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

Porous Layer Open Tubular (PLOT) Columns

"Solid"

Porous

Layer

Fused Silica

Tubing

Analysis of gases

High vapor pressure solutes

Increased retention (k)

Unique selectivity (a) compared to WCOT

Challenges:

Stationary phase particle shedding

Detector spikes impacts results

Changes restriction interferes with

instrument control/tuning

Risks switching valves,

CFT devices & connectors

Can not be combined with GCMS

2

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

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

• 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

2.5m Integrated

particle trap at

front and back

end of the

column

PLOT

column

part

4

The Column and Integrated Particle Trap

5

6

No Detector Spikes Observed on PT Columns

with Repeated Temperature and Pressure Cycling

140130120110100908070605040302010

75,000

70,000

65,000

60,000

55,000

50,000

45,000

40,000

35,000

30,000

25,000

20,000

15,000

10,000

5,000

0

-5,000RT [min]

µV 4_20_2011 14_30_05_GC 1 Pressure test_1019658_9270800_1.DATA [MIBASB02 Chan 2 FID B]

130120110100908070605040302010

20,000

18,000

16,000

14,000

12,000

10,000

8,000

6,000

4,000

2,000

0

-2,000

-4,000

-6,000

-8,000

-10,000

-12,000

-14,000

-16,000

-18,000 RT [min]

µV Spiketest GC1415_7_12_2011 8_26_18 AM.DATA [MIBASB01 Chan 1 FID A]

•Temperature:

150°C + 20°C/min

250°C;15 times

• Pressure 3x optimum

• Each run switch off/on

carrier gas 10 times

PLOT Column with Integrated Particle Trap

Standard PLOT column

Detector signal spikes

The unusual

“chromatogram“

shows the detector

signal profile of the

temp and pressure

cycling

FID Baseline Testing from 220°C to 280°C

7

min 10 20 30 40 50 60

pA

4

6

8

10

12

14

16

18

20

Column: PoraBond Q PT, 25m×0.25mm,3um

(30 meter total length)

Carrier : Helium, 36cm/s @220 ℃

Oven: : 220 °C for 30 min

220 °C - 280 °C at 10°C/min

280 °C for 30 min

Detector: FID, 300 ℃

<5 PA @ 220 °C

<18 PA @ 280 °C

No spikes

MSD! Baseline Testing from 220°C to 280°C

15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00 100000 200000 300000 400000 500000 600000 700000 800000 900000

1000000 1100000 1200000 1300000 1400000 1500000 1600000 1700000 1800000 1900000 2000000 2100000 2200000 2300000 2400000 2500000 2600000 2700000 2800000 2900000 3000000

Time-->

Abundance

TIC: bk-20.D\data.ms

<2e+5

<3e+6

Column: PoraBond Q PT, 25m×0.25mm,3um

(30 meter total length)

Carrier : Helium, 34cm/s @220 ℃

Oven: : 220 °C for 30 min

220 °C - 280 °C at 5°C/min

280 °C for 30 min

Detector: MSD, 280 ℃ Transfer line, full Scan at m/z 40-300

No spikes

8

“Clean” Mass Spectrum, PoraBond Q PT at 280°C

40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 4000

20000

40000

60000

80000

100000

120000

140000

160000

180000

200000

220000

240000

260000

280000

300000

320000

340000

m/z-->

Abundance

Scan 16880 (70.567 min): bk-20.D\data.ms104

78

207

130

51

281

191147

341

325249 265163 356222 399297 383

117

104

78

51

Styrene

9

Particle trap Siloxanes

DVB porous polymer

Similar Selectivity Solvent Analysis

min0 5 10 15 20 25 30 35

pA

50

100

150

200

250

300

min0 5 10 15 20 25 30 35

pA

50

100

150

200

250

300

PoraPLOT Q PT

PoraPLOT Q

1

2

34

5

6

7

8 9 10

11

12

12

11

1098

7

6

21

4

5

3

Carrier : Helium, 5.25 mL/min

Oven: 150℃

Inlet: 200 ℃, split ratio=60:1

Detector: FID 250℃

Inj. Vol: 0.2uL

1. Methanol

2. Ethanol

3. Acetonitrile

4. Acetone

5. Methylene Chloride

6. Diethyl ether

7. 1-propanol

8. Trichloromethane

9. Ethyl acetate

10.Hexane

11.Benzene

12.Heptane

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

Similar Selectivity Important Application C2 – C3

4.34.24.143.93.83.73.63.53.43.33.23.132.92.82.72.62.52.42.32.22.121.91.8

19

18

17

16

15

14

13

12

11

10

9

8

7

6

5

4

3 RT [min]

pA GC35a2_6_20_2012 11_08_45 AM.DATA

3.63.53.43.33.23.132.92.82.72.62.52.42.32.22.121.91.81.71.61.51.4

26

25

24

23

22

21

20

19

18

17

16

15

14

13

12

11

10

9

8

7

6

5

4 RT [min]

pA GC35a3_6_20_2012 2_32_52 PM.DATA

15.815.615.415.21514.814.614.414.21413.813.613.413.21312.812.612.412.21211.811.611.411.2

9

8.5

8

7.5

7

6.5

6

5.5

5

4.5

4

3.5

3

RT [min]

pA GC35a2_6_20_2012 11_08_45 AM.DATA

13.613.413.21312.812.612.412.21211.811.611.411.21110.810.610.410.210

10.5

10

9.5

9

8.5

8

7.5

7

6.5

6

5.5

5

4.5

4

3.5

3RT [min]

pA GC35a3_6_20_2012 2_32_52 PM.DATA

PoraBOND Q :C1-C2 PoraBOND Q: C3

With PT

Without PT

4.74.64.54.44.34.24.143.93.83.73.63.53.43.33.23.132.92.82.72.62.52.42.32.22.121.91.81.7

32

30

28

26

24

22

20

18

16

14

12

10

8

6

4

2 RT [min]

pA GC36a-2_6_20_2012 11_09_18 AM.DATA

4.54.44.34.24.143.93.83.73.63.53.43.33.23.132.92.82.72.62.52.42.32.22.121.91.81.71.61.5

28

26

24

22

20

18

16

14

12

10

8

6

4

2RT [min]

pA GC36a-3_6_20_2012 2_45_12 PM.DATA

2120.52019.51918.51817.51716.51615.51514.5

11

10.5

10

9.5

9

8.5

8

7.5

7

6.5

6

5.5

5

4.5

4

3.5

3

2.5

2 RT [min]

pA GC36a-2_6_20_2012 11_09_18 AM.DATA

20.52019.51918.51817.51716.51615.51514.514

8.5

8

7.5

7

6.5

6

5.5

5

4.5

4

3.5

3

2.5

2RT [min]

pA GC36a-3_6_20_2012 2_45_12 PM.DATA

PoraPLOT Q :C1-C2 PoraPLOT Q: C3

With PT

Without PT

11

Similar Selectivity Important Application C1 – C2

4.44.243.83.63.43.232.82.62.42.221.81.61.41.21

27

26

25

24

23

22

21

20

19

18

17

16

15

14

13

12

11

10

9

8

7

6

5

4RT [min]

pA GC35b5_6_25_2012 1_13_31 PM.DATA

4.44.243.83.63.43.232.82.62.42.221.81.6

19

18

17

16

15

14

13

12

11

10

9

8

7

6

5RT [min]

pA GC35b5_6_23_2012 2_13_58 AM.DATA

PoraPLOT U: C1-C2

With PT

Without PT

12

Influence of integrated particle traps on selectivity

(Aluminum oxide PLOT)

6.565.554.543.532.521.510.5

24

23

22

21

20

19

18

17

16

15

14

13

12

11

10

9

8

7

6

5

4

3

1.69

1.77

1.83

2.00

2.31

2.69

2.73

3.50

3.67

3.88

4.08

4.49 4.87

5.87

6.29

RT [min]

pA GC35back1_7_2_2013 9_20_06 AM.DATA

6.565.554.543.532.521.510.50

24

23

22

21

20

19

18

17

16

15

14

13

12

11

10

9

8

7

6

5

4

1.56

1.64

1.70

1.87

2.19

2.57

2.61

3.39

3.56

3.78

3.98 5.79

6.21

RT [min]

pA GC35back2_7_2_2013 12_35_31 PM.DATA

• First test with

integrated particle

traps

• Second test after

removal of particle

traps (pressure

adjusted to correct

for length

difference)

With particle traps

Without particle traps

Meth

ane

Meth

ane

Eth

ane

Eth

ane

Eth

ene

Eth

ene

Pro

pane

P

ropane

Pro

pene

Pro

pene

Pro

padie

ne

Pro

padie

ne

B

uta

ne+

Eth

yne

B

uta

ne+

Eth

yne

Tra

ns-2

-Bute

ne

Tra

ns-2

-Bute

ne

1-B

ute

ne

1-B

ute

ne

Isobute

ne

Is

obute

ne

Cis

-2-B

ute

ne

C

is-2

-Bute

ne

1,3

-Buta

die

ne

1,3

-Buta

die

ne

Pro

pyne

Pro

pyne

13

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

14

Lifetime test PoraPLOT U PT

1350 injections Methanol / 10% water

614.0

616.0

618.0

620.0

622.0

624.0

626.0

628.0

630.0

632.0

634.0

510.0

512.0

514.0

516.0

518.0

520.0

522.0

524.0

526.0

528.0

530.0

0 200 400 600 800 1000 1200

Rete

nti

on

in

dex E

thyla

ceta

te

Rete

nti

on

In

dex D

ieth

yle

ther

an

d A

ceto

n

Injections

Lifetime - Retention Index

RI Diethylether

RI Aceton

RI Ethylacetate

15

Lifetime test PoraPLOT U PT

1350 injections Methanol / 10% water

0

5000

10000

15000

20000

25000

30000

35000

40000

0 500 1000

Pla

ten

um

ber

Eth

yla

ceta

te

Injections

Lifetime - Platenumber Ethylacetate

0.00

1.00

2.00

3.00

4.00

5.00

6.00

0 500 1000

k E

thyla

ceta

te

Injections

Lifetime - k Ethylacetate

16

Conclusion: No change in performance of the column after multiple injections

(Similar results for all porous polymer PLOT PT columns)

Lifetime Test Al2O3 – PT

50m x 0.32mm

Na2SO4 Before lifetime test After lifetime test

6509513 total st dev total st dev Difference

RI ethene 242.9 0.1 243.3 0.1 0.4

RI propene 357.4 0.0 357.8 0.0 0.4

RI propadiene 396.6 0.2 396.7 0.1 0.1

RI ethyne 400.0 0.0 400.0 0.0 0.0

RI t-2-butene 445.8 0.0 446.1 0.0 0.3

RI 1-butene 453.4 0.0 453.7 0.0 0.4

RI isobutene 461.8 0.0 462.2 0.0 0.5

RI c-2-butene 468.9 0.0 469.2 0.0 0.4

RI 1,3-butadiene 514.9 0.0 515.2 0.0 0.4

RI propyne 522.6 0.1 523.1 0.1 0.5

N 1,3-butadiene 150900 1001 148253 209 -2647

k 1,3 butadiene 2.4 0.0 2.5 0.0 0.0

N/m 1,3-butadiene 2744 18 2696 4 -48

u (cm/sec) 54.2 0.0 54.2 0.0 0.0

CFR 1.1 0.0 1.1 0.0 0.0

KCl Before lifetime test After lifetime test

6509506 total st dev total st dev Difference

RI ethene 234.8 0.1 234.9 0.0 0.1

RI propene 347.7 0.1 347.7 0.0 0.0

RI ethyne 362.1 0.0 361.7 0.1 -0.4

RI propadiene 385.2 0.0 385.0 0.0 -0.2

RI t-2-butene 439.2 0.0 439.1 0.0 -0.1

RI 1-butene 443.5 0.0 443.5 0.0 0.0

RI isobutene 450.6 0.0 450.6 0.0 0.0

RI c-2-butene 458.7 0.0 458.7 0.0 0.0

RI propyne 485.9 0.0 485.4 0.1 -0.4

RI 1,3-butadiene 499.3 0.0 499.3 0.0 0.0

N 1,3-butadiene 153264 836 155972 1105 2707

k 1,3 butadiene 1.5 0.0 1.5 0.0 0.0

N/m 1,3-butadiene 2787 15 2836 20 49

u (cm/sec) 51.8 0.0 51.8 0.0 0.0

CFR 1.0 0.0 1.0 0.0 0.0

Temperature program: 40°C + 10°C/min --> 200°C (40 min.)

Carrier gas N2, 50 kPa. FID

In 3 weeks 450 runs, 300 hours at the maximum T of 200°C.

Please note: No PDMS degradation at 200°C!

17

Lifetime Test Molsieve 5A

30m x 0.53 mm 50µm Molsieve 5A PT

Before lifetime test After lifetime test

9278538 Average StDev Average StDev Difference

Asym Carbonmonoxide 1.49 0.00 1.55 0.04 0.05

N methane 32177 5 31037 8 -1140

K methane 2.35 0.00 2.35 0.00 0.00

Res He/Ne 1.10 0.00 1.09 0.00 -0.02

Res Ar/O2 1.17 0.00 1.16 0.00 -0.01

CFR 1.04 0.00 1.05 0.00 0.01

Before lifetime test After lifetime test

9257038 Average StDev Average StDev Difference

Asym Carbonmonoxide 1.52 0.02 1.57 0.11 0.05

N methane 36336 13 35603 472 -733

K methane 2.41 0.00 2.41 0.00 0.00

Res He/Ne 0.97 0.00 1.11 0.01 0.14

Res Ar/O2 1.23 0.01 1.22 0.01 -0.01

CFR 1.11 0.00 1.11 0.00 0.01

Temperature program: 40°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 204 hours at 200°C and

44 hours at the maximum temperature of 300°C.

18

Lifetime Test Conclusions

After prolonged exposure at high operating temperature

there is no significant change of the chromatographic

performances of the Molsieve 5A and Al2O3 columns.

The bleed of the particle traps (front end) has no negative

effect on the PLOT phases.

19

Ideal for Solvent Analysis by GCMS

Column: PoraBond Q PT, 25m×0.25mm,3um

(30m total length)

Carrier : Helium, 43cm/s @90 ℃

Oven: : 90 °C- 140 °C at 10°C/min

140 °C for 6min

140 °C - 200 °C at 5°C/min

200 °C for 10 min

Injection: Split, 250 ℃, split ratio1:160

Detector: MSD, 280 ℃ Transfer line, full Scan at

m/z 30-350

1. Methyl Alcohol

2. Acetaldehyde

3. Ethanol

4. Acetonitrile

5. Acetone

6. Methylene Chloride

7. Isopropyl Alcohol

8. 2-Propanamine

9. Ethyl Formate

10. 1-Propanol

11. Ethyl ether

12. t-Butyl alcohol

13. 1,2-Ethanediol

14. Trichloromethane

15. 2-Butanone (MEK)

16. Ethyl Acetate

17. sec-Butyl alcohol

18. MTBE

19. 2-chlorobutane

20. 1-Butanol

21. Benzene

22. 1,1,1-Trichloroethane

23. 1-chlorobutane

24. Carbon Tetrachloride

25. Hexane

26. 1,4-Dioxane

27. Pyridine

28. Dimethyl Formamide (DMF)

29. Isoamyl Alcohol

30. Dimethyl Sulfoxide (DMSO)

31. Toluene

32. Heptane

33. Paraldehyde

34. Chlorobenzene

35. Ethylbenzene

36. m-Xylene

37. p-Xylene

38. o-xylene 6

6

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00 22.00 24.00 26.00

4.80 5.00 5.20 5.40 5.60 5.80 6.00 6.20 6.40 6.60

5

7 9

10

11

2

1

3

4

5

7

8

9

10

11

12

13

14,15

16 17

18

20

21

23,24

22 25

26

27

28

29

30

31 32

19

33

34

35

36

37

38

8

20

Excellent Peak Shape for Alcohols by GCMS

1. Methyl Alcohol

2. Acetaldehyde

3. Ethanol

4. Acetonitrile

5. Acetone

6. Methylene Chloride

7. Isopropyl Alcohol

8. 2-Propanamine

9. Ethyl Formate

10. 1-Propanol

11. Ethyl ether

1.50 2.00 2.50 3.00 3.50 4.00 4.50 5.00 5.50 6.00 6.50

methanol

2

Ethanol

Acetonitrile

6

7

2-Propanamine

1

3

4

5

IPA

8

9

10

11

1-Propanol

Column: PoraBond Q PT, 25m×0.25mm,3um

(30 m total length)

Carrier : Helium, 43cm/s @90 ℃

Oven: : 90 °C- 140 °C at 10°C/min

140 °C for 6min

140 °C - 200 °C at 5°C/min

200 °C for 10 min

Injection: Split, 250 ℃, split ratio1:160

Detector: MSD, 280 ℃ Transfer line, full Scan at

m/z 30-350

21

Halocarbons by GCMS

Column: PoraPLOT Q PT, 25m×0.32mm,10um (P/N CP7551PT)

(30m total length)

Carrier : Helium, 42cm/s @55 ℃

Oven: : 55 °C for 5min

55 °C - 200 °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 45-185

Sample: 1uL

1. Fluoroform (Freon-23)

2. 1,1,1-trifluoroethane (Freon-143a)

3. Pentafluoroethane (Freon-125)

4. Bromotrifluoromethane (Freon-13b1)

5. 1,1,1,2-Tetrafluoroethane (Freon-134a)

6. 1,1-difluoroethane (Freon-152a)

7. Difluorochloromethane (Freon-22)

8. 1,1,2,2-tetrafluoroethane (Freon-134)

9. 1-chloro-1,1-difluoroethane (Freon-142)

10. Bromochlorodifluoromethane (Freon-12b1)

11. Ethyl Chloride (Freon-160)

12. Fluorodichloromethane (Freon-21)

13. Trichloromonofluoromethane (Freon-11)

14. 1,1-Dichloro-1-fluoroethane (Freon-141)

15. 2,2-dichloro-1,1,1-trifluoroethane (Freon-123)

16. 1,1,2-trichloro-1,2,2-trifluoroethane (Freon-113)

17. 1,2-dibromo-1,1,2,2-tetrafluoroethane (Freon-114b2)

18. Trichloromethane (Freon-20)

19. 1,2-dichloroethane

20. 1,1,1-trichloro-ethane

21. Trichloroethylene

22. 1,1,2-trichloroethane

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00

1 2

3

4

5

6

7

8

9 10

11

12

13

14

15

16

17

18 19

20

21

22

22

Coal to Chemical Process Gas Analysis

min 2 4 6 8 10 12 14

25 µV

10

20

30

40

50

60

70

80

90

min 2 4 6 8 10 12 14

25 µV

10

20

30

40

50

60

70

80

90

HP-PLOT Q PT

30m×0.53mm,40um

(35m total length)

HP-PLOT Q

30m×0.53mm,40um

Carrier : H2, 36cm/s @32 ℃

Oven: : 32 °C for 5 min

32 °C - 180 °C at 15°C/min

Injection: 170 ℃ , split ratio 5:1

Detector: TCD, 250 ℃

Sample: 250uL

1

2 3

4 5 6 7

8 9

10

11 12 13

1

2 3

4 5

6 7

8 9

10

11 13

12

1. Carbon monoxide

2. Methane

3. Carbon dioxide

4. Ethylene

5. Ethane

6. Hydrogen sulfide

7. Water

8. Propylene

9. Propane

10. Dimethyl ether

11. Methanol

12. 1-Butene

13. Butane

23

Coal to Chemical Process Gas Analysis Identify compounds by MSD

CO

CH4

CO2

Ethylene

Ethane

H2S H2O

Propylene

Propane

DME

MeOH

1-Butene

Butane

Column: HP-PLOT Q PT, 30m×0.32mm,20um (P/N 19091P-Q04PT)

(35m total length)

Carrier : Helium, 1mL/min

Oven: : 32 °C for 3 min

32 °C - 180 °C at 15°C/min

Injection: 170 ℃ , split 5:1

Detector: MSD, 280 ℃ Transfer line, full Scan at m/z 10-100

Sample: 250uL

1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00

24

Excellent Peak Shape of Hydrogen Sulfide on

HP-PLOT U PT Column

min 2 4 6 8 10 12 14 16

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

1

2 3

4

5 6

7,8

9

10 11,12

1

2

3

4 5

6

7,8

9

10

11,12

1. Carbon monoxide

2. Methane

3. Carbon dioxide

4. Ethylene

5. Ethane

6. Hydrogen sulfide

H2O

HP-PLOT U PT, 30m×0.53mm,20um

(35m total length)

Carrier : H2, 40cm/s @32 ℃

Oven: : 32 °C for 5 min,32 °C - 70 °C at 30°C/min

70 °C for 5 min,70 °C - 140 °C at 10°C/min

Injection: 170 ℃ , split ratio 5:1

Detector: TCD, 250 ℃

Sample: 250uL

HP-PLOT U PT, 30m×0.32mm,10um

(35m total length)

Carrier : H2, 35cm/s @32 ℃

Oven: : 32 °C for 5 min,32 °C - 70 °C at 30°C/min

70 °C for 5 min,70 °C - 140 °C at 10°C/min

Injection: 170 ℃ , split ratio 5:1

Detector: MSD, 280 ℃ Transfer line,

full Scan at m/z 10-100

Sample: 250uL

7. Propylene

8. Propane

9. Dimethyl ether

10. Methanol

11. 1-Butene

12. Butane

25

No spikes at Fixed Gases Analysis

on CP-Molsieve 5Å PLOT PT column

26

CP-Molsieve 5Å showing spikes when particle traps are removed (Red trace).

No spikes with manufacturer integrated particle trap (Blue Trace).

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

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 Na2SO4

•NEW! Molsieve – CP-Molsieve 5A

Custom PLOT PT columns are

available for these phases

27

Phase type Part number Description DimensionsCP7348PT 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

CP7354PT 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

CP7554PT PoraPLOT Q PT 25m x 0.53mm x 20µm

CP7557PT PoraPLOT Q-HT PT 25m x 0.32mm x 10µm

115-3432PT GS-Q PT 30m x 0.53mm

19091P-QO3PT HP-PLOT Q PT 15m x 0.32mm x 20µm

19091P-QO4PT HP-PLOT Q PT 30m x 0.32mm x 20µm

19095P-QO3PT HP-PLOT Q PT 15m x 0.53mm x 40µm

19095P-QO4PT HP-PLOT Q PT 30m x 0.53mm x 40µm

CP7584PT PoraPLOT U PT 25m x 0.53mm x 20µm

19095P-UO4PT HP-PLOT U PT 30m x 0.53mm x 20µm

CP7515PT CP-Al2O3/KCl PT 50m x 0.32mm x 5µm

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

115-3352PT GS-Alumina/KCl PT 50m x 0.53mm

CP7565PT CP-Al2O3/Na2SO4 PT 50m x 0.32mm x 5µm

CP7568PT CP-Al2O3/Na2SO4 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

115-3532PT GS-Alumina PT 30m x 0.53mm

115-3552PT GS-Alumina PT 50m x 0.53mm

19095P-M25PT HP-PLOT Al2O3 M PT 50m x 0.53mm x 15µm

CP7534PT CP-Molsieve 5A PT 30m x 0.32mm x 10µm

CP7536PT 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

Molsieve

Al2O3 Na2SO4

deactivated

Al2O3 with

proprietary

deactivation

PLOT Q

PLOT U

Al2O3 KCl

deactivated

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

Now Let’s Switch Gears…

New DB-Sulfur SCD

for GC-SCD Analysis of

Sulfur Compounds

29

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

Challenges for Sulfur Analysis

Low levels often require maximum sensitivity

Matrix interference from the hydrocarbons present

Highly reactive and polar molecules

31

Detectors for Sulfur Analysis

Why not use an FID or MSD?

32

Detector GC-FPD GC-PFPD GC-SCD

Supplier Agilent OI Agilent

MDL Sulfur 3.6 pg/sec 1 pg/sec <0.5 pg/sec

Selectivity

Dynamic

Range 105

Quenching yes yes no

Equimolar

response

No No yes

Packed Col

Compatible yes No,

< 1ml/min yes

Other

Elements

P, Sn P N

Cost $ $$ $$$

103 103

106 106 107

Sulfur Detection

33

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 Description

ASTM D6228 Volatile sulfur in C1, C2, C3 and C4 monomers and LPG

ASTM D6628 Volatile Sulfur in NGA, fuel gas

ASTM D5504 Sulfur in gas fuels by SCD

ASTM D5623 Sulfur in light petroleum liquids by SCD

34

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: G6602-67000 $356 USD

• Dual plasma burner kit: G6602-60037 $459 USD.

Plus the self repair time of 4 hours and several days to stabilize.

35

SCD Ceramic Combustion Tubes & Burner

36

What is required of GC column for Sulfur Analysis?

Response

Retention &

Selectivity

Loadability/Capacity

Linearity of response from ppm – ppb

100% sulfur recovery

Minimal detector quenching

Low detection limits

Large injection volumes

Low detection limits

Robust/Low Bleed

Stable detector response

Low SCD maintenance

37

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 C24

Optimized for the lowest possible contribution to SCD

reaction tube fouling.

38

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

G3903-63001 DB-Sulfur SCD 60m, 0.32mm, 4.2um 250°/270°C

G3903-63002 DB-Sulfur SCD 40m, 0.32mm, 0.75um 270°/290°C

G3903-63003 DB-Sulfur SCD 70m, 0.53mm, 4.3um 250°/270°C

G3903-63004 DB-Sulfur SCD 40m, 0.32mm, 3um 250°/270°C

39

DB-Sulfur SCD: sulfur standards in Toluene

Good resolution of H2S and COS at room temperature

1 Hydrogen sulfide

2 Carbonyl sulfide

3 Methanethiol

4 Ethanethiol

5 Dimethyl sulfide

6 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

14 1-Butanethiol

15 Methyl disulfide

16 2-Methylthiophene

17 3-Methylthiophene

18 Diethyl disulfide

19 5-Methylbenzothiophene

20 3-Methylbenzo(b)thiophene

21 Diphenyl sulfide (Int Std)

min 5 10 15 20 25 30

1

2

3

4 5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

Thiophene and 2-Methyl-1-propanethiol can be baseline separated

Column: Agilent J&W DB-Sulfur SCD, 60 m x 0.32 mm, 4.2 μm (p/n G3903-63001)

40

Typical chromatogram of Sulfur compounds in

Light Petroleum Liquids by ASTM D5623

0.0 4.0 8.0 12.0 16.0 20.0 24.0 28.0

Time (minutes)

12

34

5 67

8

9

1011

12

13

14

15

17

1. Ethanethiol

2. Dimethyl sulfide

3. Carbon disulfide

4. 2-Propanethiol

5. 2-Methyl-2-propanethiol

6. 1-Propanethiol

7. Ethylmethyl sulfide

8. Thiophene/ 2-Methyl-1-propanethiol

9. Dimethyl Disulfide

10. 2-Methylthiophene

11. 3-Methylthiophene

12. C2-thiophenes

13. Diethyl disulfide

14. Benzothiophene

15. C1-benzothiophenes

17. Diphenyl sulfide (Int Std)

16

16. C2-benzothiophenes

Sulfur Compounds in Gasoline

… the industry standard

41

DB-Sulfur SCD: Real Samples

min 5 10 15 20 25 30

15 µV

0

5000

10000

15000

20000

25000

min 5 10 15 20 25 30

15 µV

0

5000

10000

15000

20000

25000

min 5 10 15 20 25 30

15 µV

0

5000

10000

15000

20000

25000

pyrolysis gasoline

naphtha

Sulfur standards

Int Std

Int Std

Int Std

1

2

3 4

5

6

7 8

9 10 11

12

13 14

15

16

1

3

17 18

19

20

17 16

6

11

11

4

7

8 10

9

14 13

15

16

42

DB-Sulfur SCD: Sulfur Sensitivity

min 5 10 15 20 25 30

15 µV

0

200

400

600

800

1000

1200

Peak No. 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

S/N 3.0 3.1 2.7 4.4 2.8 2.1 2.9 3.3 3.5 3.0 3.8 3.5 6.3 3.2 4.4 6.3 3.1 2.9

3 4 5

6

7 8 9 10 11

12 13

14

15

16 17

18

19 20

Int Std Sample: 400ppb sulfur standard

Inj. Vol: 1uL

Split ratio: 160:1

Approximately 2.5pg for each compound on column

(calculated)

Low bleeding at 250 °C

43

Repeatability

No Compound

10 ppm 1ppm 0.1ppm

RSD% RSD% RSD%

1 Methyl mercaptan 2.94 4.46 5.12

2 Ethyl mercaptan 2.53 3.00 4.38

3 Methyl sulfide 2.53 2.79 4.79

4 Carbon disulfide 2.13 3.29 5.43

5 2-Propanethiol 2.49 3.98 4.85

6 2-Methyl-2-propanethiol 2.89 4.47 4.41

7 1-Propanethiol 2.81 3.88 4.91

8 Ethyl methyl sulfide 2.34 4.17 5.24

9 Thiophene 2.24 3.06 3.49

10 2-Methyl-1-propanethiol 1.87 2.31 5.86

11 Diethyl sulfide 2.00 2.97 4.80

12 1-Butanethiol 2.46 3.36 6.47

13 Methyl disulfide 3.62 4.15 4.23

14 2-Methylthiophene 3.59 4.62 5.95

15 3-Methylthiophene 2.85 3.90 4.90

16 Diethyl disulfide 2.74 3.16 6.34

17 3-Methylbenzothiophene 2.48 4.87 5.29

18 5-Methylbenzo(b)thiophene 2.42 4.25 7.37

No Compound 10 ppm 1ppm 0.1ppm

RSD% RSD% RSD%

1 Methyl mercaptan 2.94 4.46 5.12

2 Ethyl mercaptan 2.53 3.00 4.38

3 Methyl sulfide 2.53 2.79 4.79

4 Carbon disulfide 2.13 3.29 5.43

5 2-Propanethiol 2.49 3.98 4.85

6 2-Methyl-2-propanethiol 2.89 4.47 4.41

7 1-Propanethiol 2.81 3.88 4.91

8 Ethyl methyl sulfide 2.34 4.17 5.24

9 Thiophene 2.24 3.06 3.49

10 2-Methyl-1-propanethiol 1.87 2.31 5.86

11 Diethyl sulfide 2.00 2.97 4.80

12 1-Butanethiol 2.46 3.36 6.47

13 Methyl disulfide 3.62 4.15 4.23

14 2-Methylthiophene 3.59 4.62 5.95

15 3-Methylthiophene 2.85 3.90 4.90

16 Diethyl disulfide 2.74 3.16 6.34

17 3-Methylbenzothiophene 2.48 4.87 5.29

18 5-Methylbenzo(b)thiophene 2.42 4.25 7.37

N=6

44

DB-Sulfur SCD: Sulfur Sensitivity

min 0 1 2 3 4 5

15 µV

200

400

600

800

1000

1200

AIB1 B, Back Signal (R-1\L-2PPM000021.D) AIB1 B, Back Signal (R-1\L-2PPM000022.D) AIB1 B, Back Signal (R-1\L-2PPM000023.D) AIB1 B, Back Signal (R-1\L-2PPM000024.D) AIB1 B, Back Signal (R-1\L-2PPM000025.D)

H2S

COS

Compound S/N RSD%

(N=5)

H2S 9.5 3.14

COS 5.3 3.25

2ppm

45

Linearity

Compound Concentration

Range

Linearity

(R2)

Hydrogen sulfide 2ppm-25ppm 0.9976

Carbonyl sulfide 2ppm-25ppm 0.9990

Methanethiol 0.1ppm-10ppm 0.9987

Ethanethiol 0.1ppm-50ppm 0.9998

Dimethyl sulfide 0.1ppm-10ppm 0.9991

Carbon disulfide 0.1ppm-10ppm 0.9990

2-Propanethiol 0.1ppm-50ppm 0.9999

2-Methyl-2-

propanethio

0.1ppm-10ppm 0.9989

1-Propanethiol 0.1ppm-10ppm 0.9990

Ethyl methyl sulfide 0.1ppm-50ppm 0.9998

Compound Concentration

Range

Linearity

(R2)

Thiophene 0.1ppm-50ppm 0.9997

2-Methyl-1-propanethiol 0.1ppm-10ppm 0.9991

Diethyl sulfide 0.1ppm-10ppm 0.9992

1-Butanethiol 0.1ppm-10ppm 0.9990

Methyl disulfide 0.1ppm-10ppm 0.9987

2-Methylthiophene 0.1ppm-50ppm 0.9991

3-Methylthiophene 0.1ppm-50ppm 0.9996

Diethyl disulfide 0.1ppm-10ppm 0.9990

5-Methylbenzothiophene

0.1ppm-10ppm 0.9984

3-Methylbenzothiophene 0.1ppm-50ppm 0.9988

46

Configuration to test SCD Quenching Issue

Inlet

Pulsed SCD

FID

4:5

Thick film PDMS type Column

325 torr

710 torr

CFT splitter

1:5

47

Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada

Traditional PDMS column– SCD Ceramic Reaction

Tube Deactivation

11/1/2013 48

500000

550000

600000

650000

700000

750000

800000

850000

900000

950000

1000000

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

Are

a C

ou

nts

Day 1 Day 2

Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada

Traditional PDMS column- Coking (desensitization)

of Reactor Tubes

11/1/2013 49

Overlay of before (green) and after 2 x 2 uL neat toluene Injection (red)

1. Hydrogen Sulfide

2. Carbonyl Sulfide

3. Methyl Mercaptan

4. Ethyl Mercaptan

1 2 3

FID: No response changes

4 3

4

SCD:

10% drop in

sensitivity

Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada

New DB-Sulfur SCD column

Last Three Runs of the day (n=20, 100 ppmv std)

250C Cool down

1. H2S

2. COS

3. CH3SH

4. C2H5SH

1

2 3

4

FID

SCD

40C 3

4

50

Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada

Sulfides and Thiophenes (n=5)

1. Dimethyl sulfide (100 ppm)

2. Ethyl methyl sulfide (50 ppm)

3. Thiophene (100 ppm)

4. Diethyl sulfide (75 ppm)

5. Dimethyl disulfide (25 ppm)

6. 2-methyl thiophene (75 ppm)

7. 3-methyl thiophene (100 ppm)

8. Diethyldisulfide (20 ppm)

9. Benzothiophene (75 ppm)

10. 3-methylbenzothiophene (100 ppm)

52

Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada

Chromatograms of 50 ppmv each of sulfides and mercaptans and

500 ppmv each of hydrocarbons in nitrogen

1. Hydrogen sulfide

2. Carbonyl sulfide

3. Methyl mercaptan

4. Ethyl mercaptan

1. Methane

2. Ethane

3. Propane

4. Butane

5. Pentane

6. Hexane

SCD

FID

1 2

3 4

1 2

3 4

5

6

53

Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada

1. Ethyl mercaptan (100 ppm)

2. Carbonyl sulfide (20 ppm)

3. Isopropyl mercaptan (100 ppm)

4. Tert-butyl mercaptan (50 ppm)

5. N-propyl mercaptan (100 ppm)

6. Sec-butyl mercaptan (50 ppm)

7. Isobutyl mercaptan (100 ppm)

8. N-Butyl mercaptan (50 ppm)

1. Isooctane (mixed solvent)

2. Toluene (mixed solvent)

Chromatogram of carbon disulfide and alkyl mercaptans

SCD

FID

1 3 5

6

7

8

4 2

2 1

54

Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada

Chromatogram of sulfides, disulfides, thiophene, alkyl thiophenes,

benzothiophene, and alkyl benzothiophenes

1. Dimethyl sulfide (100 ppm)

2. Ethyl methyl sulfide (50 ppm)

3. Thiophene (100 ppm)

4. Diethyl sulfide (75 ppm)

5. Dimethyl disulfide (25 ppm)

6. 2-methyl thiophene (75 ppm)

7. 3-methyl thiophene (100 ppm)

8. Diethyldisulfide (20 ppm)

9. Benzothiophene (75 ppm)

10. 3-methylbenzothiophene (100 ppm)

1. Isooctane (solvent)

2. Toluene (solvent)

SCD

FID

1

3

4 5

6

7

8

9

10

2

1 2

55

Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada

Chromatogram volatile sulfur odorants in

commercially available natural gas

1. Hydrogen sulfide

2. Methyl mercaptan

3. Tert-butyl mercaptan

4. Methyl ethyl sulfide

SCD

FID 1. Methane

2. Propane

3. Iso-butane

4. N-Butane

5. Iso-pentane

6. N-Pentane

7. Hexanes

8. Heptanes

1

3

1

3 4

5 6 7

8

2

4

2

56

Data courtesy of Jim Luong, Ronda Gras, Myron Hawryluk of Dow Chemical Canada

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 6 months, no SCD maintenance!

57

Application Notes and Literature:

ASTM D5623 and ASTM D5504

Brochure number 5991-2977EN

58

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