Hydrocarbon Characterization of FACE Aromatic Streams

72 Pages·2010·3.2 MB·English

FINAL REPORT

HYDROCARBON CHARACTERIZATION OF FACE AROMATIC STREAMS

R. Gieleciak, D. Hager, C. Lay, and C. Fairbridge.
CanmetENERGY–DEVON

Work performed for:
CanmetENERGY, Natural Resources Canada;
Fuels for Advanced Combustion Engines Working Group

AUGUST 2010

DIVISION REPORT 2010-082 (INT)
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DISCLAIMER
This report and its contents, the project in respect of which it is submitted, and
the conclusions and recommendations arising from it do not necessarily reflect the
views of the Government of Canada, its officers, employees, or agents.

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EXECUTIVE SUMMARY
CanmetENERGY was asked by the Coordinating Research Council Fuels for
Advanced Combustion Engines (FACE) Working Group to provide standard and
advanced analytical characterization analyses of four samples used for FACE
research diesel fuel testing.
This report provides standard as well as detailed chemical and structural
hydrocarbon type information for the aromatic hydrocarbon streams. The results
presented in this report consist of data obtained using the following analytical
techniques: PIONA (n-paraffin, iso-paraffin, olefin, naphthene and aromatic, ASTM
D5443M), DHA (detailed hydrocarbon analysis, ASTM D6730), GC-FIMS (gas
chromatography-field ionization mass spectrometry), GC-MS (gas chromatography-
mass spectrometry, ASTM D2786 and D3239), and GCxGC (comprehensive two-
dimensional gas chromatography). The following table presents a summary of the
analyses.
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CONTENTS

DISCLAIMER.....................................................................................................................i
EXECUTIVE SUMMARY................................................................................................ii
1.0 INTRODUCTION..................................................................................................1
2.0 EXPERIMENTAL..................................................................................................1
2.1 HYDROCARBON TYPE COMPOSITION OF PETROLEUM
DISTILLATES BY ASTM D2786/D3239.............................................................1
2.2 GAS CHROMATOGRAPHY – FIELD IONIZATION MASS
SPECTROMETRY (GC-FIMS).............................................................................2
2.3 COMPREHENSIVE TWO-DIMENSIONAL GAS
CHROMATOGRAPHY (GCXGC)........................................................................3
3.0 RESULTS AND DISCUSSION.............................................................................6
3.1 HYDROCARBON TYPE COMPOSITION OF PETROLEUM
DISTILLATES BY ASTM D2786/D3239.............................................................6
3.2 GC-FIMS................................................................................................................9
3.3 COMPREHENSIVE TWO-DIMENSIONAL GAS
CHROMATOGRAPHY.......................................................................................13
3.3.1 GCXGC-FID.........................................................................................................13
3.4 GCXGC-TOFMS/FID..........................................................................................22
4.0 ACKNOWLEDGEMENTS..................................................................................31
APPENDIX A: SIMDIS ASTM D2887..........................................................................32
APPENDIX B: PIONA DATA........................................................................................36
APPENDIX C: DHA DATA...........................................................................................39
APPENDIX D: SPE-GC-MS AND PIONA DATA........................................................43
APPENDIX E: GC-FIMS................................................................................................46
APPENDIX F: GCxGC – FID.........................................................................................54
APPENDIX G: GCxGC – TOFMS/FID...........................................................................59

TABLES

Table 1 – Sample names, sample tags, and some known properties a)...............................1
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Table 2 – Operating conditions for GCxGC-FID analysis.................................................5
Table 3 – Operating conditions for GCxGC-TOFMS/FID analysis...................................5
Table 4 – Quantitative group type results of GCxGC-FID separation.............................16
Table 5 – Results of GCxGC-TOFMS/FID speciation.....................................................23
Table A1 – SimDis table...................................................................................................33
Table B1 – PIONA data for COSDENOL 104.................................................................37
Table B2 – PIONA data for ATOSOL 115......................................................................38
Table C1 – DHA analysis by boiling point and by carbon number for
COSDENOL 104..................................................................................................40
Table C2 – DHA analysis by boiling point and by carbon number for
ATOSOL 115........................................................................................................41
Table D1 – SPE-GC-MS + PIONA analysis for COSDENOL 104 and
ATOSOL 115 (no SPE-GC-MS data for ATOSOL 115 because its
initial boiling point is < 200°C)............................................................................44
Table D2 – SPE-GC-MS +analysis for COSDENOL 180 and RB SOLV
200B (no PIONA data for this samples because their initial boiling
point is > 200°C)...................................................................................................45
Table E1 – GC-FIMS + PIONA data for COSDENOL 104.............................................47
Table E2 – GC-FIMS data for COSDENOL 180.............................................................48
Table E3 – GC-FIMS data for RB SOLVENT 200B.......................................................49

FIGURES

Figure 1 – Chromatogram showing alignment of subsequent simultaneous
response of dual detectors TIC (orange) and FID (green)......................................4
Figure 2 – SimDis curves for four aromatic streams (based on ASTM
D2887)....................................................................................................................6
Figure 3 – PIONA results for Cosdenol 104: S - saturates; U - unsaturates.
Recovery of < 200ºC fraction from SimDis (ASTM 2887): 76.50%.....................7
Figure 4 – PIONA results for Atosol 115. S - saturates; U - unsaturates.
Recovery of < 200ºC fraction from SimDis (ASTM 2887): 96.30%.....................7
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Figure 5 – SPE-GC-MS data for Cosdenol 104..................................................................8
Figure 6 – SPE-GC-MS data comparison for Cosdenol 180 and RB solv
200B........................................................................................................................9
Figure 7 – GC-FIMS and PIONA data comparison for (a) Cosdenol 104
and (b) Atosol 115................................................................................................10
Figure 8 – GC-FIMS and PIONA data comparison for (a) Cosdenol 180
and (b) RB Solvent 200B......................................................................................11
Figure 9 – Differentiation plots for (a) Cosdenol 104 & Atosol 115 and (b)
Cosdenol 180 & RB Solvent 200B.......................................................................12
Figure 10 – Schematic example of compound class distribution using
traditional column set combination. Meaning of symbols: a6 – 6
carbon aromatics, c5 – 5 carbon ring aliphatic, c6 – 6 carbon ring
aliphatic.................................................................................................................14
Figure 11 – Examples of compounds assigned to groups used in GCxGC-
FID typing.............................................................................................................15
Figure 12 – Graphic results of GCxGC-FID speciation...................................................17
Figure 13 – GCxGC-FID bubble plot chromatograms of (a) Cosdenol 104
and (b) Atosol 115 with selected groups...............................................................18
Figure 14 – GCxGC-FID bubble plot chromatograms of (a) Cosdenol 180
and (b) RB Solvent 200B with selected groups...................................................19
Figure 15 – Differentiation plots for (a) Cosdenol 104 & Atosol 115 and
(b) Atosol 115 & Cosdenol 104............................................................................20
Figure 16 – Differentiation plots for (a) Cosdenol 180 & RB Solvent 200B
and (b) RB Solvent 200B & Cosdenol 180...........................................................20
Figure 17 – (a) ‘global’ SimDis based on GCxGC for Cosdenol 104 (blue)
and Atosol 115 (red) (b) ‘group type’ SimDis based on selected
classification regions.............................................................................................21
Figure 18 – (a) ‘global’ SimDis based on GCxGC for Cosdenol 180 (blue)
and RB Solvent 200B (red) (b) ‘group type’ SimDis based on
selected classification regions...............................................................................21
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Figure 19 – GCxGC-TOFMS/FID chromatograms of example sample: (a)
‘normal’ column combination (b) ‘reversed’ column combination......................22
Figure 20 – Example of identification of compounds in selected region for
RB Solvent 200B..................................................................................................24
Figure 21 – GCxGC-TOFMS/FID chromatograms of (a) Cosdenol 104
and (b) Atosol 115 with selected groups. Compound classes are
marked with different colors (e.g., C2-benzene <green>, C3-
benzene <red>, C4-benzene <yellow>)................................................................25
Figure 22 – GCxGC-TOFMS/FID chromatograms of (a) Cosdenol 180
and (b) RB Solvent 200B with selected groups. Compound classes
are marked with different colors (e.g., naphthalenes <red>, C11-
benzene <brown>,cyclohexylbenzenes <pink., C1-C4-
dphenyethanes <dark blue>).................................................................................26
Figure 23 – Comparison of detailed GCxGC-TOFMS hydrocarbon type
analyses for Cosdenol 104 and Atosol 115...........................................................27
Figure 24 – Comparison of detailed GCxGC-TOFMS hydrocarbon type
analyses for Cosdenol 180 and RB Solvent 200B................................................28
Figure 25 – Examples of compounds used in GCxGC-TOFMS/FID
comparative analysis.............................................................................................29
Figure 26 – Differentiation plots for (a) Cosdenol 104 & Atosol 115 and
(b) Atosol 115 & Cosdenol 104............................................................................30
Figure 27 – Differentiation plots for (a) Cosdenol 180 & RB Solvent 200B
and (b) RB Solvent 200B & Cosdenol 180...........................................................30
Figure E1 – GC-FIMS and PIONA for COSDENOL 104...............................................50
Figure E2 – GC-FIM and PIONA for ATOSOL 115.......................................................51
Figure E3 – GC-FIMS and PIONA for COSDENOL 180...............................................52
Figure E4 – GC-FIMS and PIONA for RB SOLV 200B.................................................53
Figure F1 – GCxGC-FID chromatograms of Cosdenol 104: (a) 2D view,
(b) 3D view, (c) 2D view together with classification regions.............................55
Figure F2 – GCxGC-FID chromatograms of Atosol 115: (a) 2D view, (b)
3D view, (c) 2D view together with classification regions...................................56
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Figure F3 – GCxGC-FID chromatograms of Cosdenol 180: (a) 2D view,
(b) 3D view, (c) 2D view together with classification regions.............................57
Figure F4 – GCxGC-FID chromatograms of RB Solvent 200B: (a) 2D
view, (b) 3D view, (c) 2D view together with classification regions...................58
Figure G1 – GCxGC-TOFMS/FID chromatograms of Cosdenol 104: (a)
2D view together with classification regions (b) 3 D view..................................60
Figure G 2 – GCxGC-TOFMS/FID chromatograms of Atosol 115: (a) 2D
view together with classification regions (b) 3 D view........................................61
Figure G3 – GCxGC-TOFMS/FID chromatograms of Cosdenol 180: (a)
2D view together with classification regions (b) 3 D view..................................62
Figure G4 – GCxGC-TOFMS/FID chromatograms of RB Solvent 200B:
(a) 2D view together with classification regions (b) 3D view..............................63
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1.0 INTRODUCTION
A description of the samples provided for analysis is presented in Table 1.
Table 1 – Sample names, sample tags, and some known properties a)

Cosdenol 104 Cosdenol 180 RB Solvent 200B Atosol 115
CanmetENERGY ID 10-1041 10-1042 10-1043 10-1044
CAS# 64741-68-0 64742-94-5 147952-37-2 70693-06-0
Physical state liquid liquid liquid liquid
Flash points >37.8ºC 82.2ºC 136.1ºC 46.1ºC
Specific gravity (Water = 1.00) 0.88 0.98 0.978 0.86-0.88
Boiling/Condensation Point 160–246ºC 236–318ºC 232ºC 145–185ºC
a) Taken from Material Safety Data Sheet.
2.0 EXPERIMENTAL
2.1 HYDROCARBON TYPE COMPOSITION OF PETROLEUM
DISTILLATES BY ASTM D2786/D3239
First, simulated distillation (SimDis) analysis (ASTM D2887), which provides
the boiling point distribution of petroleum products for the boiling range between C5
(35ºC) and C44 (538ºC), is performed on each sample. The distillation method is
simulated by the use of gas chromatography (in this case, an Analytical Control
Systems, Inc. SimDis custom analyzer based on the HP-6890 series gas
chromatograph), where a nonpolar capillary column is used to elute the hydrocarbon
components of the sample in order of increasing boiling point.
Secondly, the samples are pre-separated by solid-phase extraction (SPE)
analysis, which is an in-house method developed to separate hydrocarbon samples
containing little or no polar species into saturate, olefin, and aromatic fractions. This
is accomplished by eluting the sample through SPE cartridges containing different
stationary phases using different solvents (mobile phases). The eluted fractions are
concentrated to a known volume before being quantified using GC-FID.
Thirdly, saturate and aromatic fractions are characterized using GC-MS to
identify and quantify their individual component types. A sample’s components that
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