Ultratrace oxygenate analysis by GC/MS

Innovations in PetrochemistryUltratrace Oygenate Analysis

www.is-x.be

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Introduction

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.

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Observation

New generation catalysts are more sensitive to poisoning by oxygenates.

Standard technology is unable to address the increasing need for more sensitive analyses.

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Current state-of-the-art ISX

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 backflushPolar column is a ‘Lowox’ column.

Lowox column ISX

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.

Target compounds ISX

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

HC/oxygenates

Oxygenates

FID

Rxi-1, 15 m x 530 µm

Lowox, 10 m x 530 µm

BF

Typical set-up ISX

Remarkable trend ISX

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).

Innovation

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.

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Strengths of MS

New benchmarks for,

Identification of unknowns Trace quantification of target analytes Superior accuracy with isotope dilution

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Our approach ISX

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.

Set-up for MS ISX

ISQ

Rxi-1, 15 m x 530 µm

Lowox, 10 m x 530 µm

BF

Restriction, 5 m x 250 µm

HC/oxygenates

Oxygenates

Thermo Trace GC Uitgerust met GSV, LSV, S/SL & vaporizer.

Thermo ISQ Fast scanning single quadrupool MS.

Instrument details ISX

Experiments ISX

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

GC conditions ISX

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/SIM

Oven kept at 200°C when idle. Backflush activated in order to avoid accumulation of siloxane bleed.

FID analysis ISX

10 ppm standard

C:\Xcalibur\...\Backflush\lowox10_006 5/12/2011 2:21:52 PMlowox 1ul zonder backflush

RT: 9.33 - 25.61

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25Time (min)

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21.27

14.0912.93 14.2921.8112.65

20.4919.9718.1717.63

11.4815.66

16.6814.9513.69 18.39

11.8216.31

24.5624.36 25.0219.65 22.9916.79 22.6319.34

10.84

9.71 10.28

NL:3.60E4FID_Right Analog lowox10_006

MS in scan mode ISXC:\Xcalibur\...\Deans\Lowox10ppm_014 7/6/2011 11:21:50 AMEV4 ON --> Lowox op FID EV OFF op 1.4min. Nieuwe fleske

RT: 9.86 - 35.58

10 12 14 16 18 20 22 24 26 28 30 32 34Time (min)

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11.85

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21.72 33.71

21.3434.6619.45

18.97

27.46 31.4528.40

16.91 32.3712.2323.98

22.71

25.7228.68

20.65

17.46 26.0125.00 31.0633.5630.63

16.4715.07 18.3012.519.94 14.94

NL:7.58E8TIC MS Lowox10ppm_014

10 ppm standard

C:\Xcalibur\...\Deans\Lowox10ppm_014 7/6/2011 11:21:50 AMEV4 ON --> Lowox op FID EV OFF op 1.4min. Nieuwe fleske

RT: 24.30 - 27.59 SM: 5B

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 27.4Time (min)

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RT: 27.47AA: 1448900376SN: 421RMS

RT: 25.72MA: 861248696SN: 208RMS

RT: 26.02AA: 190896618SN: 58RMS

RT: 25.00AA: 180287915SN: 53RMS

RT: 25.49AA: 174796812SN: 48RMS

RT: 26.93AA: 130996047SN: 40RMS

26.12 26.28 26.61 27.2024.34 26.51 26.8425.1724.8524.50 24.72

RT: 25.72MA: 762981197SN: 6013RMS

RT: 27.47AA: 317826969SN: 3097RMS

RT: 26.01AA: 22502668SN: 241RMS

RT: 26.93AA: 19025095SN: 198RMS

RT: 25.49AA: 18239560SN: 180RMS

RT: 26.25AA: 971450SN: 14RMS

RT: 26.46AA: 873581SN: 11RMS

RT: 24.36AA: 828757SN: 10RMS 27.3424.71 27.0824.93 25.14 25.29

NL:3.15E8TIC MS Lowox10ppm_014

NL:1.13E8m/z= 42.50-43.50+57.50-58.50 MS Lowox10ppm_014

Influence of ion extraction ISX

Acetone in scan mode

MS in SIM mode ISXC:\Xcalibur\...\Deans\Lowox10ppm_024 8/26/2011 12:13:39 PMEV4 OFF --> alles op MS SIM

RT: 27.89 - 28.97 SM: 5B

27.9 28.0 28.1 28.2 28.3 28.4 28.5 28.6 28.7 28.8 28.9Time (min)

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RT: 28.35AA: 691361100SN: 28640

RT: 28.70AA: 2025302SN: 110

RT: 28.12AA: 493968SN: 21

RT: 28.35MA: 485789577SN: 186

RT: 28.67AA: 2515062SN: 115

RT: 28.79AA: 984212SN: 58

RT: 28.23AA: 124392SN: 28

RT: 28.10AA: 522135SN: 24

RT: 27.94AA: 271516SN: 16

RT: 28.85AA: 38161SN: 10 28.9428.04

NL: 1.35E8TIC F: {0,0} + c EI SIM ms [28.50-29.50, 56.50-57.50, 57.50-58.50] MS ICIS Lowox10ppm_024

NL: 9.71E7m/z= 28.50-29.50+56.50-57.50+57.50-58.50 MS lowox10ppm_023

Propanol in SIM and scan mode

Overview of results ISX

Name FID, S/NMS (FS),

S/NMS (EIC),

S/NMS (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 

Continued… ISX

Name FID, S/NMS (FS),

S/NMS (EIC),

S/NMS (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 

Average sensitivity gains ISX

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.

C:\Xcalibur\...\Deans\Lowox10ppb_ITS_001 9/7/2011 9:24:05 AMEV4 OFF --> alles op MS SIM

RT: 17.84 - 57.02

18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56Time (min)

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39.41

36.3332.99

32.69

46.50

45.4941.6449.62

44.97

46.7036.6743.7041.07

49.10 53.6549.95 53.9942.6039.2119.03 35.3831.8925.9225.66 27.46 31.0823.3919.38

NL:8.11E8TIC MS Lowox10ppb_ITS_001

Oxygenates at 10 ppb ISX

DIPE

Methanol

Acetaldehyde C:\Xcalibur\...\Deans\Lowox10ppb_ITS_002 9/7/2011 11:49:13 AMEV4 OFF --> alles op MS SIM

RT: 20.49 - 27.54

20.5 21.0 21.5 22.0 22.5 23.0 23.5 24.0 24.5 25.0 25.5 26.0 26.5 27.0 27.5Time (min)

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25.38

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NL: 1.83E7TIC F: {0,0} + c EI SIM ms [28.50-29.50, 43.50-44.50] MS Lowox10ppb_ITS_002

Repeatability ISX

Acetaldehyde

c:\xcalibur\...\datas\deans\spiab_006 8/25/2011 3:50:51 PMEV4 OFF --> alles op MS SIM

RT: 24.27 - 27.44 SM: 5B

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 27.4Time (min)

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27.3327.2027.0926.9226.7626.6826.5326.3426.2225.34 25.54 26.1425.8725.8125.2625.0124.9324.8124.6024.4924.34

RT: 25.59MA: 22935403

27.2927.1927.0926.9526.61 26.7026.5526.3326.2425.9725.8025.27 25.4625.0324.8524.7724.5824.46

RT: 25.56MA: 20650477

27.3027.1827.0026.8526.6526.5126.4126.2025.67 25.9525.4625.2824.92 25.0524.8424.6924.38 24.60

RT: 25.56MA: 21944573

27.23 27.4327.0826.9526.8126.7226.5326.4626.2225.65 25.92 26.1025.21 25.2925.1024.61 24.70 24.8824.45

RT: 25.51MA: 21203332

27.3427.2026.9626.7326.6026.5226.4126.2726.1025.8725.6625.3125.2325.0724.8424.7824.6324.49

NL:6.10E6m/z= 28.50-29.50+43.50-44.50 MS SPIAB_002

NL:4.92E6m/z= 28.50-29.50+43.50-44.50 MS spiab_003

NL:4.45E6m/z= 28.50-29.50+43.50-44.50 MS spiab_004

NL:5.05E6m/z= 28.50-29.50+43.50-44.50 MS spiab_005

NL:4.54E6m/z= 28.50-29.50+43.50-44.50 MS spiab_006

Continued… ISXc:\xcalibur\...\datas\deans\spiab_006 8/25/2011 3:50:51 PMEV4 OFF --> alles op MS SIM

RT: 32.73 - 34.84 SM: 5B

32.8 33.0 33.2 33.4 33.6 33.8 34.0 34.2 34.4 34.6 34.8Time (min)

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34.1233.83 34.27 34.6433.45 34.52 34.8034.3433.60 33.7832.99 33.0832.76 33.3733.1632.89 33.29

RT: 33.92MA: 8671376

34.0333.83 34.15 34.55 34.8334.6533.62 34.4234.3233.25 33.5333.4333.10 33.3532.9732.9132.74

RT: 33.89MA: 8517965

34.0633.78 34.11 34.7534.6734.44 34.6034.3534.2433.6533.5233.26 33.33 33.4032.99 33.1032.9032.81

RT: 33.86MA: 8452666

33.9534.01 34.5434.26 34.4633.78 34.40 34.5934.18 34.8133.24 34.7033.5033.14 33.5833.4333.05 33.2632.9432.76

RT: 33.85MA: 8791114

33.9933.76 34.4534.05 34.3234.19 34.8134.56 34.7632.75 32.93 33.5833.4733.3333.12 33.2532.98

NL:1.61E6m/z= 42.50-43.50+57.50-58.50 MS SPIAB_002

NL:1.04E6m/z= 42.50-43.50+57.50-58.50 MS spiab_003

NL:1.10E6m/z= 42.50-43.50+57.50-58.50 MS spiab_004

NL:1.03E6m/z= 42.50-43.50+57.50-58.50 MS spiab_005

NL:1.58E6m/z= 42.50-43.50+57.50-58.50 MS spiab_006

Acetone

Isobutylene feed ISXC:\Xcalibur\...\datas\Deans\SPIAB_007 8/26/2011 1:45:55 PMEV4 OFF --> alles op MS SIM

RT: 0.78 - 57.02

5 10 15 20 25 30 35 40 45 50 55Time (min)

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25.4536.72

49.8147.87 56.2151.9247.2541.8338.9236.5428.51 32.34

24.7123.1420.1718.69

NL:1.38E8TIC MS SPIAB_007

Dimethylether

Acetaldehyde

Methanol

t-Butanol Ethanol

2-Propanol

Aceton

C:\Xcalibur\...\Deans\Naphta_ITS_002 9/7/2011 2:21:29 PMEV4 OFF --> alles op MS FS

RT: 15.01 - 57.00

16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56Time (min)

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22.5617.20 21.29

20.6217.5816.32

23.74

24.34 26.41

26.70

27.5228.15

28.36

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29.81 31.09

43.3940.56 46.0737.5834.4431.55

39.79 45.0737.1833.19 41.5739.4046.45 48.57 49.17 56.1852.72 54.40

NL:3.53E10TIC MS Naphta_ITS_002

Naphta feed in scan mode ISX

C:\Xcalibur\...\Deans\Naphta_ITS_001 9/7/2011 12:55:07 PMEV4 OFF --> alles op MS SIM

RT: 19.57 - 56.81

20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56Time (min)

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26.43

27.53

26.07

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40.5620.6031.10 43.39

46.0728.20

34.4520.74

28.5839.80

31.8224.45 34.05 45.0841.4121.54 30.0522.3639.3636.19

33.4837.60 46.60 47.30 49.76 50.81 52.66 54.46 56.64

NL:3.27E9TIC MS Naphta_ITS_001

Naphta feed in SIM mode ISX

Acetaldehyde

TAME

MethanolC:\Xcalibur\...\Deans\Naphta_ITS_001 9/7/2011 12:55:07 PMEV4 OFF --> alles op MS SIM

RT: 32.01 - 34.18

32.2 32.4 32.6 32.8 33.0 33.2 33.4 33.6 33.8 34.0Time (min)

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32.92

33.12

32.7432.52 32.53

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32.47

32.39

NL: 7.79E7TIC F: {0,0} + c EI SIM ms [28.50-29.50, 30.50-31.50, 31.50-32.50] MS Naphta_ITS_001

Concluding remarks ISX

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.

Additional opportunities ISX

Other questions that might be addressed by means of hyphenated MS solutions,

Analysis of raw materials Dedicated customer support Address customer complaints Competitor intelligence

Contact details ISX

For more details on this study, please contact

Dr. Joeri [email protected]++32-(0)10/45.00.25

www.is-x.be