Hernan J. Cortes, Robert A. Shellie, Jim Luong, Kayte ... · Hernan J. Cortes, GCxGC, Toronto, Canada. January 2013 16 . 4 Oven Wall Suggested internal diameters for the collection

1

Hernan J. Cortes, Robert A. Shellie,

Jim Luong, Kayte Parlevliet.

HJ Cortes Consulting, LLC., Midland, MI USA, University of

Tasmania, Hobart, Tasmania and SGE, Melbourne,

Australia.

Hernan J. Cortes, GCxGC, Toronto, Canada. January 2013

Migration from tube based flow systems to planar microchannel systems to deliver flexible and innovative chromatographic solutions

1. Suitable for fast moving molecules 2. Doesn’t require cryogen 3. In-Oven with no moving parts

Capillary flow technology (first generation) SilFlow technology (second generation)

Hernan J. Cortes, GCxGC, Toronto, Canada. January 2013 2

Like capillary flow technology:

• Chemically inert

• Low to no dead volume

• Super operational stability (thermal cycle)

• Easy to install and leak free

Unlike capillary flow technology:

• Much lower thermal mass; by 300%

• Substantially lower cost, by 400%

• Smaller in size = flexibility for system application


FID-1 Inlet

30 m x 0.32 mm-id x 20 µm HP-PLOT Q

Transfer line

Configuration of a three-port splitter device for parallel chromatography

30 m x 0.32 mm-id x 10 µm Rtx-Alumina BOND MAPD

FID-2


4

•. Luong, R. Gras, R.A. Shellie, H.J. Cortes – J. Sep. Sci., 30 (2013) 182-191

PW1/2=0.007648 min

PW1/2=0.0102 min

HPLOT Q 1. Methane

2. Acetylene

3. Ethylene

4. Ethane

5. Propylene

6. Propane

Al2O3

1

4

3

6 5

2

5

6

4

3

2 1

30 m x 0.32 mm-id x 20 µm HP-PLOT Q



Luong, R. Gras, R.A. Shellie, H.J. Cortes – J. Sep. Sci., 30 (2013) 182-191

FID Inlet 1 m x 0.32 mm-id fused silica

Configuration of a three-port splitter device for column effluent splitting

30 m x 0.32 mm-id x 5 µm CP-Sil 5CB

SCD

2 m x 0.20 mm-id fused silica


6

J. Luong, R. Gras, R.A. Shellie, H.J. Cortes – J. Sep. Sci., 30 (2013) 182-191

FID

P-SCD

1. Hydrogen sulfide

2. Carbonyl sulfide

3. Methyl mercaptan

4. Ethyl mercaptan

5. Impurity

6. Impuritiy

Hydrocarbons in natural gas

1 2 3 4

5

6



FID-1

Inlet Pressure (P1)

Transfer line

Fused silica restrictor

Pressure control

module (P2)

10 m x 0.32 mm-id x 1 µm VF-Waxms

FID-2




Column 1: 10 m x 0.32 mm x 1 µm VF-WAXms

Column 2: 30 m x 0.32 mm Rtx-AluminaBOND MAPD

VF-WAXms 1. Methane

2. Ethane

3. Ethylene

4. Propane

5. Propylene

6. Acetylene

7. Butane

8. Pentane

9. Hexane

1,2,3,4,5,6,7,8,9

Water if present Backflush

4

3

2

1 9 8 7

6

5

Rtx-AluminaBOND MAPD


•J. Luong, R. Gras, H.J. Cortes, R.A. Shellie –J. Chromatogr A, 1271 (2013) 185-191

Column 2

Column 1

Transfer line

Flow profiles:

• P1>>P2 = forward

• P1>P2 = isolate Column 2

• P2>>P1 = backflush

Inlet Pressure (P1)

Pressure control

module (P2)

FID

TCD



Minutes

1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2 6.4

Volt

-0.01

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

Volt

-0.01

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

0.10

1.667

1.791

2.886

Hydr

ogen

3.144

Oxyg

en 3.7

80

Nitro

gen 4.7

68

(Meth

ane)

Front TCD

TCD Porabond Q and RT U Bond no stripper no aux

NameRetention Time

Minutes

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Volt

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Volt

-0.05

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

Carb

on M

onox

ide

2.59

0M

etha

ne 2.

736

Carb

on D

ioxide

3.64

8

Ethy

lene 4.

439

Etha

ne 5.

168

Acet

ylene

5.58

7

Prop

lyene

10.1

78

Prop

ane

10.6

20

12.0

84

12.8

08

15.7

18

19.7

03

Back FID

Porabond Q and RT U Bond no stripper

Name

Retention Time

TCD – MS5A

FID – PoraBOND Q/Methanizer

9. Hydrogen

10. Oxygen

11. Nitrogen

1. Carbon monoxide

2. Methane

3. Carbon dioxide

4. Ethylene

5. Ethane

6. Acetylene

7. Propylene

8. Propane

1 2 6

7

8 4 5 3

9

10

11



Al2O3

VF-WAXms 1. Methane

2. Ethane

3. Ethylene

4. Propane

5. Propylene

6. Acetylene

7. Butane

8. Pentane

9. Hexane

10. Methanol

11. Ethanol

12. Propanol

13. Butanol

1,2,3,4,5,6,7,8,9 11 10

12

13

1

2

4

5 6

7 3

8 9



First detector

Second detector

Inlet (P1)

Column 1

Restrictor

Column 2

Ba

ckflo

w p

rote

ctio

n re

stric

tor

Pressure control

Module (P2)

Three-way solenoid

= Connection port


13


min2 4 6 8 10 12

pA

0

50

100

150

200

250

300

350

FID2 B, (DEANSWITCH\C1R000127.D)

2.2

63

2.6

25

2.7

77

2.9

84

3.0

34

3.2

56

3.4

78

3.7

57

4.8

65

min2 4 6 8 10 12

pA

0

50

100

150

200

250

300

350

FID1 A, (DEANSWITCH\C2D000127.D)

2.5

53

2.6

20

8.5

73

9.1

86

9.6

56 1. Light hydrocarbons

2. Methanol

3. Ethanol

4. Propanol

VF-1ms

CP-Lowox 1

2

2

3


14


• Flow modulation with SilFlow

• Performance and operating characteristics

• Configurations and applications with auxiliary ovens (LTM)

• Industrial Applications

• Summary

• Acknowledgements

15 Hernan J. Cortes, GCxGC, Toronto, Canada. January 2013

Flow modulation is an option for implementation of comprehensive GCxGC

Strengths: • Does not require cryogen • Simple to construct (connection fittings, three-way

gas switching valve, a timing device) • Ideal for fast moving molecules • Handles heavy hydrocarbons

Limitations: • Unlike thermal modulation where modulation period

can be readily changed, parameter optimization can be more intensive and careful attention to k in the second dimension is important


4

Oven Wall

Suggested internal diameters for

the collection loop: 0.45mm,

0.32mm, 0.53mm

Be aware of peak broadening

as collection channel size increases Column 1 In Column 2 out

From PCM

3 way

micro

valve

External Fused Silica collection

loop

N. O.


18

First dimension column

1 mL/min

Second dimension column

22 mL/min

Inlet Pressure control module

20 mL/min

Detector

Modulator with two

Three-three port

SilFlow


19

Design Key Attribute

External Channel Easy to setup and use

Variable External Loop [1] Fine tune for application

External Loop with reverse

flow pulse [2]

Can improve modulated

peak shapes with larger ID

columns in 1st dimension

1. J. V. Seeley J. Chromatogr. A. 1255, (2012) 24

2. Griffith et al., J. Chromatogr. A. 1226 (2012) 116


Along with other commercially available fluidic

devices, aids in reducing FM-GCxGC to practice:

• No moving parts

• Low thermal mass

• Inert

• In-column switching


21

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5

Fir

st

co

lum

n f

low

ml/

min

Modulation Period in seconds


22 Analysis of modulated C13, no retention time correction applied

Single pulse


Column 1: 10 m x 0.18 mm x 0.18 µm DB1

Column 2: 5 m x 0.25 mm x 0.15 µm DB-INNOwax

Column 1 flow: 0.4 mL/min

Column 2 flow: 21mL/min

Modulation Timing

Load: 2.895 sec.

Inject: 0.114 sec.

Period: 3.009 sec.

23

Lower primary flow allows longer modulation period

Typical “general purpose” setup


24

Column 1: 10 m x 0.18 mm x 0.18 um DB1

Column 2: 5 m x 0.25 mm x 0.15 um DB-INNOwax


25

Three Independent temperature programs

FID FID FID

Column 2 S/S Inlet

Column 1

PCM Micro Valve

S/S Inlet

Column 1

PCM Micro Valve

S/S Inlet

Column 1

PCM Micro Valve

Modulator

FID FID FID

Column 3

FID FID LTM

FID FID LTM

Splitter LTM = Low Thermal Mass



Picture courtesy of Dr. Peter Dawes, SGE Analytical Science, Australia

27

Column Heated By Column Dimensions Comments

First D 7890 Oven 20 m x 0.18um x 0.10

µm VF-5ms

Rugged

2nd D - I LTM I 5 m x 0.25 mm x 0.15

µm INNOwax

Polar

2nd D - II LTM II 5 m x 0.25 mm x 0.15

µm DB17 HT

Mid-polarity


28

1. Nonane

2. 3-methyl nonane

3. Decane

4. 3-methyl decane

5. Undecane

6. 3-methyl 1-undecane

7. Dodecane

8. 4-methyl-dodecane

9. 3-methyl-dodecane

10. Tridecane

11. Tetradecane

1 2 3 4

5 6 7 8 9 10 11

12 13

14 15 16 17

18

19

20

21

22

12. Butyl benzene

13. 1-methyl 4 propyl benzene

14. 1-methyl-4-(1-methylpropyl)-benzene

15. Penty lbenzene

16. 1-methyl butyl benzene

17. Hexyl benzene

18. 1,3 dimethyl butyl benzene

19. 1-methyl hexyl benzene

20. 1-methyl 2-n-hexyl benzene

21. 1-butylhexyl-benzene

22. 1-propyl heptyl-benzene



30

1. Methane

2. Ethylene

3. Acetylene

4. Propylene

5. Propane

6. Methanol

7. Ethanol

8. Propanol

1

2

5

4

7

6 8

3


Because pulsed flow modulation does not

rely on thermal focusing, hydrocarbons

to over C70-C80 can be successfully

modulated


Fuels and lubricants are complex samples,

often encountered in manufacturing processes

- knock-out pots, pipelines, exchangers etc.

Current analytical tools for the identification of

fuels and lubricants are adequate but not

ideal

FM-GCxGC has the potential of offering fast,

efficient and accurate identification of oils


Classical GC Comprehensive 2D-GC

33

Diesel

Mine Oil


Diesel

Petroleum Distillate

Gasoline

Mine Oil

Various type of fuels and lubricants by FM-GCxGC



System cleanliness is essential for successful implementation of the technique

FM-GCxGC typically requires longer method development when compared to conventional GC or thermally modulated GCxGC


University of Tasmania SGE Analytical Science Robert Shellie, Jim Luong, Kayte Parlevliet


• J. Luong, R.A. Shellie, H. J. Cortes, R. Gras, T. Hayward, J. Chromatogr. A, 1229 (2012) 223-229 o Ultra trace analysis of morpholine, cyclohexylamine and diethylaminoethanol in steam condensate by GC with MMI-FID

• J. Luong, R. Gras, R.A. Shellie, H.J. Cortes, J. Sep. Sci., 35 (2012) 1486-1493 o Direct measurement of part-per-billion level of dimethyl sulfoxide in water by GC with stacked injection and

chemiluminescence detection

• J. Luong, R. Gras, H.J. Cortes, R.A. Shellie, J. Chromatogr. A, 1231 (2012), 216-220 o Multi-dimensional gas chromatography with a planar microfluidic device for the characterization of oxygenated compounds

• J. Luong, R. Gras, H.J. Cortes, R.A. Shellie, J. Chromatogr. A, 1261 (2012) 136-141 o Temperature Programmable low thermal mass silicon micromachined gas chromatography and differential mobility detection

for the fast analysis of trace level of ethylene oxide in medical work place atmospheres

• J. Luong, E. Nazarov, R. Gras, R.A. Shellie, H.J. Cortes, IJMS, 3 (2012) 179-187 o Resistively heated temperature programmable silicon micromachined gas chromatography with differential mobility

spectrometry

• . Luong, R. Gras, R.A. Shellie, H.J. Cortes – J. Sep. Sci., 30 (2013) 182-191 o Applications of planar microfluidic devices and gas chromatography for complex problem solving

• J. Luong, R. Gras, H.J. Cortes, R.A. Shellie –J. Chromatogr A, 1271 (2013) 185-191 o Multidimensional gas chromatography for the characterization of permanent gases and Light Hydrocarbons in catalytic

cracking process

• J. Luong, R. Gras, R.A. Shellie H.J. Cortes – J. Chromatogr. A; accepted. o Planar microfluidic device and low thermal mass GC in multi-dimensional gas chromatography for the characterization of

targeted volatile organic compounds


Documents

Hernan J. Cortes, Robert A. Shellie, Jim Luong, Kayte ... · Hernan J. Cortes, GCxGC, Toronto, Canada. January 2013 16 . 4 Oven Wall Suggested internal diameters for the collection