Slide 1: Solutions for light hydrocarbons and gasses: PLOT columns
Solutions for light hydrocarbons and gasses: PLOT columns 1 April 17, 2019 Separation Superhero Seminar Tour
Slide 2: Solutions for Light Hydrocarbons and Gasses: PLOT Columns
Solutions for Light Hydrocarbons and Gasses: PLOT Columns Allen K. Vickers Agilent Technologies Folsom Technology Center California, USA April 18, 2019 2
Slide 3: Table of Boiling Point Fractions
Table of Boiling Point Fractions Carbon No. C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 Bpt of n-Paraffin at 760 mm Hg Centigrade -161 -89 -42 -0.5 +36 69 98 126 151 174 196 216 235 253 270 287 Fahrenheit -259 -127 -44 +31 97 156 209 258 303 345 384 421 421 488 519 548 Refinery off gas Na
Slide 4: Wall Coated Open Tubular (WCOT) Columns
Wall Coated Open Tubular (WCOT) Columns Fused Silica Tubing Stationary phase Gas Flow Stationary phase Kc => Large Kc => Small 4 April 17, 2019 Separation Superhero Seminar Tour
Slide 5: WCOT Ethylene Analysis
WCOT Ethylene Analysis 6 April 17, 2019 Separation Superhero Seminar Tour
Slide 6: PLOT Ethylene Analysis
PLOT Ethylene Analysis 7 April 17, 2019 Separation Superhero Seminar Tour
Slide 7: What Is a PLOT Column?
What Is a PLOT Column? "Solid" Porous • Porous layer (surface) on the inner wall of the capillary Layer • Porosity achieved by the deposition of porous particles on the wall from a suspension Fused Silica Tubing • Porous layer serves as stationary phase • Separation mechanism (gas-solid chromatograp
Slide 8: Selectivity Interactions in PLOT Phases
Selectivity Interactions in PLOT Phases Shape/size Surface Zeolites Al2O3 Porous polymers Bonded carbon Bonded silica Molecular sieves 8 April 17, 2019 Separation Superhero Seminar Tour
Slide 9: Porous Layer Open Tubular (PLOT) Columns Advantages
Porous Layer Open Tubular (PLOT) Columns Advantages • Retention for high vapor pressure solutes – No cryogenics needed – Useful for multicolumn and valve switching, heart cutting techniques. • Variety adsorbents – Porous polymers, alumina, molecular sieve, and so on – Selectivity for isomeric compou
Slide 10: Agilent PLOT Columns Portfolio
Agilent PLOT Columns Portfolio Porous Polymers Alumina HP-PLOT Q, U Al2O3/KCl, HP-PLOT Al2O3/KCl PoraBOND Q, U Al2O3/Na2SO4, HP-PLOT Al2O3 S PoraPLOT Q, U, S GS-Q GS-Alumina PoraPLOT Q-HT Select MAPD Zeolites Silica Porous HP-Molesieve GS-GasPro CP- Molsieve 5A SilicaPLOT Oxygenates Graphitized Carb
Slide 11: Compounds and Columns
Compounds and Columns • Permanent gases – Noble gases, O2, N2, H2, CO, CO2, CH4 Molsieve Select Perm. Gases • Light hydrocarbons Alumina Silica – C1 – C8, saturated, unsaturated – Aromatics, natural gas, C2, C3, C4 streams Carbon Porous polymers • Volatile sulfur compounds Select Low Sulfur Silica –
Slide 12: Porous Polymer PLOT Columns
Porous Polymer PLOT Columns • Analyses of polar and nonpolar volatile compounds – Oxygenates, gases, halogenated compounds, hydrocarbons C1 – C6, ketones, solvents • Most versatile adsorbent materials • Suitable for aqueous injections • Elution of water as a sharp peak + quantification of water • Re
Slide 13: Porous Polymer PLOT Columns
Porous Polymer PLOT Columns • HP-PLOT Q, GS-Q and PoraPLOT Q – Separation ethane/ethylene, propane/propylene – % levels, not ppm impurities in C2, C3 matrix • H2S and COS – Refinery gas analysis – 100 ppm – %, not low ppm • Precolumn with CP-Molsieve columns for O2, N2, CH4, CO • Poor C4 isomer sepa
Slide 14: Refinery Fuel Gas and Porous Polymer Separation
Refinery Fuel Gas and Porous Polymer Separation HP- PLOT Q To CP-Molsieve column for further separation 14 April 17, 2019 Separation Superhero Seminar Tour
Slide 15: Porous Polymer PLOT, Aqueous Injections
Porous Polymer PLOT, Aqueous Injections Before acetone methanol acetonitrile pentane Retention times are the ethanol same for all compounds After Samples containing 5 x 5 µL water, splitless, at 80 °C water can be analyzed Isothermal and short cycle time 15 April 17, 2019 Separation Superhero Semina
Slide 16: Agilent BOND Technology
Agilent “BOND” Technology Particle PLOT Q PoraBOND Q Particle size: 0.1 -2 µm Bonded polymer layer Number: >1012 No particle traps PLOT column Particle trap Detector 17 April 17, 2019 Separation Superhero Seminar Tour
Slide 17: Solvent Analysis on PoraBOND Q
Solvent Analysis on PoraBOND Q 19 April 17, 2019 Separation Superhero Seminar Tour
Slide 18: Alumina Adsorbent and PLOT Columns
Alumina Adsorbent and PLOT Columns Best selectivity for hydrocarbon separations • General C1 – C6 (C9) hydrocarbons • Natural gas • Ethylene streams, impurities • Impurities in propylene • Butylene streams, impurities and complex C4 composition • Environmental hydrocarbons distributions 20 April 17,
Slide 19: Alumina Adsorbent and Columns
Alumina Adsorbent and Columns Separation depends on: • Degree of hydrocarbon saturation – Elution order: alkane, alkene, alkyne, (dialkenes) • Types of deactivation – KCl, Na2SO4 and proprietary • Operating conditions – Column flow and oven temperature • Presence of water – Al2O3 columns are sensiti
Slide 20: Selectivity Difference KCl and Na2SO4
Selectivity Difference KCl and Na2SO4 1. Methane 2. Ethane 3. Ethene KCl 4. Propane 5. Propene 6. Cyclopropane 7. Ethyne 8. Iso-butane 9. Propadiene 10. n-Butane 11. t-2-Butene 12. 1-Butene Na2SO4 13. Iso-butene 14. c-2-Butene 15. 1,3-Butadiene 16. Propyne 22 April 17, 2019 Separation Superhero Semi
Slide 21: Impurities in 1,3 Butadiene
Impurities in 1,3 Butadiene 50 m x 0.32 mm Al2O3/KCl, 5 µm 100 ºC – 200 ºC, 6 ºC/min isobutane 1,3-butadiene trans-2-butene iso-butene 1-butene methylacetylene butane propane c-2B= 15 min 23 April 17, 2019 Separation Superhero Seminar Tour
Slide 22: MAPD Methyl Acetylene PropaDiene
Select Alumina Column MAPD Methyl Acetylene PropaDiene 24 April 17, 2019 Separation Superhero Seminar Tour
Slide 23: Response of Hydrocarbons
Response of Hydrocarbons Standard Al2O3 Select Al2O3 MAPD (%) MA PD 14 25 April 17, 2019 Separation Superhero Seminar Tour
Slide 24: Improved Response on Select for MAPD
Improved Response on Select for MAPD Select for MAPD 30 m x 0.53 mm BD MA PD Courtesy: J. Luong, Dow Chemical Canada 26 April 17, 2019 Separation Superhero Seminar Tour
Slide 25: Silica
Silica • Light hydrocarbon separation, C1 – C4 • Extended hydrocarbon range compared to other PLOT substrates (+C10) • Inert enough for light sulfurs, H2S, COS, mercaptans • CFCs • GS-GasPro • CP-SilicaPLOT • Not sensitive to moisture in carrier gas • MSD compatible 26 April 17, 2019 Separation Supe
Slide 26: GS-GasPro: Inorganic Gases
GS-GasPro: Inorganic Gases 28 April 17, 2019 Separation Superhero Seminar Tour
Slide 27: GS-GasPro: Halocarbons
GS-GasPro: Halocarbons 29 April 17, 2019 Separation Superhero Seminar Tour
Slide 28: Molecular Sieves
Molecular Sieves • Noble gases, Kr, He, Ar, Xe • N2, O2, H2, CH4, CO (not CO2) • CP-Molsieve 5 A • HP-Molesieve • Very sensitive to moisture/CO2 in carrier gas/sample – Conditioning needed – Gas Clean moisture filters in carrier gas essential 29 April 17, 2019 Separation Superhero Seminar Tour
Slide 29: PLOT Columns for Oxygenate Analysis
PLOT Columns for Oxygenate Analysis • Light oxygenates in hydrocarbon streams (ppm) • C1 – C5 alcohols, ethers, ketones • One column solution for ethylene, propylene, butylene feeds • CP-Lowox • GS-OxyPLOT • Highly sensitive to moisture in carrier gas – Conditioning needed – Gas Clean moisture filte
Slide 30: Oxygenates in Hydrocarbons
Oxygenates in Hydrocarbons • Oxygenates blended in gasoline – Additives to boost octane content, prevent engine “knocking” – MTBE, ETBE, ethanol – % level oxygenates – GC analyses on WAX or TCEP polar liquid phase columns • Oxygenate in intermediates (monomers, naphthas) • Lower catalyst effectivene
Slide 31: Analyzing Oxygenates in Hydrocarbon Matrix
Analyzing Oxygenates in Hydrocarbon Matrix • Low ppm concentration level oxygenates • FID detection (MS rarely) • High selectivity columns hydrocarbons/oxygenates Hydrocarbons Oxygenates Acetone C12 C6 Separation on Lowox 32 April 17, 2019 Separation Superhero Seminar Tour
Slide 32: Rotary Valve Configuration for ASTM Trace Oxygenate Analysis Methods
Rotary Valve Configuration for ASTM Trace Oxygenate Analysis Methods Transfer of Oxygenates Venting Hydrocarbons Valve Off Valve On S/Sl Vent AUX S/Sl Vent AUX Inlet EPC Inlet EPC 1 1 4 4 2 Off 2 On Non-polar 3 Non-Polar 3 column Column Back Back FID FID Oxygen Oxygen Column Column 34 April 17, 2019
Slide 33: Hydrocarbons and Oxygenates Separation using DB-1 Stripper Column and GS-OxyPLOT
Hydrocarbons and Oxygenates Separation using DB-1 Stripper Column and GS-OxyPLOT Separation Column 1. Dimethyl ether 13. Acetone Column 1: DB1, 25 m x 0.53 mm x 1 µm 2. Diethyl ether 14. Isovaleraldehyde Benzene p/n: 125-102J 3. Acetaldehyde 15. Valeraldehyde Column 2: GS-Oxy-PLOT, 10 m x 0.53 mm Is
Slide 34: GS-CarbonPLOT
GS-CarbonPLOT Monolithic carbon molecular sieve Phase formed in situ Extended temperature limit of 360 ºC Unique selectivity 35 April 17, 2019 Separation Superhero Seminar Tour
Slide 35: C1 to C3 Hydrocarbon Split Injector
C1 to C3 Hydrocarbon Split Injector GS-CarbonPLOT 1. Methane 7 30 m x 0.32 mm id, 1.5 µm 2. Acetylene Carrier: He at 30 cm/s 3. Ethylene Oven: 125 °C for 2 min 4. Ethane 125 °C to 225 °C at 20 °C/min 5. Propyne Injector: Split 1:20, 250 °C 6. Propylene 2 Detector: MSD, SIM 7. Propane 4 3 5 6 1 0.50
Slide 36: PLOT Column with Integrated Particle Trap
PLOT Column with Integrated Particle Trap • Zero particle shedding when using steep temperature gradients and pressure ranges • Integrated to column – no unions and fittings • Compatible with multicolumn valve switching systems and systems with CFT technology – Particle traps integrated on both ends
Slide 37: Proof of Agilent PLOT PT Column Performance
Proof of Agilent PLOT PT Column Performance Regular PLOT columns • 150 °C to 250 °C at 20 °C/min Spikes • Pressure 3x higher than optimal pressure • 15 cycles • Carrier gas off and on 10 times With integrated particle trap 39 April 17, 2019 Separation Superhero Seminar Tour
Slide 38: PLOT Column with Integrated Particle Trap
PLOT Column with Integrated Particle Trap Integrated particle trap at front and PLOT column back of the column part 40 April 17, 2019 Separation Superhero Seminar Tour
Slide 39: Example of Chromatographic performance
Example of Chromatographic performance Column: PoraBond Q PT, 30 m × 0.25 mm, 3 µm 1. Methyl Alcohol 14. Trichloromethane 27. Pyridine 2. Acetaldehyde 15. 2-Butanone (MEK) 28. Dimethyl Formamide (DMF) Carrier : Helium, 43 cm/s at 90 ℃ 3. Ethanol 16. Ethyl Acetate 29. Isoamyl Alcohol Oven: : 90 °C –
Slide 40: Considerations for PLOT Column Analysis
Considerations for PLOT Column Analysis • Inlet issues – Split versus direct injection – Gas sampling valves • Inlet issues – Low dead volume –• Column split versus direct id and flowinjection rate • gas sampling valves • low dead volume • Detector issuesID and flow rate • column – Particle generati
Slide 41: Considerations for PLOT Column Analysis
Considerations for PLOT Column Analysis • Column issues – Selectivity – Capacity; overloaded peaks – Inertness – Temperature limits • Column contamination – Efficiency loss; “ghost peaks”; increase in bleed – Water, CO2, high molecular weight hydrocarbons? – Carrier gas purifiers 43 April 17, 2019 S
Slide 42: Gas Clean Offer More Reliable Data
Gas Clean Offer More Reliable Data Bottom Line: By removing impurities from the carrier gas stream, Gas Clean filters improve separation and repeatability while using PLOT columns. We suggest: For a 7890 GC: CP17988 Gas Clean carrier gas kit (1/8 in fittings) For a 6890 GC: CP17974 Gas Clean carrier
Slide 43: Summary
Summary • Agilent supplies the largest selection of PLOT columns in the market for all gases and volatiles applications. Agilent has dedicated columns for challenging analyses in the petrochemical industry. • Fully QC tested to assure column-to-column reproducibility with excellent peak shape perfor
Slide 44: Contact Agilent Chemistries and Supplies Technical Support
Agilent Restricted 47 Contact Agilent Chemistries and Supplies Technical Support 1-800-227-9770 option 3, option 3: Option 1 for GC and GC/MS columns and supplies Option 2 for LC and LC/MS columns and supplies Option 3 for sample preparation, filtration and QuEChERS Option 4 for spectroscopy supplie