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Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform
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Combining Methods CAN/CGSB-3.0 and ASTM D-5580 in a Single GC Platform

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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. …

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.

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  • 1. Combining Methods CAN/CGSB-3.0 andASTM D-5580 in a Single GC PlatformZhuangzhi ‘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
  • 2. IntroductionTo improve productivity and lower the capital cost, a single gas chromatograph hasbeen 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 gaschromatographic method. The Canadian standard CAN/CGSB-3.0 requires cryogenictemperature programing to provide better separation of early-eluting components thanconventional non-cryogenic DHA measurements. Determination of aromatics in thepresence 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. Themethods of three tests – one for CAN/CGSB-3.0 and two for ASTM D-5580, can beswitched smoothly with minimum effort. Automated software control providesseparation of hydrocarbons in groups and reporting of the results for methodCAN/CGSB-3.0. Repeatability (%RSD) of ASTM D-5580 was less than 1.2% foranalysis 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 toother finished products such as blend alcohol and other new green energy products.
  • 3. InstrumentationGC-2010Plus Columns:  20% TCEP, 0.558m X 0.75mm PONA  Rtx-1 30m X 0.53mm X 5µm LN2 Cryo-cooling TCEP Injection Volume: 1 µL Valve box Temp: 80°C APC1 Pressure: 210.0KPa Rtx-1 GCSolution ver. 2.41 PONASolution ver. 2.60
  • 4. Canadian PONA Method CAN/CGSB-3.0 Objective Separation of hydrocarbons into types Paraffins, Olefins, Naphthene, Aromatics Separation of each type according to carbon number Method Single capillary column separation of all components, followed by grouping with a post-run program - PONA Solution
  • 5. Canadian PONA Experimental Column: Rtx-1 PONA 100mX0.25mmX0.5µm Sample: Premium Gas Carrier Gas: He, Linear velocity: 25.6cm/sec Split ratio: 270, Gas Saver: On (split ratio 270 to 5 after 5min) Injector temperature: SPL 275˚C Oven Temperature: 0˚C hold 15min, 1˚C/min to 50˚C, 2˚C/min to 130˚C, 4˚C/min to 270˚C Detector: FID 300 ˚C Injection volume: 0.5 µL
  • 6. Chromatogram uV(x10,000)5.0 Chromatogram4.54.03.53.02.52.01.51.00.50.0-0.5 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 0.5µL injection of premium gas
  • 7. Manual Chromatogram Quantification All components are identified and classified
  • 8. Canadian PONA Report Hydrocarbon RetentionSample name Premium Gas Peak Name Type Time % by Mass % by Mole % by VolumeSample ID Premium Gas Isobutane P 8.66 0.09 0.091 0.121Operater Admin 1-Butene X 9.44 0.019 0.018 0.023ID table CanadianPONA Isobutene O 9.48 0.013 0.013 0.016Comments Premium Gas n-Butane A 9.83 0.88 0.889 1.132Sampling date 2/21/2012 trans-2-Butene X 10.3 0.054 0.053 0.064Analysis date 4/6/2011 cis-2-Butene O 11.02 0.062 0.06 0.072Identified peaks [323/367] 3-Methyl-1-butene O 13.15 0.087 0.085 0.1Total area 19776176 Isopentane O 14.71 5.616 5.636 6.72 1-Pentene P 16.34 0.262 0.256 0.295 Hydrocarbon Type % by Mass % by Mole % by Volume 2-Methyl-1-butene O 17.17 0.451 0.44 0.5Paraffins 3.81 3.80 4.46 n-Pentane P 17.68 1.337 1.342 1.585Isoparaffins 39.31 39.49 42.53 trans-2-Pentene P 18.78 1.042 1.017 1.161Olefins 11.37 11.66 12.14 cis-2-Pentene O 19.79 0.495 0.483 0.544Naphthenes 4.97 5.09 4.79 2-Methyl-2-butene N 20.44 1.267 1.236 1.379Aromatics 29.53 31.95 25.11 "2,2-Dimethylbutane" O 22.51 0.406 0.405 0.461Oxygenates 11.02 8.01 10.99 Cyclopentene O 25.07 0.205 0.195 0.186 4-Methyl-1-pentene O 26.24 0.038 0.038 0.042Density(15deg) 0.75 g/cm3 3-Methyl-1-pentene O 26.32 0.069 0.067 0.074Average molecular Cyclopentane P 26.85 0.254 0.248 0.247weight 99.34 "2,3-Dimethylbutane" O 27.58 1.397 1.395 1.561Reseach Octane Number 89.79Vapor Methyl-tert-butylether O 27.98 7.979 10.963 10.937pressure(37.78deg) 41.56 kPa "2,3-Dimethyl-1-butene" P 28.45 0.031 0.03 0.033 2-Methylpentane P 28.63 2.516 2.513 2.846 trans-4-Methyl-2-pentene P 29.08 0.133 0.13 0.144 3-Methylpentane X 31.17 1.546 1.543 1.719 2-Methyl-1-pentene A 32.33 0.194 0.19 0.206 1-Hexene X 32.55 0.087 0.085 0.094
  • 9. ASTM D5580-02Scope:Determination of benzene, toluene, ethylbenzene,xylenes, C9 and heavier aromatics, and totalaromaticsSample:Finished motor gasoline
  • 10. Two Step AnalysisNo.1Determination of benzene and toluene, with 2-Hexanone as internal standard; backflush C8+aromatics and hydrocarbonsNo.2Determination of ethylbenzene, xylenes, and C9+aromatics, with 2-Hexanone as internal standard
  • 11. 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: 80.0°C  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
  • 12. TCD Chromatogram uV(x10,000) Chromatogram1.21.1 Benzene1.00.9 Ethylbenzene0.80.7 o-Xylene Toluene0.6 2-Hexanone0.50.40.30.2 T1 T20.10.0-0.1 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0 19.0 min
  • 13. Analysis No.1 uV(x1,000,000) 2-Hexanone Toluene Chromatogram3.00 Backflush Peak2.75 C8+ aromatics and hydrocarbons2.502.252.001.751.501.251.00 Benzene0.750.500.250.00-0.25 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
  • 14. Calibration Curves: Benzene & Toluene
  • 15. Premium Gas Analysis No.1 uV(x10,000,000) %RSD < 1.2%1.21.11.0 (n=8)0.90.80.70.60.50.40.30.20.10.0-0.1 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
  • 16. Analysis No.2 uV(x1,000,000) Chromatogram 1,2,4-Trimethylbenzene6.05.55.04.54.0 o-Xylene3.5 2-Hexanone Ethylbenzene3.02.52.01.51.00.50.0-0.5 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
  • 17. Calibration Curves Ethylbenzene, o-Xylene, and1,2,4-Trimethylbenzene
  • 18. Premium Gas Analysis No.2 uV(x1,000,000) Chromatogram6.05.5 %RSD < 1.8%5.0 (n=8)4.54.03.53.02.52.01.51.00.50.0-0.5 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
  • 19. 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.
  • 20. 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.

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