Analysis of Permanent Gases: More Challenging Than You ...

1 Analysis of Permanent Gases: more Challenging than You Might ThinkMark SinnottOctober 9, 2018 October 9, 2018 Agilent J&W DB-HeavyWAX1 Analysis of Permanent Gases Sample Introduction Syringes and valves General discussion on PLOT columns The molesievecolumn is at the heart of Permanent gas separations Techniques when CO2+ C2 s, C3 s, etc. is also needed Column Isolation Parallel columns Cryogenic separations Unique selectivity packed columns Techniques for low level detection of hydrogenOctober 9, 2018 Agilent J&W DB-HeavyWAX2 Gas Sampling ValveOctober 9, 2018 Agilent J&W DB-HeavyWAX3 Syringes for Gas injectionOctober 9, 2018 Agilent J&W DB-HeavyWAX4 Tight SyringesOctober 9, 2018 Agilent J&W DB-HeavyWAX5 PLOT columnsOctober 9, 2018 Agilent J&W DB-HeavyWAX6 Column TypePhase TypeChromatographic ProcessStationary PhasesWCOTL iquidGas-Liquid partitioningPolysiloxanesPEGPLOTS olidGas -SolidadsorbtionPorous PolymersAl2O3, Zeolites, etcWCOT= Wall Coated Open TubularPLOT= Porous Layer Open TubularWhy use a PLOT column?

2 Highly retentive (can resolve gases at non-cryotemperatures) Unique selectivity Permits higher initial oven temperatures than WCOTO ctober 9, 2018 Agilent J&W DB-HeavyWAX7 October 9, 2018"Solid"PorousLayerFused Silica TubingIdeal for the Analysis of gases due totheir increased retention (k) and uniqueselectivity (a) compared to WCOTPLOT Columns8 WCOT Ethylene AnalysisPLOT Ethylene AnalysisJW Column PLOT column Portfolio-DB, HP, CP11HP-PLOT Al2O3GS-AluminaGS-Alumina KClHP-PLOT Al2O3 SHP-PLOT Al2O3 MCP-Al2O3/KCLCP-Al2O3/Na2SO4CP-SilcaPLOT CP-CarboBONDCP-CarboPLOTP7GS-CarbonPLOTC P-PoraPLOTA minesCP-PoraPLOTSCP-PoraBONDQCP-PoraPLOT QCP-PoraPLOTQ-HTHP-PLOT QCP-PoraBONDUHP-PLOT UGS-QCP-PoraPLOTUHP-PLOT MolesieveCP-Molsieve 5 AGS-GasProShinCarbonSTSelect Permanent Gas ColumnDial 1-816-650-0621 for e-Seminar AudioSelectivity Interactions in PLOT PhasesShape / SizeSurfaceZeolitesBonded Carbon / Molecular SievesPorous PolymersBonded SilicaAl2O3 MolesieveMolesieveCarbonPLOTPLOT-Q/UGasP roSilicaPLOTA luminaGraphic of type KFI molecular sieve obtained from the International Zeolite Association web site ( ).

3 FlowZeolite "Backbone"Size SelectivityGas Flowd-d-d+d+neutral+++++++++++++++++++++ +++++Vapor pressure always plays a leading role in solute interactionsMolesieveColumnOctober 9, 2018 Agilent J&W DB-HeavyWAX13 Separation based mostly on molecular size and shape Excellent at what it does but very limited H2, O2, N2, CH4, CO Noble Gases NO2 SF6 use CO2 Water C2HC s and largerMolesieveSeparationsOctober 9, 2018 Agilent J&W DB-HeavyWAX14 MolesieveSeparationsOctober 9, 2018 Agilent J&W DB-HeavyWAX15 Tips for using a Molesievecolumn Molesivematerial is commonly used as a moisture trap Samples must be reasonably dry Separation will change as column absorbs water over time Resolution loss between CH4 and CO indicates when column should be reconditioned (300 c 8 hours +)October 9, 2018 Agilent J&W DB-HeavyWAX16CH4 COBut I also need to analyze for getting 9, 2018 Agilent J&W DB-HeavyWAX17 Recall that CO2cannot be done on a molesievecolumn (absorbed) Alternative options: 2 unique injections on 2 columns Molesieve+ PLOT-Q 1 injection on 1 column at Cryotemps (-80 c!)

4 GasPro 1 Injection on 1 column ShinCarbonST (packed column) 1 injection with 2 columns + valve to direct traffic Column Isolation -Molesieve+ PLOT-Q 1 injection with 2 columns in parallel Select Permanent Gas Column -Molesieve+ PLOT-Q ..did I mention this would get complicated?? PLOT-QOctober 9, 2018 Agilent J&W DB-HeavyWAX18 GasPro-CryoOctober 9, 2018 Agilent J&W DB-HeavyWAX19 ShinCarbonSTOctober 9, 2018 Agilent J&W DB-HeavyWAX20 Argon CarrierHelium CarrierOctober 9, 2018 Agilent J&W DB-HeavyWAX21 Courtesy Diablo AnalyticalValves1 Injection 2 Columns + Valve ..Column IsolationOctober 9, 2018 Agilent J&W DB-HeavyWAX22H2 O2 N2 CH4 COCO2C2 s C3 s PLOT-QMolesieveVariable RestrictorCO / CH4 / N2 / O2 / H2C3 s / C2 s / CO2C3 s / C2 s / CO2CO / CH4 / N2 / O2 / H2/SampleIntroductionColumn isolation: Setting up valve timingOctober 9, 2018 Agilent J&W DB-HeavyWAX23 Column isolationOctober 9, 2018 Agilent J&W DB-HeavyWAX24 Column Isolation Flexibility of Elution 9, 2018 Agilent J&W DB-HeavyWAX251 Injection 2 Columns in Permanent Gas ColumnOctober 9, 2018 Agilent J&W DB-HeavyWAX26 Select Permanent Gas ColumnOctober 9, 2018 Agilent J&W DB-HeavyWAX27 Select Permanent Gas ColumnOctober 9, 2018 Agilent J&W DB-HeavyWAX28So you think that was what if I need to analyze for hydrogen 9, 2018 Agilent J&W DB-HeavyWAX29 The trouble with hydrogen Must use TCD Sensitivity is carrier gas dependent Creates unique issues related sensitivity Recall the negative hydrogen peak from earlierTCD When using He carrier sensitivity for hydrogen is on the order of only ~10% No problem right?

5 I ll use Argon or Nitrogen carrier and get down to ppm levels for This is true, however now sensitivity for all the other compounds is now very real catch 22 .. Lets see why this is the 9, 2018 Agilent J&W DB-HeavyWAX30 Thermal Conductivity Detector -TCDO ctober 9, 2018 Agilent J&W DB-HeavyWAX31 Conductivity @ 400 K (mWm-1K-1) 9, 2018 Agilent J&W DB-HeavyWAX32 Argon CarrierHelium CarrierWorkarounds for low level hydrogen detection 2 unique injections: 1 for hydrogen using Argon or N2 carrier 2ndinjection for all other gases using helium carrier 1 injection using column isolation and argon carrier + methanizer TCD coupled to FID Methanizerplaced after TCD but before FID to convert CO/CO2to methane for enhanced detection of these gases by FID Sabatier Reaction (1897): CO2+ 4 H2CH4+ 2H2O Transformer Oil Gas Analyzer (TOGA) October 9, 2018 Agilent J&W DB-HeavyWAX33400 cNiConversion of CO/CO2 to methane Discovered by French chemist Paul Sabatier in 1897 (Sabatier Reaction)October 9, 2018 Agilent J&W DB-HeavyWAX34 TCDM ethanizer(H2 + Ni )350 c FIDO ctober 9, 2018 Agilent J&W DB-HeavyWAX35 Transformer Oil Gas Analyzer (TOGA) ChromatogramsOctober 9, 2018 Agilent J&W DB-HeavyWAX36 Transformer Oil Gas Analyzer (TOGA) ChromatogramsOctober 9, 2018 Agilent J&W DB-HeavyWAX37H2O2N2 TCDT ransformer Oil Gas Analyzer (TOGA) ChromatogramsOctober 9, 2018 Agilent J&W DB-HeavyWAX38 SummaryAnalytesColumnTechniqueH2/O2/N2/C H4/COMolesieve 1 Injection 1 ColumnH2/O2/N2/CH4/CO + ArMolesieve(thick film) 1 Injection 1 ColumnH2/O2/N2/CH4/CO + CO2+ C2 s etcMolesieve+ PLOT-Q 2 Injections 2 Columns 1 Injection + Valve (Column Isolation) 1 Injection Parallel Columns(Select Perm Gas Column)H2/O2/N2/CH4/CO + CO2+ C2 s etcGasPro Cryo(-80 c)

6 H2/O2/N2/CH4/CO + CO2+ C2 s etcShinCarbon Packed onlyH2/O2/N2/CH4/CO + CO2+ C2 s etc+ Low level HydrogenMolesieve+ PLOT-Q Single injection onto molesievefor H2 detection only Argon carrier + Methanizer(TOGA)October 9, 2018 Agilent J&W DB-HeavyWAX39 Contact Agilent Chemistries and Supplies Technical Support1-800-227-9770 Option 3, Option 3:Option 1 for GC/GCMS Columns and SuppliesOption 2 for LC/LCMS Columns and SuppliesOption 3 for Sample Preparation, Filtration and QuEChERSO ption 4 for Spectroscopy SuppliesAvailable in the USA 8-5 all time 40 Agilent RestrictedWe are always here to help!OutlineOctober 9, 2018 Agilent J&W DB-HeavyWAX41 Plot columns General discussion PLOT vs WCOT Molesieve Very narrow functionality Great for resolving O2/N2 at non-cryotemps Traps CO2 and water The Problem with CO2 and HC larger than C1 Option 1: Make 2 unique injections Option 2: Cryo+ GasPro Option 3: Column isolation Option 4: ShinCarbon Detection issues when there is a need for H2 Explanation of TCD (catch 22) Work arounds: 2 unique injections Argon carrier + Methanizer(TCD + FID in series)Flow ChartOctober 9, 2018 Agilent J&W DB-HeavyWAX42Y/NPermanent gases Only (No CO2or C2 s +)MolesieveYesMolesiev