New Specialized GC Columns for the Petroleum Industry -Integrated Particle Trap PLOTs -DB-Sulfur SCD

Transcription

1 New Specialized GC Columns for the Petroleum Industry -Integrated Particle Trap PLOTs -DB-Sulfur SCD Daron Decker GC Columns Technical Specialist Agilent Technologies, Inc. October 29, 2013

2 Porous Layer Open Tubular (PLOT) Columns Challenges: Stationary phase particle shedding "Solid" Porous Layer Fused Silica Tubing Analysis of gases High vapor pressure solutes Increased retention (k) Unique selectivity (a) compared to WCOT Detector spikes impacts results Changes restriction interferes with instrument control/tuning Risks switching valves, CFT devices & connectors Can not be combined with GCMS 2

3 Solutions for PLOT Column issue--- stationary phase particle shedding 1. Install a particle trap on the end of the column Drawbacks: set-up time, prone to leaks, clog, add labor cost 2. Install inline filters Drawbacks: eventually clog and cause flow restriction over time 3. Just live with it - majority of analysts 3

4 What is an Integrated Particle Trap PLOT Column? PLOT columns with 2.5 meter integrated particle traps on both ends virtually eliminates the classic particle shedding problem Particle traps are integrated no unions and/or fittings 2.5m Integrated particle trap at front and back end of the column PLOT column part Compatible with capillary GC, GC/MS and valve switching GC systems including Capillary Flow Technology (CFT) Similar selectivity, plates and peak shape performance to existing Agilent J&W PLOT columns

5 The Column and Integrated Particle Trap 5

6 No Detector Spikes Observed on PT Columns with Repeated Temperature and Pressure Cycling 75,000 70,000 5,000 0,000 55,000 50,000 5,000 0,000 35,000 30,000 25,000 20,000 15,000 10,000 5, , ,000 18,000 1,000 1,000 12,000 10,000 8,000,000,000 2, ,000 -,000 -,000-8,000-10,000-12,000-1,000-1,000-18, µv _20_2011 1_30_05_GC 1 Pressure test_101958_ _1.data [MIBASB02 Chan 2 FID B] Detector signal spikes Standard PLOT column µv Spiketest GC115_7_12_2011 8_2_18 AM.DATA [MIBASB01 Chan 1 FID A] PLOT Column with Integrated Particle Trap RT [min] RT [min] Temperature: 150 C + 20 C/min 250 C;15 times Pressure 3x optimum Each run switch off/on carrier gas 10 times The unusual chromatogram shows the detector signal profile of the temp and pressure cycling

7 FID Baseline Testing from 220 C to 280 C Column: PoraBond Q PT, 25m 0.25mm,3um (30 meter total length) Carrier : Helium, Oven: : 220 C for 30 min 220 C C at 10 C/min 280 C for 30 min Detector: FID, 300 No spikes pa < C <5 220 C min 7

8 MSD! Baseline Testing from 220 C to 280 C Column: PoraBond Q PT, 25m 0.25mm,3um (30 meter total length) Carrier : Helium, Oven: : 220 C for 30 min 220 C C at 5 C/min 280 C for 30 min Detector: MSD, 280 Transfer line, full Scan at m/z Abundance Time--> <2e+5 TIC: bk-20.d\data.ms <3e No spikes 8

9 Clean Mass Spectrum, PoraBond Q PT at 280 C Styrene 10 Abundance m/z--> 0 DVB porous polymer Scan 1880 (70.57 min): bk-20.d\data.ms Particle trap Siloxanes

10 Similar Selectivity Solvent Analysis Carrier : Helium, 5.25 ml/min Oven: 150 Inlet: 200, split ratio=0:1 Detector: FID 250 Inj. Vol: 0.2uL pa pa PoraPLOT Q PT PoraPLOT Q min 1. Methanol 2. Ethanol 3. Acetonitrile. Acetone 5. Methylene Chloride. Diethyl ether 7. 1-propanol 8. Trichloromethane 9. Ethyl acetate 10.Hexane 11.Benzene 12.Heptane min Differences observed between our standard PLOT columns and their PLOT PT counterparts shows that the variability in results is generally within the column to column reproducibility range for PLOT column manufacturing 10

11 Similar Selectivity Important Application C2 C3 PoraBOND Q :C1-C2 PoraBOND Q: C3 With PT 2 pa pa GC35a3 20_2012 2_32_52 PM.DATA RT [min] GC35a3 20_2012 2_32_52 PM.DATA RT [min] pa 19 GC35a2 20_ _08_5 AM.DATA 9 pa GC35a2 20_ _08_5 AM.DATA Without PT RT [min] RT [min] PoraPLOT Q :C1-C2 PoraPLOT Q: C3 With PT 32 pa GC3a-2 20_ _09_18 AM.DATA RT [min] pa GC3a-2 20_ _09_18 AM.DATA RT [min] pa GC3a-3 20_2012 2_5_12 PM.DATA pa GC3a-3 20_2012 2_5_12 PM.DATA Without PT RT [min] RT [min]

12 Similar Selectivity Important Application C1 C2 PoraPLOT U: C1-C pa GC35b5 23_2012 2_13_58 AM.DATA With PT RT [min] Without PT pa GC35b5 25_2012 1_13_31 PM.DATA RT [min]

13 Propadiene Propyne Methane Ethene Trans-2-Butene Cis-2-Butene 1,3-Butadiene Ethane Propane Propene Butane+Ethyne 1-Butene Isobutene Propadiene Propyne Methane Ethene Trans-2-Butene Cis-2-Butene 1,3-Butadiene Ethane Propane Propene Butane+Ethyne 1-Butene Isobutene Influence of integrated particle traps on selectivity (Aluminum oxide PLOT) pa pa With particle traps GC35back1_7_2_2013 9_20_0 AM.DATA 5.87 Without particle traps.29 RT [min] GC35back2_7_2_ _35_31 PM.DATA RT [min] First test with integrated particle traps Second test after removal of particle traps (pressure adjusted to correct for length difference)

14 Lifetime test: Porous Polymer PLOT PT columns Test done with PPQ, PPU,PBQ and HP-PLOT-Q Lifetime test performed by a high number of injections of methanol with 10% water 350 to 1350 injections are done After these injections, the columns are tested again No change in performance is observed 1

15 Retention Index Diethylether and Aceton Retention index Ethylacetate Lifetime test PoraPLOT U PT 1350 injections Methanol / 10% water Lifetime - Retention Index RI Diethylether RI Aceton RI Ethylacetate Injections

16 k Ethylacetate Platenumber Ethylacetate Lifetime test PoraPLOT U PT 1350 injections Methanol / 10% water Lifetime - k Ethylacetate Injections Lifetime - Platenumber Ethylacetate Injections Conclusion: No change in performance of the column after multiple injections (Similar results for all porous polymer PLOT PT columns) 1

17 Lifetime Test Al 2 O 3 PT 50m x 0.32mm Temperature program: 0 C + 10 C/min --> 200 C (0 min.) Carrier gas N2, 50 kpa. FID In 3 weeks 50 runs, 300 hours at the maximum T of 200 C. KCl Before lifetime test After lifetime test total st dev total st dev Difference RI ethene RI propene RI ethyne RI propadiene RI t-2-butene RI 1-butene RI isobutene RI c-2-butene RI propyne RI 1,3-butadiene N 1,3-butadiene k 1,3 butadiene N/m 1,3-butadiene u (cm/sec) CFR Please note: No PDMS degradation at 200 C! Na2SO Before lifetime test After lifetime test total st dev total st dev Difference RI ethene RI propene RI propadiene RI ethyne RI t-2-butene RI 1-butene RI isobutene RI c-2-butene RI 1,3-butadiene RI propyne N 1,3-butadiene k 1,3 butadiene N/m 1,3-butadiene u (cm/sec) CFR

18 Lifetime Test Molsieve 5A 30m x 0.53 mm 50µm Molsieve 5A PT Temperature program: 0 C + 10 C/min --> 200 C (23 min) + 10 C/min --> 300 C (5min) Carrier gas N2, 25 kpa. TCD In 3 weeks 531 runs, with 20 hours at 200 C and hours at the maximum temperature of 300 C. Before lifetime test After lifetime test Average StDev Average StDev Difference Asym Carbonmonoxide N methane K methane Res He/Ne Res Ar/O CFR Before lifetime test After lifetime test Average StDev Average StDev Difference Asym Carbonmonoxide N methane K methane Res He/Ne Res Ar/O CFR

19 Lifetime Test Conclusions After prolonged exposure at high operating temperature there is no significant change of the chromatographic performances of the Molsieve 5A and Al 2 O 3 columns. The bleed of the particle traps (front end) has no negative effect on the PLOT phases. 19

20 Ideal for Solvent Analysis by GCMS Column: PoraBond Q PT, 25m 0.25mm,3um (30m total length) Carrier : Helium, Oven: : 90 C- 10 C at 10 C/min 10 C for min 10 C C at 5 C/min 200 C for 10 min Injection: Split, 250, split ratio1:10 Detector: MSD, 280 Transfer line, full Scan at m/z Methyl Alcohol 2. Acetaldehyde 3. Ethanol. Acetonitrile 5. Acetone. Methylene Chloride 7. Isopropyl Alcohol 8. 2-Propanamine 9. Ethyl Formate Propanol 11. Ethyl ether 12. t-butyl alcohol 13. 1,2-Ethanediol 1. Trichloromethane Butanone (MEK) 1. Ethyl Acetate 17. sec-butyl alcohol 18. MTBE chlorobutane Butanol 21. Benzene 22. 1,1,1-Trichloroethane chlorobutane 2. Carbon Tetrachloride 25. Hexane 2. 1,-Dioxane 27. Pyridine 28. Dimethyl Formamide (DMF) 29. Isoamyl Alcohol 30. Dimethyl Sulfoxide (DMSO) 31. Toluene 32. Heptane 33. Paraldehyde 3. Chlorobenzene 35. Ethylbenzene 3. m-xylene 37. p-xylene 38. o-xylene , ,

21 Excellent Peak Shape for Alcohols by GCMS Column: PoraBond Q PT, 25m 0.25mm,3um (30 m total length) Carrier : Helium, Oven: : 90 C- 10 C at 10 C/min 10 C for min 10 C C at 5 C/min 200 C for 10 min Injection: Split, 250, split ratio1:10 Detector: MSD, 280 Transfer line, full Scan at m/z Methyl Alcohol 2. Acetaldehyde 3. Ethanol. Acetonitrile 5. Acetone. Methylene Chloride 7. Isopropyl Alcohol 8. 2-Propanamine 9. Ethyl Formate Propanol 11. Ethyl ether Acetonitrile methanol 1 Ethanol Propanamine IPA Propanol

22 Halocarbons by GCMS Column: PoraPLOT Q PT, 25m 0.32mm,10um (P/N CP7551PT) (30m total length) Carrier : Helium, Oven: : 55 C for 5min 55 C C at 12 C/min 200 C for 10min Injection: 250, splitless, 0.2min purge activation time Detector: MSD, 280 Transfer line, full Scan at m/z Sample: 1uL Fluoroform (Freon-23) 2. 1,1,1-trifluoroethane (Freon-13a) 3. Pentafluoroethane (Freon-125). Bromotrifluoromethane (Freon-13b1) 5. 1,1,1,2-Tetrafluoroethane (Freon-13a). 1,1-difluoroethane (Freon-152a) 7. Difluorochloromethane (Freon-22) 8. 1,1,2,2-tetrafluoroethane (Freon-13) 9. 1-chloro-1,1-difluoroethane (Freon-12) 10. Bromochlorodifluoromethane (Freon-12b1) 11. Ethyl Chloride (Freon-10) 12. Fluorodichloromethane (Freon-21) 13. Trichloromonofluoromethane (Freon-11) 1. 1,1-Dichloro-1-fluoroethane (Freon-11) 15. 2,2-dichloro-1,1,1-trifluoroethane (Freon-123) 1. 1,1,2-trichloro-1,2,2-trifluoroethane (Freon-113) 17. 1,2-dibromo-1,1,2,2-tetrafluoroethane (Freon-11b2) 18. Trichloromethane (Freon-20) 19. 1,2-dichloroethane 20. 1,1,1-trichloro-ethane 21. Trichloroethylene 22. 1,1,2-trichloroethane

23 Coal to Chemical Process Gas Analysis 25 µv Carrier : H2, Oven: : 32 C for 5 min 32 C C at 15 C/min Injection: 170, split ratio 5:1 Detector: TCD, 250 Sample: 250uL HP-PLOT Q PT 30m 0.53mm,0um (35m total length) min 1. Carbon monoxide 2. Methane 3. Carbon dioxide. Ethylene 5. Ethane. Hydrogen sulfide 7. Water 8. Propylene 9. Propane 10. Dimethyl ether 11. Methanol Butene 13. Butane 25 µv HP-PLOT Q 30m 0.53mm,0um min 23

24 Coal to Chemical Process Gas Analysis Identify compounds by MSD Column: HP-PLOT Q PT, 30m 0.32mm,20um (P/N 19091P-Q0PT) (35m total length) Carrier : Helium, 1mL/min Oven: : 32 C for 3 min 32 C C at 15 C/min Injection: 170, split 5:1 Detector: MSD, 280 Transfer line, full Scan at m/z Sample: 250uL CO DME CO 2 1-Butene Propylene Butane Ethane Ethylene Propane CH MeOH H 2 S H 2 O

25 Excellent Peak Shape of Hydrogen Sulfide on HP-PLOT U PT Column Carbon monoxide 2. Methane 3. Carbon dioxide. Ethylene 5. Ethane. Hydrogen sulfide 7,8 7. Propylene 8. Propane 9. Dimethyl ether 10. Methanol Butene 12. Butane ,12 HP-PLOT U PT, 30m 0.53mm,20um (35m total length) Carrier : H2, Oven: : 32 C for 5 min,32 C - 70 C at 30 C/min 70 C for 5 min,70 C - 10 C at 10 C/min Injection: 170, split ratio 5:1 Detector: TCD, 250 Sample: 250uL min ,8 H 2 O 9 11,12 10 HP-PLOT U PT, 30m 0.32mm,10um (35m total length) Carrier : H2, Oven: : 32 C for 5 min,32 C - 70 C at 30 C/min 70 C for 5 min,70 C - 10 C at 10 C/min Injection: 170, split ratio 5:1 Detector: MSD, 280 Transfer line, full Scan at m/z Sample: 250uL

26 No spikes at Fixed Gases Analysis on CP-Molsieve 5Å PLOT PT column CP-Molsieve 5Å, 25m 0.53mm,50um (30m total length) Carrier : H2, 3mL/min Oven: : 80 C isothermal Injection: 70 C, split ratio 5:1 Detector: TCD, 250 Sample: 100uL CP-Molsieve 5Å showing spikes when particle traps are removed (Red trace). No spikes with manufacturer integrated particle trap (Blue Trace). 2

27 Agilent J&W PLOT PT Columns Available PLOT PT columns: Porous polymers: PoraPLOT Q PoraBOND Q PoraBOND Q HT HP-PLOT Q GS-Q PoraPLOT U HP-PLOT U NEW! Aluminum oxide HP-PLOT Al2O3 S HP-PLOT Al2O3 M HP-PLOT Al2O3 KCl GS-Alumina GS-Alumina/KCl CP-Al2O3 KCl CP-Al2O3 Na2SO NEW! Molsieve CP-Molsieve 5A Custom PLOT PT columns are available for these phases Phase type Part number Description Dimensions PLOT Q CP738PT PoraBOND Q PT 25m x 0.25mm x 3µm CP7351PT PoraBOND Q PT 25m x 0.32mm x 5µm CP7352PT PoraBOND Q PT 50m x 0.32mm x 5µm CP7353PT PoraBOND Q PT 10m x 0.53mm x 10µm CP735PT PoraBOND Q PT 25m x 0.53mm x 10µm CP7550PT PoraPLOT Q PT 10m x 0.32mm x 10µm CP7551PT PoraPLOT Q PT 25m x 0.32mm x 10µm CP755PT PoraPLOT Q PT 25m x 0.53mm x 20µm CP7557PT PoraPLOT Q-HT PT 25m x 0.32mm x 10µm PT GS-Q PT 30m x 0.53mm 19091P-QO3PT HP-PLOT Q PT 15m x 0.32mm x 20µm 19091P-QOPT HP-PLOT Q PT 30m x 0.32mm x 20µm 19095P-QO3PT HP-PLOT Q PT 15m x 0.53mm x 0µm 19095P-QOPT HP-PLOT Q PT 30m x 0.53mm x 0µm PLOT U CP758PT PoraPLOT U PT 25m x 0.53mm x 20µm 19095P-UOPT HP-PLOT U PT 30m x 0.53mm x 20µm Al2O3 KCl CP7515PT CP-Al2O3/KCl PT 50m x 0.32mm x 5µm deactivated CP7517PT CP-Al2O3/KCl PT 25m x 0.53mm x 10µm CP7518PT CP-Al2O3/KCl PT 50m x 0.53mm x 10µm 19091P-K15PT HP-PLOT Al2O3 KCl PT 50m x 0.32mm x 8µm 19095P-K23PT HP-PLOT Al2O3 KCl PT 30m x 0.53mm x 15µm 19095P-K25PT HP-PLOT Al2O3 KCl PT 50m x 0.53mm x 15µm PT GS-Alumina/KCl PT 50m x 0.53mm Al2O3 Na2SO CP755PT CP-Al2O3/Na2SO PT 50m x 0.32mm x 5µm deactivated CP758PT CP-Al2O3/Na2SO PT 50m x 0.53mm x 10µm 19091P-S12PT HP-PLOT Al2O3 S PT 25m x 0.32mm x 8µm 19091P-S15PT HP-PLOT Al2O3 S PT 50m x 0.32mm x 8µm 19095P-S23PT HP-PLOT Al2O3 S PT 30m x 0.53mm x 15µm 19095P-S25PT HP-PLOT Al2O3 S PT 50m x 0.53mm x 15µm Al2O3 with PT GS-Alumina PT 30m x 0.53mm proprietary PT GS-Alumina PT 50m x 0.53mm deactivation 19095P-M25PT HP-PLOT Al2O3 M PT 50m x 0.53mm x 15µm Molsieve CP753PT CP-Molsieve 5A PT 30m x 0.32mm x 10µm CP753PT CP-Molsieve 5A PT 25m x 0.32mm x 30µm CP7538PT CP-Molsieve 5A PT 25m x 0.53mm x 50µm CP7539PT CP-Molsieve 5A PT 50m x 0.53mm x 50µm 27

28 Conclusions Agilent s integrated particle trap technology for PLOTs - Similar selectivity to non-pt PLOT columns - Virtually eliminates problems due to particle shedding - Possible to use MS detection, valves and CFT worry-free 28

29 Now Let s Switch Gears New DB-Sulfur SCD for GC-SCD Analysis of Sulfur Compounds 29

30 Why so much focus on Sulfur? Sulfur Compounds -can be corrosive to equipment, pipe lines, reactors -can inhibit or destroy catalysts employed in downstream processing -can impart undesirable odors to products -in fuel pollutes the air (Environmental regulations require lower levels) 30

31 Challenges for Sulfur Analysis Low levels often require maximum sensitivity Matrix interference from the hydrocarbons present Highly reactive and polar molecules 31

32 Detectors for Sulfur Analysis Why not use an FID or MSD? 32

33 Sulfur Detection Detector GC-FPD GC-PFPD GC-SCD Supplier Agilent OI Agilent MDL Sulfur 3. pg/sec 1 pg/sec <0.5 pg/sec Selectivity Dynamic Range Quenching yes yes no Equimolar No No yes response Packed Col yes No, yes Compatible < 1ml/min Other Elements P, Sn P N Cost $ $$ $$$

34 SCD for Sulfur Analysis Basis for several ASTM methods Very sensitive but. Slow to stabilize tricky to operate Prone to coking in the ceramic reaction tubes with resulting costly maintenance and slow recovery Method ASTM D228 ASTM D28 ASTM D550 ASTM D523 Description Volatile sulfur in C1, C2, C3 and C monomers and LPG Volatile Sulfur in NGA, fuel gas Sulfur in gas fuels by SCD Sulfur in light petroleum liquids by SCD 3

35 About SCD Maintenance. Ceramic reaction tube fouling/ coking Typical costs in the US: Price per incident preventative maintenance service call for GC-SCD: $1755 USD Cost of SCD ceramics: G $35 USD Dual plasma burner kit: G $59 USD. Plus the self repair time of hours and several days to stabilize. 35

36 SCD Ceramic Combustion Tubes & Burner 3

37 What is required of GC column for Sulfur Analysis? Linearity of response from ppm ppb 100% sulfur recovery Response Retention & Selectivity Minimal detector quenching Robust/Low Bleed Stable detector response Low detection limits Loadability/Capacity Low SCD maintenance Large injection volumes Low detection limits 37

38 Introducing DB-Sulfur SCD New optimized low polarity column with low bleed and exceptional inertness to sulfur even at trace levels Developed with Dow Chemical and other leading companies Excellent for a broad range of sulfur compounds from light sulfur gasses to sulfur containing hydrocarbons out to C2 Optimized for the lowest possible contribution to SCD reaction tube fouling. 38

39 DB-Sulfur SCD Easy to change from existing columns but with: Greatly improved SCD performance Increased stability Less frequent burner tube maintenance Part Number Description Temperature limits G DB-Sulfur SCD 0m, 0.32mm,.2um 250 /270 C G DB-Sulfur SCD 0m, 0.32mm, 0.75um 270 /290 C G DB-Sulfur SCD 70m, 0.53mm,.3um 250 /270 C G DB-Sulfur SCD 0m, 0.32mm, 3um 250 /270 C 39

40 DB-Sulfur SCD: sulfur standards in Toluene Good resolution of H2S and COS at room temperature Thiophene and 2-Methyl-1-propanethiol can be baseline separated Hydrogen sulfide 2 Carbonyl sulfide 3 Methanethiol Ethanethiol 5 Dimethyl sulfide Carbon disulfide 7 2-Propanethiol 8 2-Methyl-2-propanethiol 9 1-Propanethiol 10 Ethyl methyl sulfide 11 Thiophene 12 2-Methyl-1-propanethiol 13 Diethyl sulfide 1 1-Butanethiol 15 Methyl disulfide 1 2-Methylthiophene 17 3-Methylthiophene 18 Diethyl disulfide 19 5-Methylbenzothiophene 20 3-Methylbenzo(b)thiophene 21 Diphenyl sulfide (Int Std) Column: Agilent J&W DB-Sulfur SCD, 0 m x 0.32 mm,.2 μm (p/n G ) min 0

41 Typical chromatogram of Sulfur compounds in Light Petroleum Liquids by ASTM D523 Sulfur Compounds in Gasoline Ethanethiol 2. Dimethyl sulfide 3. Carbon disulfide. 2-Propanethiol 5. 2-Methyl-2-propanethiol. 1-Propanethiol 7. Ethylmethyl sulfide 8. Thiophene/ 2-Methyl-1-propanethiol 9. Dimethyl Disulfide Methylthiophene Methylthiophene C2-thiophenes 13. Diethyl disulfide 1. Benzothiophene 15. C1-benzothiophenes 1. C2-benzothiophenes 17. Diphenyl sulfide (Int Std) Time (minutes) the industry standard 1

42 DB-Sulfur SCD: Real Samples 15 µv pyrolysis gasoline Int Std 0 15 µv min naphtha Int Std 0 15 µv min Sulfur standards Int Std min 2

43 DB-Sulfur SCD: Sulfur Sensitivity Peak No S/N µv Sample: 00ppb sulfur standard Inj. Vol: 1uL Split ratio: 10:1 Int Std 800 Approximately 2.5pg for each compound on column (calculated) 00 Low bleeding at 250 C min 3

44 Repeatability N= 10 ppm 1ppm 0.1ppm No Compound RSD% RSD% RSD% 1 Methyl mercaptan Ethyl mercaptan Methyl sulfide Carbon disulfide Propanethiol Methyl-2-propanethiol Propanethiol Ethyl methyl sulfide Thiophene ppm 1ppm 0.1ppm No Compound RSD% RSD% RSD% 1 Methyl mercaptan Ethyl mercaptan Methyl sulfide Carbon disulfide Propanethiol Methyl-2-propanethiol Propanethiol Ethyl methyl sulfide Thiophene Methyl-1-propanethiol Diethyl sulfide Butanethiol Methyl disulfide Methylthiophene Methylthiophene Diethyl disulfide Methylbenzothiophene Methylbenzo(b)thiophene Methyl-1-propanethiol Diethyl sulfide Butanethiol Methyl disulfide Methylthiophene Methylthiophene Diethyl disulfide Methylbenzothiophene Methylbenzo(b)thiophene

45 DB-Sulfur SCD: Sulfur Sensitivity 15 µv AIB1 B, Back Signal (R-1\L-2PPM D) AIB1 B, Back Signal (R-1\L-2PPM D) AIB1 B, Back Signal (R-1\L-2PPM D) AIB1 B, Back Signal (R-1\L-2PPM00002.D) AIB1 B, Back Signal (R-1\L-2PPM D) 2ppm H 2 S Compound S/N RSD% (N=5) H 2 S COS COS min 5

46 Linearity Compound Concentration Range Linearity (R 2 ) Compound Concentration Range Linearity (R 2 ) Hydrogen sulfide 2ppm-25ppm Carbonyl sulfide 2ppm-25ppm Methanethiol 0.1ppm-10ppm Ethanethiol 0.1ppm-50ppm Dimethyl sulfide 0.1ppm-10ppm Carbon disulfide 0.1ppm-10ppm Propanethiol 0.1ppm-50ppm Methyl-2- propanethio 0.1ppm-10ppm Propanethiol 0.1ppm-10ppm Ethyl methyl sulfide 0.1ppm-50ppm Thiophene 0.1ppm-50ppm Methyl-1-propanethiol 0.1ppm-10ppm Diethyl sulfide 0.1ppm-10ppm Butanethiol 0.1ppm-10ppm Methyl disulfide 0.1ppm-10ppm Methylthiophene 0.1ppm-50ppm Methylthiophene 0.1ppm-50ppm Diethyl disulfide 0.1ppm-10ppm Methylbenzothiophene 0.1ppm-10ppm Methylbenzothiophene 0.1ppm-50ppm

47 Configuration to test SCD Quenching Issue Inlet Pulsed SCD 325 torr CFT splitter :5 Thick film PDMS type Column 1:5 FID 710 torr Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada 7

48 Area Counts Traditional PDMS column SCD Ceramic Reaction Tube Deactivation Hydrogen Sulfide Carbonyl Sulfide Methyl Mercaptan Response factors deteriorate as column bleed deactivates rods in subsequent runs over the day Response factor returns to baseline after 12 hour regeneration period Day 1 Day 2 Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada 8 11/1/2013

49 Traditional PDMS column- Coking (desensitization) of Reactor Tubes Overlay of before (green) and after 2 x 2 ul neat toluene Injection (red) SCD: 10% drop in sensitivity 1. Hydrogen Sulfide 2. Carbonyl Sulfide 3. Methyl Mercaptan. Ethyl Mercaptan FID: No response changes 3 Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada 9 11/1/2013

50 New DB-Sulfur SCD column Last Three Runs of the day (n=20, 100 ppmv std) SCD H2S 2. COS 3. CH3SH. C2H5SH FID 0C 3 250C Cool down Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada 50

51

52 Sulfides and Thiophenes (n=5) 1. Dimethyl sulfide (100 ppm) 2. Ethyl methyl sulfide (50 ppm) 3. Thiophene (100 ppm). Diethyl sulfide (75 ppm) 5. Dimethyl disulfide (25 ppm). 2-methyl thiophene (75 ppm) 7. 3-methyl thiophene (100 ppm) 8. Diethyldisulfide (20 ppm) 9. Benzothiophene (75 ppm) methylbenzothiophene (100 ppm) Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada 52

53 Chromatograms of 50 ppm v each of sulfides and mercaptans and 500 ppm v each of hydrocarbons in nitrogen SCD Hydrogen sulfide 2. Carbonyl sulfide 3. Methyl mercaptan. Ethyl mercaptan FID Methane 2. Ethane 3. Propane. Butane 5. Pentane. Hexane Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada 53

54 Chromatogram of carbon disulfide and alkyl mercaptans SCD Ethyl mercaptan (100 ppm) 2. Carbonyl sulfide (20 ppm) 3. Isopropyl mercaptan (100 ppm). Tert-butyl mercaptan (50 ppm) 5. N-propyl mercaptan (100 ppm). Sec-butyl mercaptan (50 ppm) 7. Isobutyl mercaptan (100 ppm) 8. N-Butyl mercaptan (50 ppm) FID 1. Isooctane (mixed solvent) 2. Toluene (mixed solvent) Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada 5

55 Chromatogram of sulfides, disulfides, thiophene, alkyl thiophenes, benzothiophene, and alkyl benzothiophenes SCD Dimethyl sulfide (100 ppm) 2. Ethyl methyl sulfide (50 ppm) 3. Thiophene (100 ppm). Diethyl sulfide (75 ppm) 5. Dimethyl disulfide (25 ppm). 2-methyl thiophene (75 ppm) 7. 3-methyl thiophene (100 ppm) 8. Diethyldisulfide (20 ppm) 9. Benzothiophene (75 ppm) methylbenzothiophene (100 ppm) FID Isooctane (solvent) 2. Toluene (solvent) Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada 55

56 Chromatogram volatile sulfur odorants in commercially available natural gas SCD 3 1. Hydrogen sulfide 2. Methyl mercaptan 3. Tert-butyl mercaptan. Methyl ethyl sulfide 1 2 FID Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada Methane 2. Propane 3. Iso-butane. N-Butane 5. Iso-pentane. N-Pentane 7. Hexanes 8. Heptanes 5

57 Conclusions The new Agilent J&W DB-Sulfur SCD with low bleed and excellent inertness can provide: Excellent resolution and peak shape Excellent linearity at ppm to ppb levels Excellent repeatability Less ceramic tube fouling/less detector maintenance Before detector maintenance every 3 weeks Now over months, no SCD maintenance! 57

58 Application Notes and Literature: ASTM D523 and ASTM D550 Brochure number EN 58

59 New Column Summary PLOT PT columns - Similar selectivity to non-pt columns - Virtually eliminates problems due to particle shedding - Possible to use MS detection, valves and CFT worry-free DB-Sulfur SCD columns - Perfect for dependable volatile sulfur compound analysis utilizing the SCD 59