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Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Zhuangzhi ‘Max’ Wang, PhD, Richard Whitney, PhD, Clifford M. Taylor, Nicole Lock, Laura Chambers, GCMS Product Manager, Shimadzu Scientific Instruments, Columbia, MD, USA, 800-477-1227, www.ssi.shimadzu.com
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To improve productivity and lower the capital cost, a single gas chromatograph has been configured to perform two standard methods: CAN/CGSB-3.0 and ASTM D-5580.
Detailed hydrocarbon (DHA) analysis of automotive gasoline has become a routine gas chromatographic method. The Canadian standard CAN/CGSB-3.0 requires cryogenic temperature programing to provide better separation of early-eluting components than conventional non-cryogenic DHA measurements. Determination of aromatics in the presence of methanol and ethanol is also an important requirement for bio-ethanol; method ASTM D-5580 is the standard method for this analysis.
In this work, the two applications have been successfully integrated into one GC. The methods of three tests – one for CAN/CGSB-3.0 and two for ASTM D-5580, can be switched smoothly with minimum effort. Automated software control provides separation of hydrocarbons in groups and reporting of the results for method CAN/CGSB-3.0. Repeatability (%RSD) of ASTM D-5580 was less than 1.2% for analysis No. 1, and less than 1.8% for analysis No. 2.
This configuration is not limited to motor gasoline analysis though; it can be applied to other finished products such as blend alcohol and other new green energy products.
Introduction
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Instrumentation
Columns: 20% TCEP, 0.558m X
0.75mm Rtx-1 30m X 0.53mm X
5µm
LN2 Cryo-cooling
Injection Volume: 1 µL Valve box Temp: 80C APC1 Pressure: 210.0KPa GCSolution ver. 2.41 PONASolution ver. 2.60
Rtx-1
TCEP
PONA
GC-2010Plus
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ObjectiveSeparation of hydrocarbons into types
Paraffins, Olefins, Naphthene, Aromatics
Separation of each type according to carbon number
MethodSingle capillary column separation of all components, followed by grouping with a post-run program - PONA Solution
Canadian PONA Method CAN/CGSB-3.0
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Column: Rtx-1 PONA 100mX0.25mmX0.5µmSample: Premium GasCarrier Gas: He, Linear velocity: 25.6cm/secSplit ratio: 270, Gas Saver: On (split ratio 270 to 5
after 5min) Injector temperature: SPL 275˚COven Temperature: 0˚C hold 15min, 1˚C/min to
50˚C, 2˚C/min to 130˚C, 4˚C/min to 270˚CDetector: FID 300 ˚C Injection volume: 0.5 µL
Canadian PONA Experimental
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Chromatogram
5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0 95.0 100.0 105.0 110.0 115.0 120.0 125.0 130.0 135.0 min-0.5
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5.0uV(x10,000) Chromatogram
0.5L injection of premium gas
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Manual Chromatogram Quantification
All components are identified and classified
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Canadian PONA ReportSample name Premium GasSample ID Premium GasOperater AdminID table CanadianPONAComments Premium GasSampling date 2/21/2012Analysis date 4/6/2011Identified peaks [323/367]Total area 19776176
Hydrocarbon Type % by Mass % by Mole % by VolumeParaffins 3.81 3.80 4.46Isoparaffins 39.31 39.49 42.53Olefins 11.37 11.66 12.14Naphthenes 4.97 5.09 4.79Aromatics 29.53 31.95 25.11Oxygenates 11.02 8.01 10.99
Density(15deg) 0.75 g/cm3Average molecular weight 99.34Reseach Octane Number 89.79Vapor pressure(37.78deg) 41.56 kPa
Peak NameHydrocarbon
TypeRetention
Time % by Mass % by Mole % by VolumeIsobutane P 8.66 0.09 0.091 0.1211-Butene X 9.44 0.019 0.018 0.023Isobutene O 9.48 0.013 0.013 0.016n-Butane A 9.83 0.88 0.889 1.132trans-2-Butene X 10.3 0.054 0.053 0.064cis-2-Butene O 11.02 0.062 0.06 0.0723-Methyl-1-butene O 13.15 0.087 0.085 0.1Isopentane O 14.71 5.616 5.636 6.721-Pentene P 16.34 0.262 0.256 0.2952-Methyl-1-butene O 17.17 0.451 0.44 0.5n-Pentane P 17.68 1.337 1.342 1.585trans-2-Pentene P 18.78 1.042 1.017 1.161cis-2-Pentene O 19.79 0.495 0.483 0.5442-Methyl-2-butene N 20.44 1.267 1.236 1.379"2,2-Dimethylbutane" O 22.51 0.406 0.405 0.461Cyclopentene O 25.07 0.205 0.195 0.1864-Methyl-1-pentene O 26.24 0.038 0.038 0.0423-Methyl-1-pentene O 26.32 0.069 0.067 0.074Cyclopentane P 26.85 0.254 0.248 0.247"2,3-Dimethylbutane" O 27.58 1.397 1.395 1.561Methyl-tert-butylether O 27.98 7.979 10.963 10.937"2,3-Dimethyl-1-butene" P 28.45 0.031 0.03 0.0332-Methylpentane P 28.63 2.516 2.513 2.846trans-4-Methyl-2-pentene P 29.08 0.133 0.13 0.1443-Methylpentane X 31.17 1.546 1.543 1.7192-Methyl-1-pentene A 32.33 0.194 0.19 0.2061-Hexene X 32.55 0.087 0.085 0.094
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ASTM D5580-02
Scope:Determination of benzene, toluene, ethylbenzene, xylenes, C9 and heavier aromatics, and total aromatics
Sample:Finished motor gasoline
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Two Step Analysis
No.1Determination of benzene and toluene, with 2-Hexanone as internal standard; backflush C8+ aromatics and hydrocarbons
No.2Determination of ethylbenzene, xylenes, and C9+ aromatics, with 2-Hexanone as internal standard
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ASTM D-5580 Experimental
INJ Temp: 200 C, Carrier Gas: He, Flow Control Mode:
Pressure, INJ Pressure: 160KPa, TCEP Column Flow: 10
mL/min, Rtx-1 column flow: 10 mL/min, Split vent flow: 100
mL/min, Purge Flow: 1mL/min, Split Ratio: 11:1
Valve Box Temp: 80.0C
Oven1 Temp: 40.0 C hold 6 min, 2 C /min to 80 C, 3
C/min to 115 C hold 2.33 min
FID Temp: 250 C, Makeup Gas: He, Makeup Flow:
20.0mL/min, H2 Flow: 40.0mL/min, Air Flow: 400.0mL/min.
TCD Temp: 200 C, Makeup Gas: He, Makeup Flow: 8
mL/min, Current: 60 mA
T1: 1.8 min, T2: 6.2 min, T3: 21.0 min, T4: 30.0 min
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uV(x10,000) Chromatogram
Ben
zene
Tolu
ene
Eth
ylbe
nzen
e
o-X
ylen
e
2-H
exan
one
TCD Chromatogram
T1 T2
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Analysis No.1
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uV(x1,000,000) Chromatogram
Be
nz
en
e
To
lue
ne
2-H
ex
an
on
e
Backflush PeakC8+ aromatics and hydrocarbons
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Calibration Curves: Benzene & Toluene
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Premium Gas Analysis No.1
0.0 2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min
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uV(x10,000,000)
%RSD < 1.2%
(n=8)
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Analysis No.2
2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min
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uV(x1,000,000) Chromatogram
2-H
ex
an
on
e
Eth
ylb
en
ze
ne
o-X
yle
ne
1,2
,4-T
rim
eth
ylb
enz
en
e
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Calibration Curves Ethylbenzene, o-Xylene, and 1,2,4-Trimethylbenzene
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2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min
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Chromatogram
Premium Gas Analysis No.2
%RSD < 1.8%
(n=8)
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Conclusions
Mechanical valve-based multidimensional GC-2010 Plus has
successfully achieved ASTM D5580 requirements.
Excellent retention time stability allows for the ease of
determining backflush times.
Excellent qualitative and quantitative results.
In addition to ASTM D-5580 method, a separate analytical
line has been incorporated to be able to run Canadian PONA
analysis on the same GC, which has lowered instrumentation
cost and improved productivity.
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Acknowledgements
Mr. Mohamed Salem and Mr. Patrick Armstrong (Shimadzu R&D group) developed Canadian PONA software.
Mr. Inoye Tataaki and Mr. Ryosuke Kamae (Shimadzu Japan) developed and supported PONASolution software.