarbon Analysis (VHA): The Next DHA

  • Use ASTM D6730 GC conditions
  • 100m x 0.25mm x 0.50µm “methyl silicone” GC column
  • Cryogenic oven start
  • Exception: no precolumn for critical separations
  • Build VUV VHA gasoline compound retention time

table using D6730 DHA Component Table

  • Use VUV Analyze software for automated data

processing

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SLIDE 17

VHA - BY THE NUMBERS

  • Currently report mass and volume

% data for 151 compounds

  • Individual compounds add up to

about 90% of gasoline composition

  • Other compounds are classed

through absorbance spectra shape and RI

  • Class carbon number report from

C3 to C15

  • Run time: 174 min
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SLIDE 18

VS

VUV VHA ASTM D8071

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SLIDE 19

Gasoline analyzed with ASTM D8071 GC-VUV 30m x 0.25mm x 0.25µm Rxi-1ms 29 min Gasoline analyzed with VHA GC-VUV 100m x 0.25mm x 0.50µm Rtx-DHA 160 min

Methylnaphthalenes Methylnaphthalenes 1,2,4-Trimethylbenzene 1,2,4-Trimethylbenzene Xylenes Xylenes Ethylbenzene Ethylbenzene Toluene Toluene

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SLIDE 20

Gasoline analyzed with VHA GC-VUV 100m x 0.25mm x 0.50µm Rtx-DHA 6 to 46 min range

Toluene Butane Ethanol iso-Pentane Pentane 2-Methyl-2-butene 2-Methylpentane Hexane Methylcyclopentane 1-Methylcyclopentene Benzene 2-Methylhexane iso-Octane Heptane Methylcyclohexane

Gasoline analyzed with ASTM D8071 GC-VUV 30m x 0.25mm x 0.25µm Rxi-1ms 1.8 to 7.8 min range

Toluene Ethanol Butane iso-Pentane

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SLIDE 21

Gasoline analyzed with VHA GC-VUV 100m x 0.25mm x 0.50µm Rtx-DHA 69 to 113 min range

1,2,4-Trimethylbenzene m-Xylene Ethylbenzene p-Xylene

  • -Xylene

Nonane Isopropylbenzene n-Propylbenzene 1-Methyl-3-ethylbenzene 1-Methyl-4-ethylbenzene 1,3,5-Trimethylbenzene 1-Methyl-2-ethylbenzene 1,2,3-Trimethylbenzene Decane

Gasoline analyzed with ASTM D8071 GC-VUV 30m x 0.25mm x 0.25µm Rxi-1ms 12.2 to 19.2 min range

Ethylbenzene m-Xylene p-Xylene

  • -Xylene

1,2,4-Trimethylbenzene 1-Methyl-3-ethylbenzene 1,2,3-Trimethylbenzene Nonane

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SLIDE 22

2-Methylnaphthalene 1-Methylnaphthalene Naphthalene 1,4-Dimethyl-2-ethylbenzene 1,2,4,5-Tetramethylbenzene 1,2,3,5-Tetramethylbenzene 1,2,4,5-Tetramethylbenzene 1,2,3,5-Tetramethylbenzene Naphthalene 2-Methylnaphthalene 1-Methylnaphthalene

Gasoline, D8071, GC-VUV 30m x 0.25mm x 0.25µm Rxi-1ms 19.2 to 25.8 min range Gasoline, VHA, GC-VUV 100m x 0.25mm x 0.50µm Rtx-DHA 112 to 147 min range

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SLIDE 23

Category MEG D8071 MEG VHA B02 D8071 B02 VHA M872 D8071 M872 VHA M873 D8071 M873 VHA Paraffin 13.7 15.2 17.6 17.5 7.93 8.18 12.8 12.9 Isoparaffin 27.6 28.5 18.9 18.7 68.6 70.0 25.1 24.5 Olefin 13.2 12.7 13.4 14.5 1.98 0.929 0.276 0.003 Naphthene 8.84 6.37 2.26 1.84 2.12 1.06 5.65 5.54 Aromatic 25.6 24.8 36.6 36.1 19.3 19.9 55.4 56.3 Di-Aromatic 0.970 0.859 0.063 0.152 0.788 0.760 Ethanol 10.1 11.5 11.1 11.4 Iso-octane 1.91 2.08 4.87 5.07 16.6 17.7 Benzene 0.426 0.479 0.222 0.234 0.446 0.451 Toluene 3.51 3.99 15.4 16.0 6.91 7.70 15.1 15.5 Ethylbenzene 0.875 0.847 1.37 1.15 1.37 1.31 3.25 3.03 Xylenes 5.55 5.83 6.50 6.81 6.88 7.40 16.1 17.2 Naphthalene 0.266 0.279 0.063 0.053 0.401 0.437 Methylnaphthalenes 0.590 0.580 0.099

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SLIDE 24

Can We Improve VUV VHA GC Run Time?

Method translation:

  • Shorter column
  • Thinner column film
  • Adjusted oven program

MUCH shorter run time: ~49 min

How are the separations?

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SLIDE 25

Gasoline analyzed with VHA GC-VUV 100m x 0.25mm x 0.50µm Rtx-DHA 160 min

Methylnaphthalenes 1,2,4-Trimethylbenzene Xylenes Ethylbenzene Toluene

Gasoline analyzed with VHA GC-VUV 60m x 0.25mm x 0.25µm Rxi-1ms 47 min

Methylnaphthalenes 1,2,4-Trimethylbenzene Xylenes Ethylbenzene Toluene

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SLIDE 26

Gasoline analyzed with VHA GC-VUV 100m x 0.25mm x 0.50µm Rtx-DHA 6 to 46 min range

Toluene Butane Ethanol iso-Pentane Pentane 2-Methyl-2-butene 2-Methylpentane Hexane Methylcyclopentane 1-Methylcyclopentene Benzene 2-Methylhexane iso-Octane Heptane Methylcyclohexane

Gasoline analyzed with VHA GC-VUV 60m x 0.25mm x 0.25µm Rxi-1ms 3.2 to 15.2 min range

Toluene Butane Ethanol iso-Pentane Pentane 2-Methyl-2-butene 2-Methylpentane Hexane Methylcyclopentane 1-Methylcyclopentene Benzene 2-Methylhexane iso-Octane Heptane Methylcyclohexane

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SLIDE 27

Gasoline analyzed with VHA GC-VUV 100m x 0.25mm x 0.50µm Rtx-DHA 69 to 113 min range

1,2,4-Trimethylbenzene m-Xylene Ethylbenzene p-Xylene

  • -Xylene

Nonane Isopropylbenzene n-Propylbenzene 1-Methyl-3-ethylbenzene 1-Methyl-4-ethylbenzene 1,3,5-Trimethylbenzene 1-Methyl-2-ethylbenzene 1,2,3-Trimethylbenzene Decane

Gasoline analyzed with VHA GC-VUV 60m x 0.25mm x 0.25µm Rxi-1ms 21 to 32.5 min range

1,2,4-Trimethylbenzene m-Xylene Ethylbenzene p-Xylene

  • -Xylene

Nonane Isopropylbenzene n-Propylbenzene 1-Methyl-3-ethylbenzene 1-Methyl-4-ethylbenzene 1,3,5-Trimethylbenzene 1-Methyl-2-ethylbenzene 1,2,3-Trimethylbenzene Decane

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SLIDE 28

2-Methylnaphthalene 1-Methylnaphthalene Naphthalene 1,4-Dimethyl-2-ethylbenzene 1,2,4,5-Tetramethylbenzene 1,2,3,5-Tetramethylbenzene

Gasoline, VHA, GC-VUV 100m x 0.25mm x 0.50µm Rtx-DHA 112 to 147 min range

2-Methylnaphthalene 1-Methylnaphthalene Naphthalene 1,4-Dimethyl-2-ethylbenzene 1,2,4,5-Tetramethylbenzene 1,2,3,5-Tetramethylbenzene

Gasoline, VHA, GC-VUV 60m x 0.25mm x 0.25µm Rxi-1ms 32.2 to 42.6 min range

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SLIDE 29

Mass % Comparison for Gasoline Analyzed with 3 GC-VUV Methods

  • ASTM D8071
  • 30m x 0.25mm x 0.25µm, no

cryo

  • ASTM D6730 VUV VHA
  • 100m x 0.25mm x 0.50µm,

cryo

  • “Fast” VUV VHA
  • 60m x 0.25mm x 0.25µm, cryo

Category 30m D8071 100m VHA 60m VHA Paraffin 13.7 15.2 13.8 Isoparaffin 27.6 28.5 27.7 Olefin 13.2 12.7 12.3 Naphthene 8.84 6.37 7.75 Aromatic 25.6 24.8 26.9 Di-Aromatic 0.970 0.859 0.994 Ethanol 10.1 11.5 10.6 Iso-octane 1.91 2.08 2.00 Benzene 0.426 0.479 0.441 Toluene 3.51 3.99 3.82 Ethylbenzene 0.875 0.847 0.913 Xylenes 5.55 5.83 5.96 Naphthalene 0.266 0.279 0.345 Methylnaphthalenes 0.590 0.580 0.615

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CONCLUSIONS

  • GC-VUV is a powerful way to analyze gasoline-range

samples

  • PIONA, select individual hydrocarbons, oxygenates
  • GC-VUV VHA is more powerful than GC-FID DHA
  • Spectral confirmation of compound with automated

processing

  • Faster GC-VUV VHA has been demonstrated
  • Similar chromatography on 100m and 60m columns
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SLIDE 31

Thank You!

Ryan.Schonert@VUVAnalytics.com VUV Analytics, https://vuvanalytics.com/