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Group/Presentation TitleAgilent Restricted
Month ##, 200XPage 1
Capillary Flow Technology – Productivity Enhancement
Tools for Hydrocarbon Processing GC Analysis
Jim McCurry Senior Applications Chemist Agilent Technologies
Capillary Flow TechnologyAgilent Restricted
Page 2
IF We Only Had A Technology That Provided Easy, Reliable Flow Structures In The GC Oven...
It would open up many new (and old) capabilities for GC– Column connections (connect pre-column) – Change MSD columns (without venting) – Backflush (Reverse flow through column)– Detector splitter (effluent split to two or more detectors)– Merge flows (2 columns to 1 MSD) – Deans switch (heart cut select peaks to 2nd column)– Comprehensive 2-D GC (cut all peaks to 2nd column) – etc.
Capillary Flow TechnologyAgilent Restricted
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Metal Fittings
Press Fit Glass
Graphite
Polyimide
Packed columns, reliable
Low dead volume, inert, low cost
High temperature
Low initial leakage
Types of Connectors Used In The GC Oven
Not inert, no ferrule for capillary columns
Difficult to assemble, comes apart
Sheds active graphite particles into sample path
Loosens and leaks with oven cycling, solvent tailing
Advantages Limitations
Capillary Flow TechnologyAgilent Restricted
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Challenges For Inside the Oven Devices
– Inertness (it is in the sample path)– Low dead volume (it is in the separation path)– Leak free (especially with repeated temp cycling)– Fast thermal response (follow rapid oven ramping)– High temp tolerance (GC oven can go over 350C)– Reliable and easy to use
Capillary Flow TechnologyAgilent Restricted
Page 5
5 Key Developments in Capillary Flow Technology
Complex flow structures with low thermal mass
Makes metal surfaces as inert as column
Backflushing now possible, change MSD columns without venting, known column outlet pressure
Accurately predict flows and pressures BEFORE installing devices
Easy to use, do not loosen or leak with oven cycling to 400°C
Manifold Plates
Deactivation of Metal
EPC
Calculators
Metal Ferrules
Capillary Flow TechnologyAgilent Restricted
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Capillary Flow Technology- Design
• Photolithographic chemical milling for low dead volume
• Diffusion bond two halves to form a single flow plate
• Small, thin profile provides fast thermal response
• Projection welded connections for leak tight fittings
• Deactivation of all internal surfaces for inertness
… a proprietary Agilent Technology
Capillary Flow TechnologyAgilent Restricted
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The Metal Ferrule
Square cut is not critical
Seal region
Does not loosen (leak) even with thousands of runs to 350CDoes not shed particles
Capillary Flow TechnologyAgilent Restricted
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3-Way Splitter With MakeupEffluent Splitter
(3 Way)
Column in
Aux EPC in Det1 out
Det2 outDet3 out
Capillary Flow TechnologyAgilent Restricted
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Capillary Flow Technology
Column 1 In
Restrictor 1
out to vent
Plate
Ferrule
Nut
Restrictor 2
or Column 2
Channel
Capillary Flow TechnologyAgilent Restricted
Page 10
Comparison of New Fitting with Polyimide Fitting
Polyimide Fitting
New Fitting
Exposure to polyimide and unpurged annular spaces is greatly reduced
Ferrule Ejector Hole
Capillary Flow TechnologyAgilent Restricted
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PolyimideFID directCapillary Flow fitting
Capillary Flow Technology fittings avoid tailing with small but well swept dead volume
1.1 1.15 1.2 1.25 1.3
0
1
2
3
4
5
6
Pentane test chromatogramFitting Design Minimizes Tailing
Capillary Flow TechnologyAgilent Restricted
Page 12
Capillary Flow Technology- Capabilities
Detector Splitting
Solvent Bypass
Heart Cutting (Deans Switch)
QuickSwap
Modulation (GCXGC)
Backflush
Capillary Flow TechnologyAgilent Restricted
Page 13
Capillary Flow Technology DevicesUltimate UnionUltimate Union
7890 GC
Column
FID
Precolumn
Gas Sampling Valve
7890 GC
Column
FID
Tube to Connector
Tube Connector
Reliable precolumn connector
Easy valve to capillary column connector
Tube is 0.25 mm id and is deactivated
Capillary Flow TechnologyAgilent Restricted
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Biodiesel Analysis by EN14105/ASTM D6584 Capillary Flow Technology Ultimate Union• Use 1 to 5 m, 0.53 mm
ID deactivated fused silica tubing
• Improves peak shape• Ultimate Union
– easy, robust connection
– deactivated– no-leak metal ferrule– optimized for high
temperatures
4.8 5 5.2 5.4 5.6
Glycerin
Butanetriol (istd 1)
No Retention Gap
1 m x 0.53 mm I.D. Retention Gap
Capillary Flow Technology Ultimate Union
Retention Gap In
Column Out
Inert, High Temp Metal Ferrule
Capillary Flow TechnologyAgilent Restricted
Page 15
Refinery Gas Analysis
Col 1: Propark Q 80/100, 0.5mCol 2: Propark Q, 80/100, 6ftCol 3: Molsieve 5A, 60/80,2mCol 4: DB-1, 2m, 0.32mm, 5um
Col 5:HP-AL/S 25m,0.32mm, 8umCol 6:CarbonPLT 15m,0.53mm,3umCol 7:HP- Molsive, 15M,0.53mm,50um
Col 5
3rd TCD Channel Carry gas N2
301
301
301
FIDS/SL
A
1
2
3
4
5
6
1
2
3
4
5
6 TCD
TCD
12
3
4
567
8
9
10
outSample in
A
12
3
4
567
8
9
10
Out
Vent
S/SLB
B
FID Channel
TCD Channel Carry gas He
Col 1
Col 2
Col 3
Col 4
Col 6 Col 7
Capillary Flow TechnologyAgilent Restricted
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Column Union Connector
Enhance Gas Analysis with Ultimate Union
Traditional connecter
New Union connecter
…… Peak shape enhancementPeak shape enhancement
Capillary Flow TechnologyAgilent Restricted
Page 17
Application and Result- RGA standards
TCD Channel
Carry gas: He
3rd TCD Channel Carry gas: N2
FID Channel
25 uV
0500
100015002000250030003500
min0 1 2 3 4 5 6 7
CO
2
O2
N2
met
hane
CO
min1 2 3 4 5 6 70
25 uV
-100
0
100
200
300
400
500
H2
met
hane
pA
0200400600800
1000120014001600
min0 1 2 3 4 5 6 7
1-pe
nten
e
prop
yne
i-pen
tane
C6+
met
hane et
hane
ethy
lene
prop
ane
cycl
opro
pane
prop
ylen
e
i-but
ane
n-bu
tane
prop
adie
neac
etyl
ene
t-2-b
uten
e1-
bute
nei-b
uten
ec-
2-bu
tene
n-pe
ntan
e
1,3-
buta
dien
e
t-2-p
ente
ne2-
met
hyl-2
-but
ene
c-2-
pent
ene
The complete analysis with one injection in 6 minutes
Capillary Flow TechnologyAgilent Restricted
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Splitters: Unpurged Tee
1:1 split FPD:uECD
Effluent Splitter WITHOUT Makeup
Auto-sampler
7890A GC
Column
0.3 m X 0.25 mm id
30 m X 0.25 mm id X 0.25 um HP-5MS
FPD P
μECD
Simultaneous detection with 2 detectors (but NOT MSD)
No external pressure source - Cannot do backflushing
Det 2 OUT
Column IN
Det 1 OUT
Capillary Flow TechnologyAgilent Restricted
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QuickSwap
MSD TransferlineAuto-sampler
7890A GC
Column
AUX EPC4 psig
171 mm X 0.121 mm id restrictor
5975C InertMSD
Change MSD columns without ventingBackflush heavy components out split vent
Capillary Flow TechnologyAgilent Restricted
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QuickSwap MSD Interface
Remove column w/o venting– Air & H2 O blocked
Safe disconnection of column from inlet for inlet maintenance
– Reversed flow through column during inlet maintenance
Backflushing– Removes heavies from column
Maintain constant flow to MSD
(flow rates exceeding 2 mL/min require an MSD with Performance Turbo)
MSD TransferLine
Aux EPC In
Column Effluent
Capillary Flow TechnologyAgilent Restricted
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Backflush with QuickSwap
S/S Inlet
QuickSwapColumn
1 psi
45 psi
MSD
Aux EPCSplit Vent Trap
During GC Run
After GC Run
S/S Inlet
QuickSwapColumn
25 psi
4 psi
MSD
Aux EPCSplit Vent Trap
Capillary Flow TechnologyAgilent Restricted
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Benefits of Backflushing
– More samples/day/instrument– Better quality data– Lower operating costs– Less frequent and faster GC & MSD maintenance– Longer column life– Less chemical background
Capillary Flow TechnologyAgilent Restricted
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Three Other Devices Provide Backflush Capability
22--Way Splitter with Way Splitter with MakeupMakeup
33--Way Splitter with Way Splitter with MakeupMakeup
Deans SwitchDeans Switch
Capillary Flow TechnologyAgilent Restricted
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Dean Switch
Cut
Deans Switch
Auto- sampler
7890A GC
FID1 FID2
Column 1 Column 2
Heart cutting 2-D GC provides extremely high chromatographic resolution
Capillary Flow TechnologyAgilent Restricted
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Heart Cut to Column 2
Trace Sulfur Compound(4,6-DMDBT)
Column 1 - FID 1
Column 2 – FID 2
0 2 4 6 8 10 12 14 16 18 min.
Hydrocarbon Matrix
Diesel Fuel
2-D Separation of Sulfur Compound in Diesel Fuel
Compound is completely resolved and can be analyzed with FID
Capillary Flow TechnologyAgilent Restricted
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Configuration for Enhanced ASTM D6584
ASTM D6584 measures trace hydrocarbons
• uses alumina PLOT column
Oxygenates best separated on HP-Innowax column
Use Deans switch to combine two methods into one
• primary column separates oxygenates
• Deans switch selectively transfers only the hydrocarbons to alumina PLOT
• HP-Innowax column protects alumina PLOT from damage
Capillary Flow Technology Deans Switch
PCM
FID 1
Inlet
FID 2
Restrictor
Primary Column HP-Innowax
(30m x 0.32mm ID x 0.5 um)
Secondary Column HP-Alumina PLOT “M”
(30 m x 0.53mm ID x 15um)
Capillary Flow TechnologyAgilent Restricted
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Complete Separation of Oxygenates and Hydrocarbons
20
40
60
80
100
120
140pA
0 5 10 15 20 25 Min.
1
2
34
67 8
9 1011
121314
1516
PLOT Alumina “M” (19095P-M23)
20
25
30
35
pA
0 5 10 15 20 25 Min.
Cut time: 2.3 – 4.3 min.
5 (methanol)HP-Innowax (19091N-213)
C1 to C4 Hydrocarbons Separated on Secondary Column
Heart-Cutting 100 ppmV Impurities in Ethylene
Capillary Flow TechnologyAgilent Restricted
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ASTM 7059 - Trace Methanol in Crude by 2-D GC
FID 1
S/S Inlet
FID 2
PCM
restrictor
Column 1 HP1
Column 2 GS-Oxyplot
Used to “heart cut”
alcohols from HP-1 column to Innowax
Capillary Flow TechnologyAgilent Restricted
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ASTM 7059 - Trace Methanol in Crude by 2-D GC
1 2 3 4 5 6 7 Min.-0.5
0
0.5
1
1.5
Second Column (Oxyplot) –
FID2
Crude Oil Hydrocarbons
Methanol
(10 ppm)
1-propanol
(500 ppm
ISTD)
backflush
1 2 3 4 5 6 7 Min.0
100
200
300
400
500
600 Cut time:
1.70 –
2.35 min.
Crude Oil Hydrocarbons
Primary Column (HP-1) –
FID1
backflush
pA
pA
Capillary Flow TechnologyAgilent Restricted
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FID A
S/S Inlet
FID B
PCM
<< 1mL/min
purgerestrictor
OffHigh boilers
Restrictor
HP-1
GC-Oxyplot
Backflush To Decrease Run Time
Valve off –
Lower Inlet pressure, Increase PCM pressue
Split vent
(high boilers)
11.14 psi9.78 psi<0.5 psi >60 psi
Capillary Flow TechnologyAgilent Restricted
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Agilent’s flow modulator design : Differential Flow
ModulationValve
FID
Split/SplitlessInlet
Column 1 (25 – 30 M)
Column 2 (5M)
Collection channel
Flow Modulator
H2
Flush Flowdirection
Collect Flow direction
Flow modulator eliminates the need for cryo. Sample compression controlledby flow ratios occurs in the collection loop and is quickly injected into the second column, resulting in very narrow and tall peaks.
Differential flow concept is designed by John V. Seeley, Oakland University
Capillary Flow TechnologyAgilent Restricted
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Flow modulation: (GC x GC) of diesel fuel: 7890A
GC x GC Chromatogram:• Showing the normal B.P. distribution (1st dimension)• Also shows hydrocarbon classes in clusters
• Consistent RT for alkanes in 1st dimension showing precise modulation• Comparable peak in 2nd dimension band shows minimum peak broadening
with flow modulation
Naphthalene
Toluene
p-xyleneo-xylene
C9 C12 C16
Alkanes
mono-Aromatics
di-AromaticsMethyl-naphthalenes
Capillary Flow TechnologyAgilent Restricted
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Agilent Flow Modulation GC x GC
• Reliable Setup: Based on capillary-flow- technology, easy to setup, high
performance chromatography, and reliable.
• No Cryogen Required: Flow modulation means no tanks of Liquid N2 or CO2
• 7890A Enabled GC x GC: Capillary- flow-technology ready, synchronized
periodic events ensure precise modulation, control from a modified TCD board
• Comparable resolution without Liquid N2: Cap Flow Technology allows low
dead volume and precise flow control, resulting in minimum peak broadening even
without cryo-focusing . Peak widths on the second column are typically 70 to 100 ms
at half maximum.
• Sensitivity: Approaches that obtained by thermally modulated systems
Capillary Flow TechnologyAgilent Restricted
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Capillary Flow Technology solves difficult application problems easily.
It opens up many new (and old) possibilities for GC and GC/MS systems.
Summary