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Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
Ultratrace oxygenate analysis by GC/MS
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Ultratrace oxygenate analysis by GC/MS

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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 …

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.

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  • 1. Innovations in IS X PetrochemistryUltratrace Oygenate Analysiswww.is-x.be
  • 2. Introduction IS X Oxygenates are known for the poisoning of catalysts.They interfere or even entirely halt processes, likepolymerisation, which results in an overall decrease inpolymer quality.Detailed information on oxygenates at trace levels isof utmost importance to the petrochemical industry.
  • 3. Observation IS X New generation catalysts are more sensitive topoisoning by oxygenates.Standard technology is unable to address theincreasing need for more sensitive analyses.
  • 4. Current state-of-the-art IS X Gas chromatography, GC/FID.Dedicated analyzer equipped with two capillarycolumns. First dimension consists of an apolar column,second dimension column is polar.Polar column is protected by backflushPolar column is a ‘Lowox’ column.
  • 5. Lowox column IS X Multi-layer PLOT column with a specific selectivity forpolar compounds.Temperature stable up to 350°C with virtually nobleed.The use of an apolar precolumn extends theapplication range from C1/C4 hydrocarbons to C12hydrocarbons.
  • 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, etcBut 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 overthe last couple of years.Latest generation of instruments are bench top size,easy to tune & calibrate and require littlemaintenance (vacuum lock technology).
  • 9. Innovation IS X Combining our knowledge on column technologywith our expertise to built custom analyzers.Fully exploiting the power of the new Thermo ISQsingle 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 (narrowbore) dimensions. It is mandatory to introduce anadequate restriction in order to avoid the MSvacuum 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 GCUitgerust met GSV, LSV, S/SL & vaporizer.Thermo ISQFast 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/minS/SL : 200°C (splitless mode)Carrier : He @ 50 kPa (constant pressure mode)FID : 200°CMS : full scan/SIMOven kept at 200°C when idle. Backflush activated inorder to avoid accumulation of siloxane bleed.
  • 16. FID analysis IS X C:Xcalibur...Backflushlowox10_006 5/12/2011 2:21:52 PMlowox 1ul zonder backflushRT: 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 AMEV4 ON --> Lowox op FID EV OFF op 1.4min. Nieuwe fleskeRT: 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 AMEV4 ON --> Lowox op FID EV OFF op 1.4min. Nieuwe fleskeRT: 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 PMEV4 OFF --> alles op MS SIMRT: 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/NDiethyl ether 421 494  1096   34369Acetaldehyde 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 7182Methanol 41 56  70  255 
  • 21. Continued… IS X Name FID, S/N MS (FS), S/N MS (EIC), S/N MS (SIM), S/NAcetone 247 190   4465  25127Valeraldehyde 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 asubstantial gain in sensitivity for all oxygenates.Minimal sensitivity gain is a factor of 5 for MEK,ethanol, isopropanol en propanol. Maximal gainequals 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 PMEV4 OFF --> alles op MS SIMRT: 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 PMEV4 OFF --> alles op MS SIMRT: 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 PMEV4 OFF --> alles op MS SIMRT: 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 28Relative 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 PMEV4 OFF --> alles op MS FSRT: 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 PMEV4 OFF --> alles op MS SIMRT: 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 ofoxygenate analysis by means of MS.Our state-of-the-art TraceOx Analyzer permitsquantitative analysis of oxygenates, sulfurs and otherrelevant components at the low ppb level withsuperior robustness and accuracy.
  • 30. Additional opportunities IS X Other questions that might be addressed by means ofhyphenated 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 contactDr. Joeri Vercammenj.vercammen@is-x.be++32-(0)10/45.00.25www.is-x.be

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