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.
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.
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)
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