Eliminating the Need for Standards and Calibration in GC/FID Analysis of Hydrocarbons and Oxygenates

Eliminating the Need for Standards and Calibration in GC/FID Analysis of Hydrocarbons and Oxygenates 20 October 2015 Andrew J. Jones, Ph.D. Co-founder

Methanol to Dimethyl Ether H + CH 3 OH CH 3 OCH 3 + H 2 O 433 K 2

Methanol to Dimethyl Ether H + CH 3 OH CH 3 OCH 3 + H 2 O 433 K MFI (Si/Al = 44) r ~ [CH 3 OH] 0 r ~ [CH 3 OH] 433 K Jones et al., J Catal., 312 (2014) 58 3

Methanol to Dimethyl Ether H + CH 3 OH CH 3 OCH 3 + H 2 O 433 K MFI (Si/Al = 44) CH 3 OH r ~ [CH 3 OH] 0 r ~ [CH 3 OH] 433 K CH 3 OCH 3 Jones et al., J Catal., 312 (2014) 58 4

Methanol to Gasoline (MTG/MTH/MTO) CH 3 OH H + Hydrocarbons >550 K Oxygenates Gasoline 5

Methanol to Gasoline (MTG/MTH/MTO) CH 3 OH H + Hydrocarbons >550 K Oxygenates Gasoline Too many compounds to calibrate accurately and regularly Time consuming analysis Degradation of standards Invisible compounds 6 Michele Sarazen in the Iglesia Group at Berkeley

Methanol to Gasoline (MTG/MTH/MTO) CH 3 OH H + Hydrocarbons >550 K Oxygenates DME Gasoline C1-C3 C2-C4 C4-C5 C5-C6 C7 C8 Too many compounds to calibrate accurately and regularly Time consuming analysis Degradation of standards Invisible compounds 7 Michele Sarazen in the Iglesia Group at Berkeley

Why calibrate? 8

Why calibrate? Flame ionization detector (FID) CHO + -200 V e - air H 2 sample Holm, T., J. Chromatogr. A, 842 (1999) 221 9

Why calibrate? Flame ionization detector (FID) FID Detection Sensitivity (per carbon) CHO + -200 V 0.97 1.04 1 1.12 0.66 e - air H 2 0.23 0.48 0.39 sample 0.01 1 2 3 4 5 6 7 8 9 Dietz, W. A., J. Gas Chromatogr., 5 (1967) 68 Holm, T., J. Chromatogr. A, 842 (1999) 221 10

Why calibrate? Reactive Chromatography Any Molecule FID Detection Sensitivity (per carbon) 0.97 1.04 1 1.12 Catalytic Reactor 0.66 0.48 0.39 0.23 0.01 xch 4 FID 1 2 3 4 5 6 7 8 9 11

Eliminate calibrations and detect more Reactive Chromatography Any Molecule FID Detection Sensitivity (per carbon) 0.97 1.04 1 1.12 Catalytic Reactor 0.66 0.48 0.39 0.23 xch 4 FID Maduskar, S., et al., Lab Chip, 15 (2015) 440 Watanabe, T., et al., Talanta, 72 (2007) 1655 12 0.01 1 2 3 4 5 6 7 8 9

Eliminate calibrations and detect more Reactive Chromatography Any Molecule FID Detection Sensitivity (per carbon) 0.97 1.04 1 1.12 0.66 0.48 0.39 0.23 0.01 xch 4 FID 1 2 3 4 5 6 7 8 9 13

Chemically convert molecules to CH 4 during GC analysis CH 3 OH H + Hydrocarbons >550 K Oxygenates DME Gasoline C1-C3 C2-C4 C4-C5 C5-C6 C7 C8 Too many compounds to calibrate accurately and regularly Time consuming analysis Degradation of standards Invisible compounds 14 Michele Sarazen in the Iglesia Group at Berkeley

Chemically convert molecules to CH 4 during GC analysis CH 3 OH H + Hydrocarbons >550 K Oxygenates DME Gasoline C1-C3 C2-C4 C4-C5 C5-C6 C7 C8 Too many compounds to calibrate accurately and regularly Time consuming analysis Degradation of standards Invisible compounds 15 Michele Sarazen in the Iglesia Group at Berkeley

Chemically convert molecules to CH 4 during GC analysis CH 3 OH H + Hydrocarbons >550 K Oxygenates Gasoline C1-C3 CH 4 /CO CO 2 Formaldehyde C 2 H 4 /C 2 H 6 Too many compounds to calibrate accurately and regularly Time consuming analysis Degradation of standards Invisible compounds Michele Sarazen in the Iglesia Group at Berkeley 16

What this means for your chemical analysis 17

What this means for your chemical analysis Peak Compound 1 ethanol 2 1,2-dichloroethane 3 aniline 4 2-chlorophenol 5 1-octanol 6 2-nonanone 7 2-dodecanol 8 methyl laurate 9 n-heptadecane 10 n-nonadecane Polar-Iso Test Mix 18

What this means for your chemical analysis Standard FID Peak Compound 1 ethanol 2 1,2-dichloroethane 3 aniline 4 2-chlorophenol 5 1-octanol 6 2-nonanone 7 2-dodecanol 8 methyl laurate 9 n-heptadecane 10 n-nonadecane Polar-Iso Test Mix 1 2 3 4 5 6 7 8 9 10 19

What this means for your chemical analysis Standard FID Peak Compound 1 ethanol 2 1,2-dichloroethane 3 aniline 4 2-chlorophenol 5 1-octanol 6 2-nonanone 7 2-dodecanol 8 methyl laurate 9 n-heptadecane 10 n-nonadecane Polar-Iso Test Mix 1 2 3 4 5 6 7 8 9 10 20

What this means for your chemical analysis Standard FID Polar-Iso Test Mix Peak Compound Area Concentration 1 ethanol 74416.5? 2 1,2-dichloroethane 387726.1? 3 aniline 233? 4 2-chlorophenol 158.5? 5 1-octanol 216.9? 6 2-nonanone 218.5? 7 2-dodecanol 231.7? 8 methyl laurate 207.8? 9 n-heptadecane 266.8? 10 n-nonadecane 259.6? 1 2 3 4 5 6 7 8 9 10 21

Compound Response (area/µmol C) What this means for your chemical analysis 40 Standard Calibration Curve Standard FID 35 30 25 y = 1.45x - 2.32 R² = 0.9948 3 20 15 10 5 0 0 5 10 15 20 25 30 EtOH Response (area/µmol C) 22

Compound Response (area/µmol C) What this means for your chemical analysis 40 35 Standard Calibration Curve 1 2 Standard FID 9 10 30 25 20 3 4 5 6 7 8 15 10 5 0 0 5 10 15 20 25 30 EtOH Response (area/µmol C) 23

Compound Response (area/µmol C) What this means for your chemical analysis 40 35 Standard Calibration Curve 1 2 Standard FID 9 10 30 25 20 3 4 5 6 7 8 15 10 Unknown 5 0 0 5 10 15 20 25 30 EtOH Response (area/µmol C) 24

Compound Response (area/µmol C) Measurement Error What this means for chemical analysis 40 Standard Calibration Curve 7% Standard FID 35 6% 30 5% 25 4% 20 15 10 Unknown 3% 2% 5 1% 0 0 5 10 15 20 25 30 EtOH Response (area/µmol C) 0% 0 2 4 6 8 10 12 Peak Number 25

Measurement Error What this means for chemical analysis Catalytic Conversion to CH 4 7% FID signal with reaction 6% 5% 4% 3% 2% 1% 0% 0 2 4 6 8 10 12 Peak Number 26

Measurement Error What this means for chemical analysis Catalytic Conversion to CH 4 7% FID signal with reaction 6% 5% 4% 3% No calibration necessary 2% 1% mol C = Area Area std mol Cstd 0% 0 2 4 6 8 10 12 Peak Number 27

Measurement Error What this means for chemical analysis FID signal with reaction Catalytic Conversion to CH 4 7% 6% 5% 4% Average Error FID: 4% With Reaction: 2% 3% No calibration necessary 2% 1% mol C = Area Area std mol Cstd 0% 0 2 4 6 8 10 12 Peak Number 28

What is the Polyarc reactor? 29

What is the Polyarc reactor? 30

What is the Polyarc reactor? 31

What is the Polyarc reactor? 32

Works on all GC-compatible hydrocarbons C5-C18 n-alkanes C5 C18 Spanjers, C. et al., Application Note, 2015, University of Minnesota, Twin Cities 33

Works on all GC-compatible hydrocarbons C5-C18 n-alkanes C5 C18 Spanjers, C. et al., Application Note, 2015, University of Minnesota, Twin Cities 34

Works on all GC-compatible hydrocarbons Spanjers, C. et al., Application Note, 2015, University of Minnesota, Twin Cities 35

Works on all GC-compatible hydrocarbons Spanjers, C. et al., Application Note, 2015, University of Minnesota, Twin Cities 36

Works on all GC-compatible hydrocarbons C1-C6 n-alkanes C 6 H 14 C 5 H 12 C 2 H 6 C 3 H 8 C 4 H 10 CH 4 37

Works on all GC-compatible hydrocarbons C1-C6 n-alkanes Response Factors C 6 H 14 C 5 H 12 RF (mol C) = 1.01 ± 0.01 C 2 H 6 C 3 H 8 C 4 H 10 CH 4 38

Designed for heteroatoms 39

Designed for heteroatoms Food/Flavors/Fragrances Carbohydrates Commodity Chemicals Pharmaceuticals Cosmetics 40

Response Factor Specially engineered long-life cartridge 1.2 EtOH/n-heptane 1 0.8 0.6 0.4 ROH RCl RC(O)OH RNH 3 RN: ROH Low priced replacement cartridges $1295 0.2 0 0 500 1000 1500 2000 2500 3000 Injections 41

Response Factor Specially engineered long-life cartridge No performance degradation with over 5000 injections 1.2 EtOH/n-heptane 1 0.8 0.6 ROH RCl RC(O)OH RNH 3 RN: ROH 0.4 0.2 0 0 500 1000 1500 2000 2500 3000 Injections 42

Response Factor Specially engineered long-life cartridge No performance degradation with over 5000 injections 1.2 EtOH/n-heptane 1 0.8 0.6 0.4 ROH RCl RC(O)OH RNH 3 RN: ROH Low priced replacement cartridges $1295 0.2 0 0 500 1000 1500 2000 2500 3000 Injections 43

Conclusions Chemical conversion to CH 4 eliminates the need for standard calibrations in quantification Full conversion and high accuracy for a variety of heteroatoms (O, N, S, Cl, Si and more) Negligible impact on separation performance Long lifetime Available Now! Only at ARC: activatedresearch.com 44

Questions? See us at Booth #346 and vote for us in the New Product Showcase Andrew Jones Brad Cleveland Kim Herzog www.activatedresearch.com 45