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Gulf Coast Conference 2012
Page 1
A Dual Channel Pre-column Backflush System
Roger L. Firor Agilent Technologies 2850 Centerville Rd Wilmington, DE USA
AUX
MMI FID 2
FID 1
Pre-column
Column 2
restrictor
In oven
Outline
• Introduction to backflush • System configuration with CFT (Capillary Flow
Technology) • Software tools • Hardware configurations • Application examples • Advanced setups
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Why use Backflush ?
Those that need: • Retention time precision • Improved spectral quality • Longer lasting calibrations • Improved quantitation • Shorter analysis time • Increased column lifetime • Reduced source maintenance
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Pre-column Backflush
• Eliminate bake out times at end of runs • Dirty samples • Late eluting compounds of no analytical interest • Need to protect column from high boilers • Interest in maximizing lab throughput and minimizing
cost of operations • Compatible with GC and GC/MSD systems • Alternative for established methods
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Advantages of Pre-column Backflush
Backflush is carried out while analysis is occurring on the analytical column
Midpoint pressure control allows analytical column to run at desired flow while pre-column is backflushed
Use of an uncoated pre-column allows transfer of components at a relatively low temperature (i.e. 35 C) and faster backflushing of the heavier components
Sample matrix has little influence
Wide choice of pre-column and analytical column dimensions and phase ratios possible to meet specific application needs
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Backflush with Coated Pre-columns
Pre-columns with thin coating (i.e. 0.10 um to 0.25 um films) can be used
Provides finer control of compounds that are backflushed
Backflush times will be much longer typically
Backflush of heavy compounds remaining on the pre-column will take longer
Better inertness
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Use Flow Start with working method
Extract pertinent method information from method files
Select BF configuration
Set up and verify hardware
Install columns and test configuration
Screen standard on new configuration
Lock with recasted RTL calibration if RTL method
Pick last peak of interest using graphical tool, from which BF timing and conditions are recommended
Verify BF works
Fine tune BF conditions if necessary
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Principle Of Backflushing
S/SL Inlet
Capillary Flow Device
1 psi
75 psi
Detector(s)
Split Vent
During GC Run
After GC Run
S/SL Inlet
Capillary Flow Device
25 psi
3.8 psi
Detector(s)
Aux EPC Split Vent
Aux EPC
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Principle Of Backflushing
Concurrent During GC
Run S/SL Inlet
Backflush Device
1 psi
Appropriate column
Pressure maintained
Detector(s)
Aux EPC Split Vent
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Backflushing After Each Injection
Backflush 20 sec Flow
Backflush 30 sec Flow
Backflush 40 sec Flow
Backflush 60 sec Flow
Column Inlet
End of/or during Run Flow
Backflushing removes heavy materials after each injection.
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AUX EPC
Pre-column
Purged Ultimate Union
Multimode Inlet Temperature programmed split
1.6 mL/min 2.0 mL/min
Analytical Column
140 mL/min
FID
Basic System Overview
Three Configurations and Two Modes of Backflush
Post-run Easiest to set up
Coated Pre-Column (split column) More set-up - Concurrent Faster Turn-Around-Time - Post Run
Uncoated Pre-Column More set up - Concurrent Even Faster Turn-Around-Time
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Pressure zeros should be set on the GC for the inlet and Aux channels before use
Post and Concurrent
BF Wizard Overview
• Software based tools to: – Guide end-user to a proposed BF configuration – Illustrate step-by step procedure to configure BF hardware /
plumbing – Develop a BF enabled method
• Automated BF development for > 8 peaks in a chromatogram
• Comparison mode for 3 ≤ # Peaks ≤ 8 • < 3 peaks in chromatogram is a manual process
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Backflush Method Setup
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Backflush Method Setup
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Backflush Setup
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Backflush Setup
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Backflush Setup
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Backflush Setup
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Backflush Setup
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Backflush Setup
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Backflush Setup
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Backflush Setup
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What Kind of Devices can be used for Backflushing?
Anything with an independent pressure or flow control
Purged Union
Purged Splitter
Deans Switch
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PUU Purged Ultimate Union (Pressure Controlled Tee)
– Primary use = Backflush – Pre-column and post column configurations
• Inlet to one detector – Note: pre-column includes mid-column
– Pre-column configurations can be implemented with diff pump
– Recommended for GC and GC/MS systems
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Effluent Splitters
• 2-way effluent splitter – Primary use = post-column splitter to two detectors – Backflush – Can be used in other configurations e.g., pre, mid, post-column
• Not best practice: must plug one port – Don't use just for BF, use if > 1 detector
• 3-Way effluent splitter
– Primary use = post-column splitter to three detectors – Backflush – Can be used in other configurations e.g., pre, mid, post-column
• Not best practice: must plug one port – Don't use just for BF, use if > 2 detectors
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Backflush with Purged Union: Polywax 500 Sample: C5-C18 plus PW500
C26, 10 min
C36, 14 min
C42, 16 min
2 m x 0.53 mm Uncoated retention gap
Pre-column Backflush of C5-C18 Mix After C14
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Retention time STD’s < 0.0019 min
1M x 0.32mm retention gap, 100M x 0.25mm x 0.50um DB-PETRO
C14
C12
Crude Oil Backflush with Coated 2 m x 0.32 mm x 0.10 um DB-1 Pre-column Conditions: Pre-column flow 1.6 ml/min, Analytical column flow 2.0 ml/min MMI: 250 °C(0.5 min) to 425 °C @ 200 °C/min Oven Program: 35 °C (4 min) to 200 °C (1 min) @ 2.0 °C/min Analytical column: 100m x 0.25mm x 0.5um DB-Petro
Backflush time: 4 min
Backflush time: 8 min
C10
C11
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2M x 0.32mm x 0.10um Pre-column: 12 Run Overlay of Crude Oil
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Single Channel Configuration
FID
He or H2
EPC1 P2
IN
Oven
Purged Union
30 m x 0.25 mm x 0.25 um HP-1
30 m x 0.25 mm x 0.50 um HP- INNOWax
Bleed
MMI
P1
restrictor
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Improved stability at low flows
CFT Splitters Configured for Analytical and Pre-column Monitor Channels
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Two un-purged splitters are used
AUX
MMI FID 2
FID 1
Pre-column
Column 2
restrictor
In oven
CFT Splitter Configuration
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Pre-column in
Pressure source in
Pre-column monitor
Column 2
Light Crude: Backflush after C14 Monitor channel in red, 3 m x 0.32 mm x 0.25 um pre-column
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Analytical column: 100m x 0.25mm x 0.5um DB-Petro
Iso-Paraffinic Kerosene
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Analytical column: 100m x 0.25mm x 0.5um DB-Petro
Monitor channel in blue, 3 m x 0.32 mm x 0.10 um pre-column
Synthetic Iso-Paraffinic Kerosene
BF = 6 min BF=8 min
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Analytical column: 100m x 0.25mm x 0.5um DB-Petro Monitor channel in red, 3 m x 0.32 mm x 0.10 um pre-column
SPK Sample Overlay of runs at 8 and 10 min backflush times
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D3606 Parameters with Hydrogen Carrier
Oven: 80 °C isothermal
Column 1: 30 m x 0.25 mm x 0.25 um HP-1
Column 2: 30 m x 0.25 mm x 0.50 um HP-INNOWax
Column 1: 22.9 psig
Column 2: 15.0 psig
Backflush at 4.10 min
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HP-1/INNOWax System
D3606 Parameters with Hydrogen Carrier
Oven: 65 °C isothermal
Column 1: 30 m x 0.25 mm x 0.25 um HP-1
Column 2: 50 m x 0.25 mm x 0.40 um CP-TCEP
Column 1: 26.8 psig
Column 2: 20.5 psig
Backflush at 4.00 min
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HP-1/TCEP System
Column Setup for Backflush
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HP-1/TCEP System for D3606
D3606
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Benzene
Toluene
HP-1/INNOWax System, 80 °C
Overlay of Calibration Mix and Shell 89
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HP-1/TCEP System for D3606 BF at 4.00 min
Overlay Calibration Mix with Shell 89
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Benzene
Toluene
Column 1: 30 m x 0.25 mm x 0.25 um HP-1 Column 2: 50 m x 0.25 mm x 0.4 um TCEP
Calibration: HP-1/INNOWax System
y = 0.404x R² = 1
0
0.5
1
1.5
2
2.5
0 1 2 3 4 5 6
Benzene
y = 0.4214x R² = 1
0 1 2 3 4 5 6 7 8 9
0 5 10 15 20 25
Toluene
%LV %LV
Hydrogen carrier
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Hydrogen Carrier, Isothermal at 80 °C
Run Sample Amt Benzene Vol %
Amt Toluene Vol %
1 Reference 0.82 5.31 2 Reference 0.85 5.31
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Column Set
Column 1: 30 m x 0.25 mm x 0.25 um HP-1 Column 2: 30 m x 0.25 mm x 0.50 um HP-INNOWax
All runs are independent sample preps
Hydrogen Carrier, Isothermal at 65 °C
Run Sample Amt Benzene Vol %
Amt Toluene Vol %
1 Reference 0.86 5.58
2 Reference 0.87 5.40
1 Shell 89 1.03 5.12
2 Shell 89 1.02 5.25
3 Shell 89 1.06 5.27
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Column Set
Column 1: 30 m x 0.25 mm x 0.25 um HP-1 Column 2: 50 m x 0.25 mm x 0.4 um TCEP
All runs are independent sample preps
Advanced Configurations for Backflush
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Variable Split Bleed Saves The Day
Provides necessary bleed to allow pressure control solenoids to operate well (> 1 mL/min) Maintains low flow even during high-pressure backflush Uses normally unused pressure channel (EPC, Backpressure channel on PCM) Allows split flow to be turned OFF for leak checking Provides the opportunity to program bleed flow for custom applications
Using 2nd EPC for Bleed During Run
Set P3 < P2
2 mL/min independent of
P2
Purged Union Column 1 Column 2
Det
SV Trap
He supply
EPC1 P2
IN
Oven
IN
EPC2 P3
atmosphere 1/16” Swagelok tee
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Crude Oil GCxGC: Pre-column Backflush
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BF at 30 min, Oven programmed to 390 C
FID
PCM
FID
PCM
MMI
FID
Column 1
Column 2
PCM Micro Valve
PCM: Pressure control mode,
Modulator
AUX
Restrictor/ Pre-column
G3186B
Aux: Controls Column 1 in constant flow
21-25 ml/min typical
Summary
• CFT devices with an Aux pressure/flow source can be used for backflush applications • Relies on precise EPC midpoint pressure control
• Backflush can be concurrent while analytical column runs at constant flow
• Excellent thermal control since all parts are in the oven
• Heavy petroleum including crude oils can be routinely analyzed with complete protection of the high resolution capillary column
• The specific carbon number where backflush begins can be easily controlled and fine tuned
• Coated pre-columns offer additional control for precise compound cuts
•First or pre-column can be anything from short (2 m) retention gap to high res cap column
• Dual channel configurations allow direct monitoring of the first column
• Straight forward configurations for ASTM D3606
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