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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
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