15 liquid liquid extraction and other liquid-liquid operation and equipment
High Performance Pressurized Liquid Injection System ...Liquid Sample Introduction Systems...
Transcript of High Performance Pressurized Liquid Injection System ...Liquid Sample Introduction Systems...
High Performance Pressurized Liquid High Performance Pressurized Liquid Injection System (HPLIS) for Fast Gas Injection System (HPLIS) for Fast Gas
ChromatographyChromatography
Jim Jim LuongLuong and Ronda Grasand Ronda GrasDow Chemical Canada IncDow Chemical Canada Inc
Richard Tymko Richard Tymko Transcendent Enterprises IncTranscendent Enterprises Inc
OutlineOutline
nn Merits for Fast Gas ChromatographyMerits for Fast Gas Chromatographynn PLIS as a sample introduction device for faster GCPLIS as a sample introduction device for faster GC
nn Conventional fast GCConventional fast GCnn Vacuum outlet GC and selective detector Vacuum outlet GC and selective detector nn Silicon Silicon micromachinedmicromachined gas chromatographygas chromatographynn MicrovolumeMicrovolume injectioninjection
nn ConclusionsConclusionsnn AcknowledgementsAcknowledgements
Merits for Fast Gas Chromatography in industriesMerits for Fast Gas Chromatography in industries
nn Improve chromatographic performanceImprove chromatographic performance
nn Reproducibility and Reproducibility and detectabilitydetectabilitynn Address the needs for real time data Address the needs for real time data nn Higher sample throughputHigher sample throughput
nn Typical industrial applications for fast GC:Typical industrial applications for fast GC:nn Combinatorial chemistryCombinatorial chemistrynn Industrial hygiene/environmental monitoringIndustrial hygiene/environmental monitoringnn Catalyst studiesCatalyst studiesnn Productivity improvementsProductivity improvements
Liquid Sample Introduction SystemsLiquid Sample Introduction Systems
nn Introduction of semiIntroduction of semi--volatile liquid via automated volatile liquid via automated liquid sampler and split/liquid sampler and split/splitlesssplitless injector injector
nn Introduction of volatile liquid in GC via valve or Introduction of volatile liquid in GC via valve or vapourizervapourizer
nn Rotary valve (Valco Rotary valve (Valco ViciVici, , RheodyneRheodyne))nn Diaphragm valve (Valco)Diaphragm valve (Valco)nn Slider valve (ABB, Applied automation)Slider valve (ABB, Applied automation)nn Piston valve (M.A.T)Piston valve (M.A.T)
nn The main challenges:The main challenges:
nn Dissimilar boiling point solutes (high boiling point compounds iDissimilar boiling point solutes (high boiling point compounds in low n low boiling point matrices)boiling point matrices)nn Examples:Examples:
nn Diesel in ethaneDiesel in ethanenn Pole oil in ethylenePole oil in ethylenenn TertTert--butyl butyl catecholcatechol (TBC) in butadiene(TBC) in butadienenn DiethylhydroxylamineDiethylhydroxylamine (DEHA) in butadiene(DEHA) in butadienenn Alcohols in hydrocarbon Alcohols in hydrocarbon feedstreamsfeedstreams
nn Fractionation (Fractionation (vapourizervapourizer, rotary, diaphragm, slider valves), rotary, diaphragm, slider valves)nn Speed of injection too slow for fast gas chromatographySpeed of injection too slow for fast gas chromatography
Limitations of Sample introduction for volatile Limitations of Sample introduction for volatile liquidliquid
PLIS Design Criteria & Key FeaturesPLIS Design Criteria & Key Features
nn Fast injection speedFast injection speednn High pressure of up to 1200 psig High pressure of up to 1200 psig nn Minimal fractionation Minimal fractionation nn Sample size from Sample size from nLnL to 12 uLto 12 uLnn Low dead volumeLow dead volumenn Low maintenance and userLow maintenance and user--friendlyfriendly
Impact of Speed of InjectionImpact of Speed of Injection
Impact of Actuation Valve Pressure (Speed of Injection) on Peak Width in PLIS
0.23
0.235
0.24
0.245
0.25
0.255
0.26
0.265
0.27
35 45 55 65 75 85 95
Actuation Pressure (Psig Air)
Pea
k W
idth
(m
in)
Peak Width of Methane (min)
Pressurized Liquid Sampling Injection System Pressurized Liquid Sampling Injection System (PLIS) (PLIS)
Load and Inject PositionsLoad and Inject Positions
Courtesy of Transcendent Enterprises Inc.www.transcendent.ca
PLIS TechnologiesPLIS Technologies
Unheated PLIS Resistively Heated PLIS (HPLIS)
Resistively Heated PLIS TechnologyResistively Heated PLIS Technology
Heated PLIS Valve AssemblyShaft exposed – Non energized
Heated PLIS Valve AssemblyShaft exposed – Energized
Shaft DesignShaft Design
Shaft:
Heating Cartridge:
Sample Channel:
Performance of HPLISPerformance of HPLISComparison of syringe injection, energized and nonComparison of syringe injection, energized and non--energized valve from nCenergized valve from nC77 to nCto nC3232
Stainless steel shaft (320C)Stainless steel shaft (320C)
C7
C10C11C12 C14 C16
C18C20 C24
C8 C9
C28 C32
Energized
Non-energized
Syringe
Enlargement fromC24 to C32
C24C28 C32
Energized
Non-energized
Syringe
C24
C24
C28
C28
C32
C32
Comparison of PLIS Injection Modes to Standard Split Injection from nC7 to nC32
0.000
0.500
1.000
1.500
2.000
2.500
C7 C8 C9 C10 C11 C12 C14 C16 C18 C20 C24 C28 C32
Carbon Number
Rat
io t
o n-
Hep
tane
(C
7)
Syringe
SS(E)
SS(NE)
Performance of HPLISPerformance of HPLISComparison of various PLIS injection modes Comparison of various PLIS injection modes -- Each case, ratio to nCEach case, ratio to nC77Syringe S/S: conventional syringe split/Syringe S/S: conventional syringe split/splitlesssplitless injectioninjectionSS(E) SS(E) -- stainless shaft, energized (ca 320C)stainless shaft, energized (ca 320C)SS(NE) stainless steel shaft, nonSS(NE) stainless steel shaft, non--energized (radiant heat from injection port only)energized (radiant heat from injection port only)
C o m p a r i s o n o f P L I S I n j e c t i o n M o d e s t o S t a n d a r d S p l i t I n j e c t i o n f r o m n C 2 0 t o n C 3 2
0.000
0.050
0.100
0.150
0.200
0.250
0.300
0.350
0.400
C 2 0 C 2 4 C 2 8 C 3 2
C a r b o n N u m b e r
Syringe injection
SS(E)
SS(NE)
Performance of HPLIS Performance of HPLIS Comparison of various PLIS injection modes Comparison of various PLIS injection modes -- Each case, ratio to nCEach case, ratio to nC77Syringe S/S: conventional syringe split/Syringe S/S: conventional syringe split/splitlesssplitless injectioninjectionSS(E) SS(E) -- Stainless shaft, energized (ca 320C)Stainless shaft, energized (ca 320C)SS(NE) Stainless steel shaft, nonSS(NE) Stainless steel shaft, non--energized (radiant heat from injection port only)energized (radiant heat from injection port only)
HPLIS with Conventional Approach for HPLIS with Conventional Approach for Fast GCFast GC
nn Hydrogen carrier gasHydrogen carrier gasnn Rapid temperature programming Rapid temperature programming nn Narrow bore, short capillary columnNarrow bore, short capillary columnnn Oven InsertOven Insert
ASTM DASTM D--2887 standard diluted 10:12887 standard diluted 10:14 4 metremetre, 0.15 mm id, BPX, 0.15 mm id, BPX--5 Column Technology5 Column Technology
50 C 50 C -- 0.3 min 0.3 min -- 70C/min 70C/min -- 350 C, u = 100 cm/sec Hydrogen350 C, u = 100 cm/sec Hydrogen
min1 2 3 4 5
pA
0
500
1000
1500
2000
2500
3000
FID1 B, (HPLIS118.D)
min4 4.2 4.4 4.6 4.8 5 5.2 5.4
pA
0
10
20
30
40
50
60
FID1 B, (HPLIS118.D)
C32
C36
C40 C44
5.5 min
min5 10 15 20 25
pA
0
50
100
150
200
FID1 B, (HPLIS078.D)
min5 10 15 20 25
pA
0
50
100
150
200
250
FID1 B, (HPLIS076.D)
Comparison of energized and nonComparison of energized and non--energized PLIS Injectionenergized PLIS Injectionfor Light Hydrocarbon Condensatefor Light Hydrocarbon Condensate30 30 metremetre, 0.32 mm id, 1 micron CP, 0.32 mm id, 1 micron CP--SilSil 5CBMS5CBMS
Light condensate - unheated PLIS
Light condensate - heated PLIS
min5 10 15 20 25 30 35
pA
0
100
200
300
400
FID1 B, (HPLIS080.D)
min5 10 15 20 25 30 35
pA
0
100
200
300
400
FID1 B, (HPLIS079.D)
Heavy condensate - unheated PLIS
Heavy condensate - heated PLIS
Comparison of energized and nonComparison of energized and non--energized PLIS Injection energized PLIS Injection of Heavy Hydrocarbon Condensateof Heavy Hydrocarbon Condensate30 30 metremetre, 0.32 mm id, 1 micron CP, 0.32 mm id, 1 micron CP--SilSil 5CBMS5CBMS
40 min
Heavy and Light Hydrocarbon Condensate with Heated Heavy and Light Hydrocarbon Condensate with Heated PLIS/GC/FIDPLIS/GC/FID
4 4 metremetre, 0.15 mm id, 0.4 micron BPX, 0.15 mm id, 0.4 micron BPX--55Hydrogen carrier, 100 cm/sec, 50C Hydrogen carrier, 100 cm/sec, 50C –– 0.3 min 0.3 min –– 70C/min 70C/min –– 350 C350 C
min1 2 3 4 5 6
pA
200
400
600
800
1000
1200
FID1 B, (HPLIS106.D)
min1 2 3 4 5 6
pA
0
200
400
600
800
1000
1200
FID1 B, (HPLIS105.D)
Heated PLIS - Heavy Condensate
Heated PLIS - Light condensate
6 min
TertTert--butyl butyl catecholcatechol in butadiene by HPLIS/GC/FIDin butadiene by HPLIS/GC/FID30 30 metremetre, 0.32 mm id, 1 micron CP, 0.32 mm id, 1 micron CP--SilSil 5 CBMS5 CBMS
4-terbutyl catechol
Unheated PLIS
Heated PLIS
OverlayTBC
TBC
Comparison of sensitivity of Comparison of sensitivity of MonoethyleneMonoethylene Glycol (MEG) Glycol (MEG) with Heated vs. Non Heated PLIS Injectionwith Heated vs. Non Heated PLIS Injection
30 30 metremetre, 0.25 mm id, 0.5 micron , 0.25 mm id, 0.5 micron StabilwaxStabilwax--DA DA 50 C 50 C –– 1 min 1 min –– 20C/min 20C/min –– 200C200C
MEG
Blue - non-heatedRed - Heated
DEG
HPLIS with HPLIS with MicrovolumeMicrovolume Injection for Injection for Fast GCFast GC
nn Low pressure gas chromatographyLow pressure gas chromatographynn Short, wide bore capillary columnShort, wide bore capillary columnnn Rapid temperature programmingRapid temperature programmingnn Small sample sizeSmall sample size
PLIS for PLIS for MicrovolumeMicrovolume Injection Injection TechniqueTechnique
Channel exposed Channel covered by seal
Analysis of light hydrocarbons CAnalysis of light hydrocarbons C11 to Cto C3 3 5 5 metremetre, 0.53 mm id, Al, 0.53 mm id, Al22OO33/KCl, 12 uL Channel, inlet pressure 1.3 psig/KCl, 12 uL Channel, inlet pressure 1.3 psig
50C 50C –– 0.1 min 0.1 min –– 70C/min 70C/min –– 150C150C
min0.1 0.2 0.3 0.4
pA
25
50
75
100
125
150
175
200
FID1 B, (HPLIS133.D)
1. Methane2. Ethane3. Ethylene4. Propane5. Propylene6. Acetylene7. Impurity8. Impurity
7
1
2
3
4
5
6
8
HPLIS with Vacuum Gas HPLIS with Vacuum Gas ChromatographyChromatography
Selective Detector for Fast GCSelective Detector for Fast GC
nn Vacuum outlet GCVacuum outlet GCnn Highly selective detectorHighly selective detector
Multiple injections of a mixed sulfur standard by Multiple injections of a mixed sulfur standard by PLIS/GC/DRPLIS/GC/DR--SCDSCD
5 5 metremetre, 0.25 mm id, 0.25 micron CP, 0.25 mm id, 0.25 micron CP--SilSil 5CBMS, 250 C Isothermal, 225 cm/sec Helium5CBMS, 250 C Isothermal, 225 cm/sec Helium
Reproducibility of Total S by PLIS/GC/DR-SCD
0
50000
100000
150000
200000
250000
300000
1 2 3 4 5 6 7 8 9 10
Injection Number (#)
Are
a C
ou
nts 1232 ppm S
123.2 ppm S
12.3 ppm S
Figure of meritFigure of meritPrecision at 12.3, 123.2, and 1232.2 Precision at 12.3, 123.2, and 1232.2 ppmppm S (w/w)S (w/w)
RSD 2.82%
RSD 1. 75%
RSD 4.14%
HPLIS with HPLIS with MicromachinedMicromachined Gas Gas ChromatographyChromatography
nn Silicon Silicon micromachinedmicromachined injection systeminjection systemnn Mechanism for introduction of liquid Mechanism for introduction of liquid
samplesample
Analysis of Liquid sample with Analysis of Liquid sample with microGCmicroGC using AVSusing AVSAVS System Coupled to a AVS System Coupled to a MicroGCMicroGC
EXH
EXH
HeliumOut
HeliumIn
uTCDuGCSV-2
SV-1
SV – Solenoid ValveEXH – Exhaust/VentAVS – An experimental product of Transcendent Enterprises Inc.
PLISAdaptor
Seconds0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
mV
olt
0
10
20
30
40
50
60
70
80
90
100
mV
olt
0
10
20
30
40
50
60
70
80
90
100Channel 3 CP-4900 Column Module, 8m 5CB Heated InjMixed HC/PLIS/microGC/TCDPLISISCC038.dat
Injection of 0.2 uL of liquid hydrocarbons mixture with Injection of 0.2 uL of liquid hydrocarbons mixture with AVSAVS
8 8 metremetre, 0.32 mm id, CP, 0.32 mm id, CP--SilSil 5 CB Module Varian CP5 CB Module Varian CP--4900 4900 MicroGCMicroGC
C6
C9
C8
C7C5
air
H20
ConstraintsConstraints
nn HPLIS is designed for “medium” high speed gas HPLIS is designed for “medium” high speed gas chromatographychromatography
nn Limitations associated with split/splitless continues to Limitations associated with split/splitless continues to existexist
nn Trade off between “cool” sample chamber vs. “hot” Trade off between “cool” sample chamber vs. “hot” vaporization conevaporization cone
ConclusionsConclusionsnn The advent of HPLIS provides a new dimension in sampling The advent of HPLIS provides a new dimension in sampling
for fast gas chromatographyfor fast gas chromatography
nn PLIS was demonstrated to be compatible with a wide variety PLIS was demonstrated to be compatible with a wide variety of techniques in fast GCof techniques in fast GC
nn Despite some constraints, HPLIS has the potential to further Despite some constraints, HPLIS has the potential to further enhance the overall performance and flexibility of gas enhance the overall performance and flexibility of gas chromatographychromatography
nn PLIS results tracked conventional needle PLIS results tracked conventional needle split/splitless injection technique in split mode:split/splitless injection technique in split mode:nn Up to C18 in unheated modeUp to C18 in unheated modenn Up to C24 in heated modeUp to C24 in heated mode
AcknowledgementsAcknowledgements
nn Analytical Sciences, Separations TeamAnalytical Sciences, Separations Teamnn Analytical Sciences, Separations Leadership TeamAnalytical Sciences, Separations Leadership Teamnn Professor Dr. Professor Dr. KarelKarel CramersCramers, TU/e, TU/enn James Griffith, Analytical SciencesJames Griffith, Analytical Sciencesnn Dr. Mary Dr. Mary FairhurstFairhurst, Analytical Sciences, Analytical Sciencesnn Ian Moss, Moss and Son Engineering, CanadaIan Moss, Moss and Son Engineering, Canadann Dr. Randy Shearer, Dr. Randy Shearer, IonicsIonics InstrumentsInstrumentsnn Varian InternationalVarian International