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