innovations in high pressure liquid injection technique ... · liquid sample introduction systems...
TRANSCRIPT
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Innovations in High Pressure Innovations in High Pressure Liquid Injection Technique Liquid Injection Technique
for for Gas ChromatographyGas Chromatography
Richard Richard TymkoTymko, Transcendent Enterprises,, Transcendent Enterprises,Edmonton, Alberta, CanadaEdmonton, Alberta, Canada
Ronda Gras and Jim Ronda Gras and Jim LuongLuong, Dow Chemical Canada Inc, Dow Chemical Canada IncAnalytical Sciences, Separations TechnologyAnalytical Sciences, Separations Technology
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OutlineOutline
nn Requirements of sample introduction systemsRequirements of sample introduction systemsnn Liquid sample systemsLiquid sample systemsnn Pressurized Liquid Injection System Pressurized Liquid Injection System (PLIS)(PLIS)nn Performance and applicationsPerformance and applicationsnn ConclusionsConclusionsnn Future plansFuture plansnn AcknowledgementsAcknowledgements
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Requirements of Requirements of sample introduction systemsample introduction system
nn The sample introduction process should not depend The sample introduction process should not depend upon column operating temperatureupon column operating temperature
nn Thermal degradation, adsorption, rearrangements Thermal degradation, adsorption, rearrangements or other solute reactions should be negligibleor other solute reactions should be negligible
nn The sample system should not effect column The sample system should not effect column efficiency efficiency –– input band criticalinput band critical
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Liquid Sample Introduction SystemsLiquid Sample Introduction Systems
nn Introduction of semiIntroduction of semi--volatile liquid in GC via ALSvolatile liquid in GC via ALSnn Introduction of volatile liquid in GC via valve or Introduction of volatile liquid in GC via valve or
vapourizervapourizernn Rotary valve (Rotary valve (ValcoValco ViciVici, , RheodyneRheodyne))nn Diaphragm valve (Diaphragm valve (ValcoValco))nn Slider valve (ABB, Applied automation)Slider valve (ABB, Applied automation)nn Piston valve (M.A.T)Piston valve (M.A.T)
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nn The main challenges:The main challenges:nn Dissimilar boiling point solutes (high boiling Dissimilar boiling point solutes (high boiling
point compounds in low boiling point point compounds in low boiling point matrices)matrices)nn Examples:Examples:
nn Diesel in ethaneDiesel in ethanenn Pole oil in ethylenePole oil in ethylenenn TBC in butadieneTBC in butadienenn DEHA in butadieneDEHA in butadienenn Alcohols in hydrocarbons Alcohols in hydrocarbons feedstreamsfeedstreams
nn Fractionation (Fractionation (vapourizervapourizer, rotary, diaphragm, , rotary, diaphragm, slider valves)slider valves)
nn Speed of injection too slow for fast gas Speed of injection too slow for fast gas chromatographychromatography
Limitations of Sample introduction Limitations of Sample introduction for volatile liquidfor volatile liquid
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Stem valve conceptStem valve concept
nn Merits in injection techniqueMerits in injection techniquenn M.A.TM.A.Tnn SiemensSiemensnn Most recently, Most recently, PLISPLIS (transcendent)(transcendent)
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PLISPLIS Design Criteria & Key FeaturesDesign Criteria & Key Features
nn Fast injection speedFast injection speednn High pressure of up to 1200 psig High pressure of up to 1200 psig nn No fractionation No fractionation nn Sample size from Sample size from nLnL to 2 to 2 uLuLnn HeatableHeatable of up to 300 C (radiant with V1.0)of up to 300 C (radiant with V1.0)nn Low dead volumeLow dead volumenn Low maintenance and userLow maintenance and user--friendlyfriendly
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Pressurized Liquid Injection System Pressurized Liquid Injection System (PLIS)(PLIS)
Courtesy of Transcendent Enterprises Inc.
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PLISPLIS in Piecesin Pieces
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PLIS PLIS on Agilent HPon Agilent HP--6890 GC 6890 GC A Look At InterfaceA Look At Interface
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PLIS PLIS on 6890 GC on 6890 GC PLIS PLIS /Vacuum GC/DR/Vacuum GC/DR--SCD TechnologySCD Technology
Elimination of pressure vaporizerElimination of pressure vaporizer
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Temperature Profile of Injector vs. Temperature Profile of Injector vs. Vaporizing chamber (Vaporizing chamber (oo
CC) ) -- Unheated Unheated versionversion
Temperature Profile of Injector vs. Cone (C)
0
50
100
150
200
250
300
350
400
450
100 150 200 250 300 350 400 450
Set Temperature (C)
Act
ual
Tem
per
atu
re (C
)
Injector Temperature (C)Cone Base Temperature (C)
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Selected Chromatographic Selected Chromatographic ApplicationsApplications
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A chromatogram of Alberta Natural A chromatogram of Alberta Natural GasGas
GC/FID GC/FID -- AlAl22OO33/KCl technology/KCl technology
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Repeatability Repeatability –– Natural Gas GC/FIDNatural Gas GC/FID
PLIS Quantitative Repeatability of Natural Gas InjectionsRetention Time (min)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 5 10 15 20
Injection Number
Ret
enti
on
Tim
e (m
in)
Ethane
Propane
i-Butane
Rel. Prec. (95%) = 1.2 %
Rel. Prec. (95%) = 0.8 %
Rel. Prec. (95%) = 0.7 %
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A chromatogram of nC10 to nC24 in A chromatogram of nC10 to nC24 in HexaneHexane
GC/FID GC/FID -- 30 30 metremetre, 0.25 mm id, 1 , 0.25 mm id, 1 micron CPmicron CP--SilSil 5 CB5 CB--MSMS
min2 4 6 8 10 12
pA
0
200
400
600
800
FID1 B, (PLSI0008.D)
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A chromatogram of Diesel in HexaneA chromatogram of Diesel in HexaneGC/FID GC/FID -- 30 30 metremetre, 0.25 mm id, 1 , 0.25 mm id, 1
micron CPmicron CP--SilSil 5 CB5 CB--MSMS
min2.5 5 7.5 10 12.5 15 17.5 20
pA
0
50
100
150
200
250
300
350
FID1 B, (PLSI0011.D)
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A chromatogram of Sulfurs in EthaneA chromatogram of Sulfurs in Ethanehydrogen sulfide and carbonyl sulfide hydrogen sulfide and carbonyl sulfide
PLIS PLIS / VGC/DR/ VGC/DR--SCDSCD30 meter, 0.32 mm, 5 micron CP30 meter, 0.32 mm, 5 micron CP--SilSil 5 5
CBCB--MSMS
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A chromatogram of Sulfurs in ButaneA chromatogram of Sulfurs in ButaneMethyl and ethyl Methyl and ethyl mercaptanmercaptan –– PLIS PLIS
/VGC/DR/VGC/DR--SCDSCD30 meter, 0.32 mm, 5 micron CP30 meter, 0.32 mm, 5 micron CP--SilSil 5 5
CBCB--MSMS
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Volatile Oxygenated CompoundsMeOHMeOH, AA, EO, and , AA, EO, and EtOHEtOH GC/FID,GC/FID,
50 meter, 0.32 mm id , 5 micron CP50 meter, 0.32 mm id , 5 micron CP--SilSil 55
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Hydrocarbons and OxygenatesHydrocarbons and Oxygenates10 10 metremetre, 0.53 mm id, , 0.53 mm id, Lowox Lowox Column Column
TechnologyTechnology
1. nC142. Methanol3. Acetone4. nC155. Ethanol6. nC167. Propanol8. Iso-butanol9. Butanol
11
111
11
1
11
9
2
3
4
5
6
78
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Stack Injection TechniqueStack Injection Technique100 C100 C--1min1min--50C/min50C/min--260C 5 psig260C 5 psig
Lowox Lowox Column TechnologyColumn Technology
1. Methanol2. Ethanol3. Propanol
1
32
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PLIS / GC / FIDPLIS / GC / FIDLowox Column Technology Lowox Column Technology –– Alcohols Alcohols
in Hydrocarbonsin HydrocarbonsReproducibility of Retention Time Reproducibility of Retention Time
(min) and Area Counts(min) and Area CountsRepeatability of PLIS/GC/FID
Lowox Column Technology - Alcohols in Hydrocarbons
0
5
10
15
20
25
1 2 3 4 5 6 7 8 9 10 11
Injection Number
Ret
entio
n Ti
me
(min
)
-40000
-20000
0
20000
40000
60000
80000
Are
a C
ount
s
Methanol - RT
Ethanol - RT
Propanol - RT
Methanol -Area
Ethanol - Area
Propanol - Area
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Impurities in Ethylene OxideImpurities in Ethylene Oxide
min0.5 1 1.5 2 2.5 3
pA
18
20
22
24
26
28
FID1 A, (EOEG\22JUN005.D)
min1.95 2 2.05 2.1 2.15 2.2 2.25
pA
18
20
22
24
26
28
FID1 A, (EOEG\22JUN005.D)
1. Cyclopropane2. Acetaldehyde3. Vinyl chloride4. Ethylene Oxide
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Key Learning'sKey Learning's
nn PLISPLIS offers key advantages:offers key advantages:
nn Small and compact (10 x 3 x 4 cm)Small and compact (10 x 3 x 4 cm)nn Capability to direct couple valve to injector Capability to direct couple valve to injector
reducing void volume, cold spots, active sitesreducing void volume, cold spots, active sitesnn Minimize fractionation of sampleMinimize fractionation of samplenn Simplicity Simplicity –– ease of maintenanceease of maintenance
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Key Learning'sKey Learning's
nn Unlike a rotary valve, speed of injection is not Unlike a rotary valve, speed of injection is not critical in delivering good chromatography critical in delivering good chromatography
nn Reduction of void volume between valve and Reduction of void volume between valve and injector port injector port –– criticalcriticalnn Reduction of liner volumeReduction of liner volumenn Reduction of volume of Reduction of volume of vapourizingvapourizing chamberchambernn Volume of Volume of vapourizationvapourization chamber determined to chamber determined to
be 360 be 360 uLuLnn Helium actuation not necessary and has no impact Helium actuation not necessary and has no impact
on overall chromatography obtainedon overall chromatography obtained
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LimitationsLimitations
nn Unheated version not suitable for high boiling polar Unheated version not suitable for high boiling polar compoundscompounds
nn No long term performance data on seal(s)No long term performance data on seal(s)
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MEG, DEG, and TEGMEG, DEG, and TEGGC/FID GC/FID -- 30 30 metremetre, 0.25 mm id, 1 , 0.25 mm id, 1
micron CPmicron CP--SilSil 5 CB5 CB--MSMS
min1 2 3 4 5 6 7
pA
10
20
30
40
50
60
70
FID1 B, (CALD0085.D)
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Future ResearchFuture Research
nn Study effect of fractionationStudy effect of fractionationnn Void volume reductionVoid volume reductionnn Surface deactivationSurface deactivationnn Applications developmentApplications developmentnn Resistively heated versionResistively heated version
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AcknowledgementsAcknowledgements
nn Dow Chemical Separations Leadership TeamDow Chemical Separations Leadership Teamnn Professor Dr. Professor Dr. KarelKarel CramersCramers, TU/e, TU/enn RonyRony Van Van MeulebroeckMeulebroeck, Dow , Dow TerneuzenTerneuzennn Curt Stout, Stout EngineeringCurt Stout, Stout Engineeringnn Stephen Jefferies, Gambit ProductsStephen Jefferies, Gambit Products