The Dow Chemical Company

Applying Contemporary Gas Chromatography to Solve Industrial Analytical Problems

R. Gras, J. Griffith, M. Hawryluk, B. Harfmann, Y. Hua, J. Luong, B. Winniford, G. Yang, P. Yang

Analytical Sciences & Analytical Technology CenterMay 18th, 2017

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Gas Chromatography in Analytical Chemistry

A CENTURY OF CONTINUOUS IMPROVEMENTS and INNOVATIONS

The Roles of Gas Chromatography at Dow

A quintessential enabling analytical technique with a very large installed base

Examples of application areas:• Volatile and semi-volatile molecules• Process optimization and process control• Impurities in feeds, intermediate, and final products (CoA)• EH&S monitoring and site licensing requirements• Pyrolysis GC

Strengths: • Ubiquitous, quick and easy to use, available at virtually any site• Wide range of analytes/applicability • Multi-analyte, sensitive (sub ppm)• Selective detection• Support to other analytical techniques

Practice widely; from operators to subject-matter-experts

#Separate Molecules Unite People

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Insights to Innovations

R. Gras, M. Lee, R. Stevenson, American laboratory, 2011

Some priority items from a long list:

• Ease of use

• Alternatives to convection heating

• Smaller footprint

• Planar microfluidics

• Increase energy efficiency

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The transformation of Ease of Use – An example

1960* 2005** 2016**1990**

*Source: Google

**Source: Personal archive

Intuvo GCs at the Dow Chemical Company

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Productivity with Efficiency and Proficiency

• Smart GC

• Suitable for use by novice to expert

• Improve productivity, reliability, and high throughput

Unique heating technology

• High degree of repeatability

• Fast temperature programming of up to 250 °C/min

• Relatively fast cool down time

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Impact of Faster Temperature Programming

10 °C/min

25 °C/min

50 °C/min

100 °C/min

200 °C/min

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4.0 min

8.5 min

Revolutionary Column Form Factor

The three NOs:

• No hassle column installation

• No column positioning

• No column trimming

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Microfluidic Enabled (Gas) Chromatography

Maintenance/Rapid Configuration

• Guard chip

• Simple one dimension

• Mid point back-flush

• Stream splitting & backflush

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Guard chip

Furanic Compounds – Food & Energy

5-methyl furfural

2-fural methyl ketone

5-hydroxymethyl furfural

Furfural alcohol

Furfural

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Hydrocarbons

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30 m x 0.32 mm id x 1 µm PDMS column

40 °C – 1 min – 15 °C/min – 280 °C – 5 min

1. Cyclohexane

2. C8

3. C10

4. C12

5. C14

6. C15

7. C16

8. C18

9. C20

10. C22

11. C24

2

11

1 3 4 5 6 7

89

10

Hydrocarbons

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30 m x 0.32 mm id x 1 µm PDMS column

40 °C – 1 min – 15 °C/min – 280 °C – 5 min

C8 C10

C18 C20 C22C24

RSD Area counts: < 2% (n=9)

RSD tR: <0.005% (n=9)

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Rapid Screening of Hydrocarbons

5 m x 0.25 mm id x 0.25 µm PDMS (WW-LFS3) column, Helium @ 80 cm sec-1

40 °C – 0.1 min – X °C/min – 300 °C – 1 min

50 °C/min

250 °C/min

100 °C/min

C24

C24

C24

Adsorption Chromatography

• A sensible alternative for cryogenic chromatography

• Plays a vital role in petrochemical and environmental analysis

• Ideal for highly volatile compounds

• Complementary to partition chromatography

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V.G. Berezkin and J. de Zeeuw

Light Hydrocarbons up to C6 with WCOT

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5 m x 0.32 mm id x 5 µm PDMS Column

40 °C – 0.2 min – 150 °C/min – 200 °C – 1 min

1. Methane/Ethane

2. Propane

3. Butane

4. Pentane

5. Hexane

6. Benzene

7. Toluene

2

1

3

4

5

6

7

Light Hydrocarbons up to C6 with PLOT

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5 m x 0.32 mm id GS-GasPro column

40 °C – 0.1 min – 150 °C/min – 200 °C – 2 min

1. Methane

2. Ethane

3. Propane

4. Butane

5. Pentane

6. Hexane

50 °C/min

100 °C/min

150 °C/min

21

3 45 6

21

34

56

21

34

5 6

Light Hydrocarbons and Aromatics

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5 m x 0.32 mm id GS-GasPro column

40 °C – 0.1 min – 50 °C/min – 200 °C – 5 min

1. Methane (5%)

2. Ethane (20%)

3. Ethylene (35%)

4. Acetylene (0.4%)

5. Propane (0.1%)

6. Propylene (0.5%)

7. Iso-butane (0.1%)

8. N-butane (0.1%)

9. 1-Butene (0.1%)

10. 1,3-Butadiene (0.5%)

11. Pentane (0.1%)

12. 1-Pentene (0.1%)

13. 1,4-Pentadiene (0.1%)

14. Hexane (0.1%)

15. 1-Hexene (0.1%)

16. Benzene (0.2%)

17. Toluene (0.1%)

21

3

4

5

6

7

10

178 9 11 12

14 15

1613

Volatile Oxygenated and Sulfurs

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1. Methanol

2. Methyl mercaptan

3. Ethanol

4. Ethyl mercaptan

5. Propanol

6. Acetone

7. Propyl mercaptan

8. Butyl mercaptan

1

2

3

8

45

7

6

5 m x 0.32 mm id PoraBOND Q column

60 °C – 0.1 min – 100 °C/min – 250 °C – 1 min

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Constraints & Boundaries of 9000 series GC

•Only one inlet and one valve available

•Column form factor restrictions in diameter and length

•Without modification, not for MDGC or GCxGC

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Concluding Remarks

• Gaps identified in the past decade are valuable drivers for continuous improvements and innovations for gas chromatography

• New generation of gas chromatographs are transformational and impactful• Inertness• Microfluidic centric chromatography• Productivity tools with both efficiency and proficiency

• “See the Future – Be the Future” • Heating technology, novel column form factor, inter-column connectivity are a few

examples

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Acknowledgements

• All the GC pioneers in academia and industry over the last century

• All the collaborators in chromatography

• Leadership at the Dow Chemical Company

• Agilent AQM/Intuvo 9000 project team

• Dr. Wayde Konze, Dow Analytical Sciences

• Mr. Mike de Poortere, Dow Analytical Technology Center

• Dr. Matthias Pursch, Dow Analytical Sciences

• Dr.Tonya Stockman, Dow Analytical Sciences

• Dr. Eva Maria Fruehauf, Dow Analytical Sciences

• Dr. J.D. Tate, Dow Analytical Technology Center

• Dr. Martine Stolk, Dow (retired)

• Dr. Judy Gunderson, Dow (retired)

• Dr. Taylor Hayward, Apeel Sciences

• Ms. Shanya Kane, Agilent Technologies

• Mr. Mike McMullen, Agilent Technologies

• Ms. Mary Cuddyre, Agilent Technologies

• Mr. Dave Judd, Agilent Technologies

• Agilent colleagues at LFS, WAD, SCS, Folsom Site

• Dow 2014-2016 Technology Renewal and Development fund

And many others.....

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The Dow Chemical Company

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