A dedicated GC/MS analyzer was developed to address the increasing need for more sensitive catalyst poisoner analysis. The system combines the separation power and robustness of a classic backflush configuration with Lowox column with the selectivity and sensitivity of mass spectrometry.

1. Innovations in IS X

Petrochemistry
Ultratrace Oygenate Analysis
www.is-x.be

2. Introduction IS X

Oxygenates are known for the poisoning of catalysts.
They interfere or even entirely halt processes, like
polymerisation, which results in an overall decrease in
polymer quality.
Detailed information on oxygenates at trace levels is
of utmost importance to the petrochemical industry.

3. Observation IS X

New generation catalysts are more sensitive to
poisoning by oxygenates.
Standard technology is unable to address the
increasing need for more sensitive analyses.

4. Current state-of-the-art IS X

Gas chromatography, GC/FID.
Dedicated analyzer equipped with two capillary
columns. First dimension consists of an apolar column,
second dimension column is polar.
Polar column is protected by backflush
Polar column is a ‘Lowox’ column.

5. Lowox column IS X

Multi-layer PLOT column with a specific selectivity for
polar compounds.
Temperature stable up to 350°C with virtually no
bleed.
The use of an apolar precolumn extends the
application range from C1/C4 hydrocarbons to C12
hydrocarbons.

6. Target compounds IS X

A broad range of analytes, such as,
 Ethers, DME, MTBE, ETBE, etc
 Alcohols, MeOH, EtOH, i-PrOH, etc
 Ketones, acetone, MEK, etc
But also,
Aromatics, halogenated compounds, sulfurs, etc

7. Typical set-up IS X

BF
Rxi-1,
15 m x 530 µm
HC/oxygenates
Lowox,
10 m x 530 µm Oxygenates
FID

8. Remarkable trend IS X

MS state-of-the-art has changed dramatically over
the last couple of years.
Latest generation of instruments are bench top size,
easy to tune & calibrate and require little
maintenance (vacuum lock technology).

9. Innovation IS X

Combining our knowledge on column technology
with our expertise to built custom analyzers.
Fully exploiting the power of the new Thermo ISQ
single quadrupole mass spectrometer.

10. Strengths of MS IS X

New benchmarks for,
 Identification of unknowns
 Trace quantification of target analytes
 Superior accuracy with isotope dilution

11. Our approach IS X

Standard detector switch possible.
Lowox column is not available in MS friendly (narrow
bore) dimensions. It is mandatory to introduce an
adequate restriction in order to avoid the MS
vacuum from protruding the system.
Backflush pressure settings need careful optimization.

12. Set-up for MS IS X

BF
Rxi-1,
15 m x 530 µm HC/oxygenates
Lowox,
10 m x 530 µm
Oxygenates
Restriction,
5 m x 250 µm
ISQ

13. Instrument details IS X

Thermo Trace GC
Uitgerust met GSV, LSV, S/SL & vaporizer.
Thermo ISQ
Fast scanning single quadrupool MS.

14. Experiments IS X

Following tests were carried out,
 10 ppm oxygenates, FID
 10 ppm oxygenates, ISQ (scan mode)
 10 ppm oxygenates, ISQ (SIM mode)
 10 ppb oxygenates, ISQ (SIM mode)
 Isobutylene sample
 Naphtha sample

15. GC conditions IS X

Oven : 50°C (5 min) → 240°C (10 min) @ 5°C/min
S/SL : 200°C (splitless mode)
Carrier : He @ 50 kPa (constant pressure mode)
FID : 200°C
MS : full scan/SIM
Oven kept at 200°C when idle. Backflush activated in
order to avoid accumulation of siloxane bleed.

16. FID analysis IS X

C:Xcalibur...Backflushlowox10_006 5/12/2011 2:21:52 PM
lowox 1ul zonder backflush
RT: 9.33 - 25.61
NL:
3.60E4
48000 FID_Right
Analog
46000 lowox10_00
6
44000
42000
40000
38000
21.27
36000
34000
32000 12.93 14.09 14.29
12.65 21.81
30000 18.17 19.97 20.49
17.63
28000 11.48
Counts
15.66
26000 13.69 14.95 16.68 18.39
24000
22000
11.82
20000 16.31
19.65 24.36 24.56 25.02
16.79
19.34 22.63 22.99
18000
10.84
16000
9.71 10.28
14000
12000
10000
8000
6000
4000
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
Time (min)
10 ppm standard

17. MS in scan mode IS X

C:Xcalibur...DeansLowox10ppm_014 7/6/2011 11:21:50 AM
EV4 ON --> Lowox op FID EV OFF op 1.4min. Nieuwe fleske
RT: 9.86 - 35.58
NL:
7.58E8
105
TIC MS
11.85 Lowox10pp
100
m_014
95
90
85
11.94
80
75
70
65
Relative Abundance
21.72 33.71
60 21.34
19.45 34.66
55
50 18.97
45
27.46 31.45
40 28.40
35
12.23 16.91 32.37
30 23.98
22.71
25
25.72
28.68
20
20.65
15
17.46 25.00 26.01
10 31.06
30.63 33.56
16.47
5 9.94 12.51 14.94 15.07 18.30
10 12 14 16 18 20 22 24 26 28 30 32 34
Time (min)
10 ppm standard

18. Influence of ion extraction IS X

C:Xcalibur...DeansLowox10ppm_014 7/6/2011 11:21:50 AM
EV4 ON --> Lowox op FID EV OFF op 1.4min. Nieuwe fleske
RT: 24.30 - 27.59 SM: 5B
NL:
3.15E8
TIC MS
Lowox10pp
m_014
120 RT: 27.47
AA: 1448900376
SN: 421RMS
100
Relative Abundance
80
RT: 25.72
MA: 861248696
60
SN: 208RMS
40 RT: 25.00 RT: 25.49 RT: 26.02
RT: 26.93
AA: 180287915 AA: 174796812 AA: 190896618
AA: 130996047
SN: 53RMS SN: 48RMS SN: 58RMS
20 SN: 40RMS
24.34 24.50 24.72 24.85 25.17 26.12 26.28 26.51 26.61 26.84 27.20
0
NL:
1.13E8
m/z=
42.50-
43.50+
120 RT: 25.72 57.50-
MA: 762981197 58.50 MS
SN: 6013RMS Lowox10pp
100
m_014
80
RT: 27.47
AA: 317826969
60 SN: 3097RMS
40
RT: 25.49 RT: 26.01 RT: 26.93
20 RT: 24.36 AA: 22502668 RT: 26.25 RT: 26.46
AA: 828757 AA: 18239560 AA: 971450 AA: 873581 AA: 19025095
SN: 241RMS SN: 198RMS
SN: 10RMS 24.71 24.93 25.14 25.29 SN: 180RMS SN: 14RMS SN: 11RMS 27.08 27.34
0
24.4 24.6 24.8 25.0 25.2 25.4 25.6 25.8 26.0 26.2 26.4 26.6 26.8 27.0 27.2 27.4
Time (min)
Acetone in scan mode

19. MS in SIM mode IS X 
C:Xcalibur...DeansLowox10ppm_024 8/26/2011 12:13:39 PM
EV4 OFF --> alles op MS SIM
RT: 27.89 - 28.97 SM: 5B
RT: 28.35 NL: 1.35E8
AA: 691361100 TIC F: {0,0} + c EI SIM
SN: 28640 ms [28.50-29.50,
100
56.50-57.50,
90 57.50-58.50] MS ICIS
Lowox10ppm_024
80
Relative Abundance
70
60
50
40
30
20
RT: 28.12 RT: 28.70
10 AA: 493968 AA: 2025302
SN: 21 SN: 110
0
RT: 28.35 NL: 9.71E7
MA: 485789577 m/z=
SN: 186 28.50-29.50+
100
56.50-57.50+
90 57.50-58.50 MS
lowox10ppm_023
80
70
60
50
40
30
20
RT: 27.94 RT: 28.10 RT: 28.23 RT: 28.67 RT: 28.79 RT: 28.85
10 AA: 271516 AA: 522135 AA: 124392 AA: 2515062 AA: 984212 AA: 38161
SN: 16 28.04 SN: 24 SN: 28 SN: 115 SN: 58 SN: 10 28.94
0
27.9 28.0 28.1 28.2 28.3 28.4 28.5 28.6 28.7 28.8 28.9
Time (min)
Propanol in SIM and scan mode

20. Overview of results IS X

Name FID, S/N MS (FS), S/N MS (EIC), S/N MS (SIM), S/N
Diethyl ether 421 494 1096 34369
Acetaldehyde 440 74 1805 4377
ETBE 755 489 7462 49959
MTBE 695 411 2199 36818
Diisopropylether 795 528 5233 55688
Propanal 323 107 2083 8595
t-Amyl ether 520 592 2260 32977
Propyl ether 500 636 8395 34980
iso-Butanal 478 185 2405 18183
Butyraldehyde 323 242 1439 7182
Methanol 41 56 70 255

21. Continued… IS X

Name FID, S/N MS (FS), S/N MS (EIC), S/N MS (SIM), S/N
Acetone 247 190 4465 25127
Valeraldehyde 311 471 2604 54614
MEK 323 421 629 1385
Ethanol 414 105 497 1544
iso-Propanol 448 265 1320 2538
Propanol 420 228 666 2329
Allyl alcohol 515 178 564 6988
iso-Butanol 422 465 3424 19447
t-Butanol 408 373 858 20125
n-Butanol 290 203 546 7239

22. Average sensitivity gains IS X

Changing over from FID to MS in SIM mode results in a
substantial gain in sensitivity for all oxygenates.
Minimal sensitivity gain is a factor of 5 for MEK,
ethanol, isopropanol en propanol. Maximal gain
equals a factor of 200 for valeraldehyde.

23. Oxygenates at 10 ppb IS X

C:Xcalibur...DeansLowox10ppb_ITS_001 9/7/2011 9:24:05 AM
EV4 OFF --> alles op MS SIM
RT: 17.84 - 57.02
NL:
8.11E8
30 39.41 TIC MS
28 Acetaldehyde Lowox10pp
b_ITS_001
_002 9/7/2011 11:49:13 AM
26 25.38 NL: 1.83E7
TIC F: {0,0} + c EI
SIM ms
[28.50-29.50,
43.50-44.50] MS
24 Lowox10ppb_ITS_0
02
22
20 Methanol
Relative Abundance
18
16
25.88 25.98
14
36.33
32.99
22.0 22.5 23.0 12
23.5 24.0 24.5 25.0 25.5 26.0 26.5 27.0 27.5 32.69
Time (min)
10
46.50
8
6 DIPE 41.64
45.49
49.62
44.97
4 46.70
36.67
41.07 43.70
49.10 49.95 53.65 53.99
2 19.03 35.38 39.21 42.60
23.39
25.66 25.92 27.46 31.08 31.89
19.38
0
18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56
Time (min)

24. Repeatability IS X 
c:xcalibur...datasdeansspiab_006 8/25/2011 3:50:51 PM
EV4 OFF --> alles op MS SIM
RT: 24.27 - 27.44 SM: 5B
NL:
6.10E6
m/z=
28.50-29.50+
150 RT: 25.43
43.50-44.50
MA: 24271273 MS
100
SPIAB_002
50 24.34 24.49 24.60 24.81 24.93 25.01 25.26 25.34 25.54 25.81 25.87 26.14 26.22 26.34 26.53 26.68 26.76 26.92 27.09 27.20 27.33
0 NL:
4.92E6
m/z=
28.50-29.50+
150 RT: 25.59
43.50-44.50
MA: 22935403 MS spiab_003
100
50 24.46 24.58 24.77 24.85 25.03 25.27 25.46 25.80 25.97 26.24 26.33 26.55 26.61 26.70 26.95 27.09 27.19 27.29
0 NL:
4.45E6
Relative Abundance
m/z=
28.50-29.50+
150 RT: 25.56
43.50-44.50
MA: 20650477 MS spiab_004
100
50 24.38 24.60 24.69 24.84 24.92 25.05 25.28 25.46 25.67 25.95 26.20 26.41 26.51 26.65 26.85 27.00 27.18 27.30
0 NL:
5.05E6
m/z=
28.50-29.50+
150 RT: 25.56
43.50-44.50
MA: 21944573 MS spiab_005
100
50 24.45 24.61 24.70 24.88 25.10 25.21 25.29 25.65 25.92 26.10 26.22 26.46 26.53 26.72 26.81 26.95 27.08 27.23 27.43
0 NL:
4.54E6
m/z=
28.50-29.50+
150 RT: 25.51
43.50-44.50
MA: 21203332 MS spiab_006
100
50 24.49 24.63 24.78 24.84 25.07 25.23 25.31 25.66 25.87 26.10 26.27 26.41 26.52 26.60 26.73 26.96 27.20 27.34
0
24.4 24.6 24.8 25.0 25.2 25.4 25.6 25.8 26.0 26.2 26.4 26.6 26.8 27.0 27.2 27.4
Time (min)
Acetaldehyde

25. Continued… IS X 
c:xcalibur...datasdeansspiab_006 8/25/2011 3:50:51 PM
EV4 OFF --> alles op MS SIM
RT: 32.73 - 34.84 SM: 5B
NL:
1.61E6
m/z=
42.50-43.50+
150 RT: 33.93 57.50-58.50
MA: 9906744 MS
100
SPIAB_002
50
32.76 32.89 32.99 33.08 33.16 33.29 33.37 33.45 33.60 33.78 33.83 34.12 34.27 34.34 34.52 34.64 34.80
0 NL:
1.04E6
m/z=
42.50-43.50+
150 RT: 33.92 57.50-58.50
MA: 8671376 MS spiab_003
100
50 33.83 34.03 34.15
32.74 32.91 32.97 33.10 33.25 33.35 33.43 33.53 33.62 34.32 34.42 34.55 34.65 34.83
0 NL:
1.10E6
Relative Abundance
m/z=
42.50-43.50+
150 RT: 33.89 57.50-58.50
MA: 8517965 MS spiab_004
100
50 33.78 34.06 34.11 34.24
32.81 32.90 32.99 33.10 33.26 33.33 33.40 33.52 33.65 34.35 34.44 34.60 34.67 34.75
0 NL:
1.03E6
m/z=
42.50-43.50+
150 RT: 33.86 57.50-58.50
MA: 8452666 MS spiab_005
100
50 33.95
32.76 32.94 33.05 33.14 33.24 33.26 33.43 33.50 33.58 33.78 34.01 34.18 34.26 34.40 34.46 34.54 34.59 34.70 34.81
0 NL:
1.58E6
m/z=
42.50-43.50+
150 RT: 33.85 57.50-58.50
MA: 8791114 MS spiab_006
100
50
32.75 32.93 32.98 33.12 33.25 33.33 33.47 33.58 33.76 33.99 34.05 34.19 34.32 34.45 34.56 34.76 34.81
0
32.8 33.0 33.2 33.4 33.6 33.8 34.0 34.2 34.4 34.6 34.8
Time (min)
Acetone

26. Isobutylene feed IS X

C:Xcalibur...datasDeansSPIAB_007 8/26/2011 1:45:55 PM
EV4 OFF --> alles op MS SIM
RT: 0.78 - 57.02
NL:
1.38E8
44 TIC MS
2-Propanol
SPIAB_007
42
40
38
36 Methanol
34
33.05
32
30
Acetaldehyde 33.36
28
Relative Abundance
26
24
22
20
Dimethylether Ethanol
18
16
Aceton t-Butanol
14
12
10
8
25.45
6 36.72
4 38.92 41.83 47.25 47.87 49.81 51.92 56.21
36.54
28.51 32.34
2 24.71
18.69 20.17 23.14
0
5 10 15 20 25 30 35 40 45 50 55
Time (min)

27. Naphta feed in scan mode IS X

C:Xcalibur...DeansNaphta_ITS_002 9/7/2011 2:21:29 PM
EV4 OFF --> alles op MS FS
RT: 15.01 - 57.00
22.56 NL:
100 17.20 3.53E10
21.29
20.62
TIC MS
95 16.32 17.58
Naphta_ITS
_002
90
85
23.74
80
75
70
65
60 24.34 26.41
Relative Abundance
55
50 26.70
45 27.52
28.15
40
35 28.36
30
25
20 29.05
29.81
31.09
15
37.58 40.56 43.39 46.07
10 34.44
31.55
33.19 37.18 39.79 45.07
5 41.57
39.40
46.45 48.57 49.17 52.72 54.40 56.18
0
16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56
Time (min)

28. Naphta feed in SIM mode IS X 
C:Xcalibur...DeansNaphta_ITS_001 9/7/2011 12:55:07 PM
EV4 OFF --> alles op MS SIM
RT: 19.57 - 56.81
26.43 NL:
100 3.27E9
Methanol
TIC MS
95 Naphta_ITS
_001
90 C:Xcalibur...DeansNaphta_ITS_001 9/7/2011 12:55:07 PM
EV4 OFF --> alles op MS SIM
RT: 32.01 - 34.18
32.92 NL: 7.79E7
85 27.53
100
TIC F: {0,0} + c EI
SIM ms [28.50-29.50,
98 30.50-31.50,
31.50-32.50] MS
80 96 Naphta_ITS_001
94
75 92
90
26.07
70 88
Acetaldehyde
86
Relative Abundance
33.12
65 84
32.52 32.53
32.74
82 33.19
32.47
60 80
32.39
Relative Abundance
78
55 76
74
50 72
70
45 68
TAME
66
40 64
19.70 32.2 32.4 32.6 32.8 33.0 33.2 33.4 33.6 33.8 34.0
Time (min)
35
20.60 40.56
30 31.10 43.39
46.07
25 28.20
20 34.45
20.74
15 28.58
39.80
24.45 31.82 34.05
10 41.41 45.08
21.54 22.36 30.05
36.19 39.36
5 33.48
37.60 46.60 47.30 49.76
50.81 52.66 54.46 56.64
0
20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56
Time (min)

29. Concluding remarks IS X

We provide the first description and full validation of
oxygenate analysis by means of MS.
Our state-of-the-art TraceOx Analyzer permits
quantitative analysis of oxygenates, sulfurs and other
relevant components at the low ppb level with
superior robustness and accuracy.

30. Additional opportunities IS X

Other questions that might be addressed by means of
hyphenated MS solutions,
 Analysis of raw materials
 Dedicated customer support
 Address customer complaints
 Competitor intelligence

31. Contact details IS X

For more details on this study, please contact
Dr. Joeri Vercammen
j.vercammen@is-x.be
++32-(0)10/45.00.25
www.is-x.be