Hernan J. Cortes, Robert A. Shellie, Jim Luong, Kayte Parlevliet. HJ ...

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 

1

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) 


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 


3

Configuration of a three-port splitter device for parallel chromatography 

Inlet 

Transfer line 

30 m x 0.32 mm-id x 20 µm HP-PLOT Q 

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

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


FID-1 

FID-2 

4

30 m x 0.32 mm-id x 20 µm HP-PLOT Q 


HPLOT Q 

PW1/2=0.0102 min 

Al 2O 3 

PW1/2=0.007648 min 

1 

1 

4 

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

3 

2 

3 

4 

6 

5 

5 

6 

2 

1. Methane 

2. Acetylene 

3. Ethylene 

4. Ethane 

5. Propylene 

6. Propane 

Hernan J. Cortes, GCxGC, Toronto, Canada. January 2013 5

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

Inlet 

30 m x 0.32 mm-id x 5 µm CP-Sil 5CB 

1 m x 0.32 mm-id fused silica 

2 m x 0.20 mm-id fused silica 

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


FID 

SCD 

6

FID 

P-SCD 

1 

Hydrocarbons in natural gas 

2 3 4 

5 

6 

1. Hydrogen sulfide 

2. Carbonyl sulfide 

3. Methyl mercaptan 

4. Ethyl mercaptan 

5. Impurity 

6. Impuritiy 



7

Inlet Pressure (P1) 

10 m x 0.32 mm-id x 1 µm VF-Waxms 

Pressure control 

module (P2) 

Transfer line 

Fused silica restrictor 

FID-1 

FID-2 




8

VF-WAXms 

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

Rtx-AluminaBOND MAPD 

2 

1 

Water if present Backflush 

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

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

3 

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

4 

5 

6 

7 


8 

1. Methane 

2. Ethane 

3. Ethylene 

4. Propane 

5. Propylene 

6. Acetylene 

7. Butane 

8. Pentane 

9. Hexane 

9 

9

Inlet Pressure (P1) 

Column 1 

Flow profiles: 

• P1>>P2 = forward 

• P1>P2 = isolate Column 2 

• P2>>P1 = backflush 

Transfer line 


module (P2) 

Column 2 


FID 

TCD 


10

Volt 

Volt 

0.50 

0.45 

0.40 

0.35 

0.30 

0.25 

0.20 

0.15 

0.10 

0.05 

0.00 

-0.05 

0.10 

0.09 

0.08 

0.07 

0.06 

0.05 

0.04 

0.03 

0.02 

0.01 

0.00 

-0.01 

Back FID 

Porabond Q and RT U Bond no stripper 

Name 

Retention Time 

Carbon Monoxide 

Front TCD 

TCD Porabond Q and RT U Bond no stripper no aux 

Name 

Retention Time 

1.667 

2.590 

Methane 

Carbon Dioxide 2.736 

1.791 

1 2 

3.648 

Ethylene 

3 

4.439 

4 5 

Ethane 

5.168 Acetylene 

5.587 

6 

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

Minutes 

2.886 

Hydrogen 

3.144 

Oxygen 

3.780 

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 

Minutes 


9 

Proplyene 

10.178 

Propane 

10.620 

7 

8 

10 

12.084 

12.808 

0.50 

0.45 

FID – PoraBOND Q/Methanizer 

Nitrogen 

4.768 

11 

15.718 

1. Carbon monoxide 

2. Methane 

3. Carbon dioxide 

4. Ethylene 

5. Ethane 

6. Acetylene 

7. Propylene 

8. Propane 

TCD – MS5A 

9. Hydrogen 

10. Oxygen 

11. Nitrogen 

Hernan J. Cortes, GCxGC, Toronto, Canada. January 2013 11 

(Methane) 

19.703 

0.40 

0.35 

0.30 

0.25 

0.20 

0.15 

0.10 

0.05 

0.00 

-0.05 

0.10 

0.09 

0.08 

0.07 

0.06 

0.05 

0.04 

0.03 

0.02 

0.01 

0.00 

-0.01 

Volt 

Volt

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

10 

Al 2O 3 

1 

2 

3 

12 

4 

13 

5 

6 

7 

VF-WAXms 


8 

9 

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 

Hernan J. Cortes, GCxGC, Toronto, Canada. January 2013 12

Inlet (P1) 

First detector 

Second detector 

Restrictor 

Column 1 

Column 2 


Backflow protection restrictor 


Three-way solenoid 

= Connection port 


Module (P2) 

13

pA 

350 

300 

250 

200 

150 

100 

50 

0 

pA 

350 

300 

250 

200 

150 

100 

50 

0 

FID2 B, (DEANSWITCH\C1R000127.D) 

VF-1ms 

2.263 

2.625 

2.777 

3.0342.984 

3.256 

3.478 

3.757 

4.865 

2 

FID1 A, (DEANSWITCH\C2D000127.D) 

4 6 8 10 12 

CP-Lowox 

2.620 

2.553 

1 

2 4 6 8 10 12 



2 

8.573 

9.186 

2 

9.656 

3 

min 

1. Light hydrocarbons 

2. Methanol 

3. Ethanol 

4. Propanol 

min 

14

• Flow modulation with SilFlow 

• Performance and operating characteristics 

• Configurations and applications with auxiliary ovens 

(LTM) 

• Industrial Applications 

• Summary 

• Acknowledgements 


15

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 


16

From PCM 

3 way 

micro 

valve 

N. O. 

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 

Oven Wall 


External Fused Silica collection 

loop 

4

Inlet 

First dimension column 

1 mL/min 

Modulator with two 

Three-three port 

SilFlow 


Pressure control module 

20 mL/min 

Second dimension column 

22 mL/min 

Detector 

18

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] 

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

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


Can improve modulated 

peak shapes with larger ID 

columns in 1 st dimension 

19

Along with other commercially available fluidic 

devices, aids in reducing FM-GCxGC to practice: 

• No moving parts 

• Low thermal mass 

• Inert 

• In-column switching 


20

First column flow ml/min 

0.9 

0.8 

0.7 

0.6 

0.5 

0.4 

0.3 

0.2 

0.1 

0 

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 

Modulation Period in seconds 


21

Analysis of modulated C13, no retention time correction applied 


Single pulse 

22

Typical “general purpose” setup 

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. 

Lower primary flow allows longer modulation period 


23

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 


24

S/S Inlet 

PCM Micro Valve 

Three Independent temperature programs 

Column 1 

LTM = Low Thermal Mass 

Modulator 

Splitter 


Column 2 

FID LTM 

FID LTM 

Column 3 

FID 

FID 

25

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


26

Column Heated By Column Dimensions Comments 

First D 7890 Oven 20 m x 0.18um x 0.10 

µm VF-5ms 

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

µm INNOwax 

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

µm DB17 HT 


Rugged 

Polar 

Mid-polarity 

27

1 2 3 

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 

12 

13 

4 

14 15 16 

5 6 7 

17 

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 


18 

19 

20 

8 9 10 11 

21 

22 

28


29

1. Methane 

2. Ethylene 

3. Acetylene 

4. Propylene 

5. Propane 

6. Methanol 

7. Ethanol 

8. Propanol 


3 

1 

2 

5 

4 

6 

7 

8 

30

Because pulsed flow modulation does not 

rely on thermal focusing, hydrocarbons 

to over C70-C80 can be successfully 

modulated 


31

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 


32

Diesel 

Classical GC Comprehensive 2D-GC 

Mine Oil 


33

Various type of fuels and lubricants by FM-GCxGC 

Gasoline 

Petroleum Distillate 


Diesel 

Mine Oil 

34


35

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 


36

University of Tasmania 

SGE Analytical Science 

Robert Shellie, Jim Luong, Kayte Parlevliet 


37

• 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 


38

Hernan J. Cortes, Robert A. Shellie, Jim Luong, Kayte Parlevliet. HJ ...

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