HYDROCARBON CHARACTERIZATION OF FACE AROMATIC STREAMS

Transcription

1 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 (INT)

2 i 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.

3 ii 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 chromatographymass spectrometry, ASTM D2786 and D3239), and GCxGC (comprehensive twodimensional gas chromatography). The following table presents a summary of the analyses.

4 iii

5 iv CONTENTS DISCLAIMER... i EXECUTIVE SUMMARY... ii 1.0 INTRODUCTION EXPERIMENTAL HYDROCARBON TYPE COMPOSITION OF PETROLEUM DISTILLATES BY ASTM D2786/D GAS CHROMATOGRAPHY FIELD IONIZATION MASS SPECTROMETRY (GC-FIMS) COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY (GCXGC) RESULTS AND DISCUSSION HYDROCARBON TYPE COMPOSITION OF PETROLEUM DISTILLATES BY ASTM D2786/D GC-FIMS COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY GCXGC-FID GCXGC-TOFMS/FID ACKNOWLEDGEMENTS APPENDIX A: SIMDIS ASTM D APPENDIX B: PIONA DATA APPENDIX C: DHA DATA APPENDIX D: SPE-GC-MS AND PIONA DATA APPENDIX E: GC-FIMS APPENDIX F: GCxGC FID APPENDIX G: GCxGC TOFMS/FID TABLES Table 1 Sample names, sample tags, and some known properties a)... 1

6 v 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 Table 5 Results of GCxGC-TOFMS/FID speciation Table A1 SimDis table Table B1 PIONA data for COSDENOL Table B2 PIONA data for ATOSOL Table C1 DHA analysis by boiling point and by carbon number for COSDENOL Table C2 DHA analysis by boiling point and by carbon number for ATOSOL 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) 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) Table E1 GC-FIMS + PIONA data for COSDENOL Table E2 GC-FIMS data for COSDENOL Table E3 GC-FIMS data for RB SOLVENT 200B 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

7 vi Figure 5 SPE-GC-MS data for Cosdenol 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 Figure 8 GC-FIMS and PIONA data comparison for (a) Cosdenol 180 and (b) RB Solvent 200B Figure 9 Differentiation plots for (a) Cosdenol 104 & Atosol 115 and (b) Cosdenol 180 & RB Solvent 200B 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 Figure 11 Examples of compounds assigned to groups used in GCxGC- FID typing Figure 12 Graphic results of GCxGC-FID speciation Figure 13 GCxGC-FID bubble plot chromatograms of (a) Cosdenol 104 and (b) Atosol 115 with selected groups Figure 14 GCxGC-FID bubble plot chromatograms of (a) Cosdenol 180 and (b) RB Solvent 200B with selected groups Figure 15 Differentiation plots for (a) Cosdenol 104 & Atosol 115 and (b) Atosol 115 & Cosdenol Figure 16 Differentiation plots for (a) Cosdenol 180 & RB Solvent 200B and (b) RB Solvent 200B & Cosdenol 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 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

8 vii Figure 19 GCxGC-TOFMS/FID chromatograms of example sample: (a) normal column combination (b) reversed column combination Figure 20 Example of identification of compounds in selected region for RB Solvent 200B 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>) 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>) Figure 23 Comparison of detailed GCxGC-TOFMS hydrocarbon type analyses for Cosdenol 104 and Atosol Figure 24 Comparison of detailed GCxGC-TOFMS hydrocarbon type analyses for Cosdenol 180 and RB Solvent 200B Figure 25 Examples of compounds used in GCxGC-TOFMS/FID comparative analysis Figure 26 Differentiation plots for (a) Cosdenol 104 & Atosol 115 and (b) Atosol 115 & Cosdenol Figure 27 Differentiation plots for (a) Cosdenol 180 & RB Solvent 200B and (b) RB Solvent 200B & Cosdenol Figure E1 GC-FIMS and PIONA for COSDENOL Figure E2 GC-FIM and PIONA for ATOSOL Figure E3 GC-FIMS and PIONA for COSDENOL Figure E4 GC-FIMS and PIONA for RB SOLV 200B Figure F1 GCxGC-FID chromatograms of Cosdenol 104: (a) 2D view, (b) 3D view, (c) 2D view together with classification regions Figure F2 GCxGC-FID chromatograms of Atosol 115: (a) 2D view, (b) 3D view, (c) 2D view together with classification regions... 56

9 viii Figure F3 GCxGC-FID chromatograms of Cosdenol 180: (a) 2D view, (b) 3D view, (c) 2D view together with classification regions Figure F4 GCxGC-FID chromatograms of RB Solvent 200B: (a) 2D view, (b) 3D view, (c) 2D view together with classification regions Figure G1 GCxGC-TOFMS/FID chromatograms of Cosdenol 104: (a) 2D view together with classification regions (b) 3 D view Figure G 2 GCxGC-TOFMS/FID chromatograms of Atosol 115: (a) 2D view together with classification regions (b) 3 D view Figure G3 GCxGC-TOFMS/FID chromatograms of Cosdenol 180: (a) 2D view together with classification regions (b) 3 D view Figure G4 GCxGC-TOFMS/FID chromatograms of RB Solvent 200B: (a) 2D view together with classification regions (b) 3D view... 63

10 1 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 CAS# Physical state liquid liquid liquid liquid Flash points >37.8ºC 82.2ºC 136.1ºC 46.1ºC Specific gravity (Water = 1.00) Boiling/Condensation Point ºC ºC 232ºC ºC 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

11 2 boil above 200 C (392 F) are quantified and identified in terms of saturate and aromatic percentages using GC-MS D2786 for the saturate fraction and ASTM D3239 for the aromatic fraction. Those components boiling below 200ºC are determined by PIONA to provide hydrocarbon types by carbon number. 2.2 GAS CHROMATOGRAPHY FIELD IONIZATION MASS SPECTROMETRY (GC-FIMS) Samples are characterized by GC-FIMS, which characterizes hydrocarbon types in the boiling range of 200 to 343 C (392 to 649 F). This method provides detailed characterization of saturates (including iso-paraffins, n-paraffins, and cylcoparaffins), aromatics (mono, di, and polyaromatics), and two aromatic thiophenotypes. It does not require pre-separation of the sample. The results are reported for the total product and by carbon number (up to C21 for the diesel range) and/or by boiling point distribution. A full GC-FIMS report also consists of a series of reports by carbon number in selected temperature intervals (usually 10 C intervals). The analysis is performed using an Agilent 6890 gas chromatograph configured with a GCT Micromass multi-channel plate detector. A semi-polar DB- 5HT capillary column (30 m long 0.25 mm internal diameter 0.10 μm film thickness) is used for separation of the peaks, and identification of the components is based on the accurately determined masses. For the diesel components boiling below 200 C (392 F), the sample is injected into a PIONA analyzer (Analytical Control PIONA analyzer-reformulizer) and run according to ASTM D5443 and ASTM D6839 so that the data can be presented by carbon number. The instrument has been equipped with a prefractionator to vent off any material that boils above 200 C (392 F). The PIONA data reported for the fraction that boils below 200 C are then combined with the GC-FIMS data for the fraction that boils above 200 C to produce reports that capture the full boiling range of the diesel fuel. Two assumptions were made in presenting the PIONA data: cycloparaffins were all monocycloparaffins, and aromatics were all alkylbenzenes. Similarly, diesel components boiling below 200 C (392 F) were also analyzed by

12 3 detailed hydrocarbon analysis (DHA, ASTM D6730) operated with a prefractionator to eliminate hydrocarbons that boil above 200 C (392 F). 2.3 COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY (GCXGC) Comprehensive two-dimensional gas chromatography (GCxGC) is a hyphenated technique in which two different chromatographic separation mechanisms act in series to greatly improve component separation and identification. The system contains a jet-cool modulator between two chromatographic columns having different selectivities. The modulator repeatedly focuses a small portion of the first column eluate and injects it into the second column. All of the effluents from the second column enter the detector. The main factors influencing usefulness of this method are: high chromatographic resolution, high peak capacity, analyte detectability, and chemical compound class ordering on the chromatogram. The second dimension separation is very fast (usually 2 to 6 s), peaks are narrow, typically, 0.1 to 0.5 s. Detectors used in this system must be characterized by small internal volumes, short rise times, and high data acquisition rates. One of the detectors meeting these demands, and used in CanmetENERGY GCxGC instruments, is the flame ionization detector (FID). The FID response is linear over a very wide range of concentrations and proportional to the mass flow rate of carbon. It therefore may be considered as a general hydrocarbon detector. All quantitative analyses provided in this report were based on the FID detector. When structural information has to be provided to enable compound identification, a mass spectrometer can be used as a detector. The TOFMS (time-offlight mass spectrometer) instrument can acquire up to 500 spectra per second, which is more than enough for the accurate reconstruction of second-dimension peaks and the deconvolution of overlapping peaks. The LECO ChromaTOF software allows direct presentation of total ion current (TIC) and analytical ion current, and extractedion two-dimensional chromatograms, which assists the interpretation process. In addition to the mass spectrometer detector, the CanmetENERGY GCxGC-TOFMS is equipped with a flame ionization detector. After matching both TOFMS and FID

13 4 signals, both qualitative and quantitative results can be obtained simultaneously. An example of such a chromatogram is shown in Figure 1. Figure 1 Chromatogram showing alignment of subsequent simultaneous response of dual detectors TIC (orange) and FID (green) One of the main benefits of orthogonal GCxGC separation is that the chromatogram obtained is structurally ordered (i.e., on the GC map, continuous clusters for related homologues, congeners, and isomers are easily visible). Examples of such structured chromatograms are presented in the figures in Appendix E). The GCxGC instruments were provided by Leco Instruments and used a cryogenically cooled modulator. The column features and the operating conditions for both GCxGC-FID/SCD and GCxGC-TOFMS/FID experiments are listed in Table 2 and Table 3, respectively. Detectors used in the analysis are as follows: FID (flame ionization detector), SCD (sulfur chemiluminescence detector), and TOFMS (time-offlight mass spectrometer).

14 5 Table 2 Operating conditions for GCxGC-FID analysis 1 st column Varian Factor 4 VF5-HT, 30 m x 0.32 mm DF:0.1 Main oven program C; 5 C/min 2 nd column Varian Factor 4 VF17-MS, 1.5 m x 0.1 DF:0.2 Secondary oven program 40 C offset from main oven Inlet temperature 350 C Injection size 0.2 L Split ratio 40:1 Carrier gas He, constant flow, 1.5 ml/min Modulator temperature 55 C offset from main oven Detector FID, 350 C Acquisition rate 100 Hz Modulation period 8 s Table 3 Operating conditions for GCxGC-TOFMS/FID analysis 1 st column Varian Factor 4 VF17-MS, 30 m x 0.32 mm DF:0.1 Main oven program C; 5 C/min 2 nd column Varian Factor 4 VF5-HT,1.5 m x 0.1 DF:0.2 Secondary oven program 40 C offset from main oven Inlet temperature 350 C Injection size 0.2 L Split ratio 40:1 Carrier gas He, constant flow, 1.5 ml/min Modulator temperature 55 C offset from main oven Detector TOFMS and FID Acquisition rate 200 Hz Modulation period 6 s Data handling procedures, such as contour plotting, GCxGC peak collection, retention time measurements, and peak volume calculation were performed using ChromaTOF software provided by LECO Instruments. Chemical compounds in the samples were identified by searching for matching spectra in NIST mass spectral information. Results for each compound quantities were shown as a percentage of the total area of the quantified peaks. All quantitative analysis was based on FID output.

15 6 3.0 RESULTS AND DISCUSSION 3.1 HYDROCARBON TYPE COMPOSITION OF PETROLEUM DISTILLATES BY ASTM D2786/D3239 The SimDis analysis for the four aromatic streams is presented in Figure 2 and a tabulated version is provided in Appendix A. Such data generally show the same trends as the distillation curves obtained from ASTM D86 analysis. Trends presented during SimDis revealed similarities among analyzed samples. Clearly, Cosdenol 180 and RB Solvent 200B exhibit distillation curves that are higher than the other ones (Cosdenol 104 and Atosol 115). However, it was observed that Atosol 115 and RB Solvent 200B contain more low-boiling-point compounds than their group equivalents. Figure 2 SimDis curves for four aromatic streams (based on ASTM D2887) PIONA (paraffins, isoparaffins, olefins, naphthenes, aromatics) analysis was used to obtain a composite hydrocarbon-type analysis for samples that boil below 200 C. Data processing applied after separation allows for full hydrocarbon analysis that presents the PIONA data by carbon number (C 3 to C 11 ) for selected hydrocarbon types. The PIONA data for selected samples (Cosdenol 104 and Atosol 115) are

16 7 presented in Appendix B. Colored contour plots of the PIONA results are shown in Figure 3 and Figure 4 for the lighter streams (Cosdenol 104 and Atosol 115). Figure 3 PIONA results for Cosdenol 104: S - saturates; U - unsaturates. Recovery of < 200ºC fraction from SimDis (ASTM 2887): 76.50% Figure 4 PIONA results for Atosol 115. S - saturates; U - unsaturates. Recovery of < 200ºC fraction from SimDis (ASTM 2887): 96.30%

17 8 Based on the SimDis plot (see Figure 2), the weight fractions that boiled below 200ºC were 96.3% and 76.5% for Atosol 115 and Cosdenol 104, respectively. Therefore, for Atosol 115, the hydrocarbon content is completely described by PIONA alone. In addition to PIONA analysis, DHA (detailed hydrocarbon analysis) was also performed on the two light streams (Cosdenol 104 and Atosol 115). DHA results are presented in Appendix C by both carbon number and boiling point distribution. Fractions after SPE (solid phase extraction) were analyzed by GC-MS using ASTM D2786 for the saturates and ASTM D3239 for the aromatics boiling above 200ºC. The separate GC-MS results were combined to derive total hydrocarbon contents for the diesel fuels. These data are presented in Figure 5 and Figure 6 for Cosdenol 104 and Cosdenol 180/RB Solv 200B, respectively. Analytical data from SPE-GC-MS and PIONA analyses are provided in tabular form in Appendix D. Figure 5 SPE-GC-MS data for Cosdenol 104

18 9 Figure 6 SPE-GC-MS data comparison for Cosdenol 180 and RB solv 200B 3.2 GC-FIMS Due to detector overloading phenomena, samples were diluted prior to the GC-FIMS experiments. However, for comparative purposes GC-FIMS analyses were performed both for neat and diluted samples. The GC-FIMS data together with the PIONA data for all four aromatic streams are presented in tabulated form in Appendix E. Because the upper boiling point range for Atosol 115 is below 200ºC, GC-FIMS was not performed on this sample. Figure 7 and Figure 8 shows the distribution of hydrocarbon types by carbon number for analyzed samples using combined data from GC-FIMS and PIONA. Differentiation plots shown on Figure 9 help distinguish similarities between proper light and heavier pairs of aromatic compounds.

19 10 a) b) Figure 7 GC-FIMS and PIONA data comparison for (a) Cosdenol 104 and (b) Atosol 115

20 11 a) Figure 8 GC-FIMS and PIONA data comparison for (a) Cosdenol 180 and (b) RB Solvent 200B b)

21 12 a) Figure 9 Differentiation plots for (a) Cosdenol 104 & Atosol 115 and (b) Cosdenol 180 & RB Solvent 200B b)

22 COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY Two-dimensional gas chromatography was used for both quantitative and qualitative analysis. The following pages present the advanced characterization of aromatic samples in more detail and include two-dimensional chromatograms from both the GCxGC-FID and GCxGC-TOFMS/FID instruments GCXGC-FID The CanmetENERGY GCxGC-FID instrument is equipped with a traditional column set combination (see Table 2). The first column is nonpolar and the second column is polar. Using this column combination, the first-dimension separation is governed by volatility and, consequently, a boiling point separation is obtained. The separation on the second column is dependent on specific relationships between the stationary phase and analytes. This setup provides a structured group separation as shown schematically in Figure 10. The ordered structures enable rapid profiling and quantification. Selected representatives from compound classes are shown in Figure 11.

23 14 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.

24 15 Figure 11 Examples of compounds assigned to groups used in GCxGC-FID typing

25 16 All GCxGC-FID results presented in this report were based on neat (not diluted) samples. The compound classes presented in Figure 10 and Figure 11 were used for reporting the results of group type separations for all analyzed samples. GCxGC-FID chromatograms obtained from the analysis of all four aromatic samples are shown in Appendix F (Figures F1 F4). Retention time in the first dimension is shown on the x-axis, and retention time in the second dimension is shown on the y-axis. Signal intensity is illustrated on a color scale. For the first series (Figures F1a F4a), blue represents the baseline and red represents the most intense peaks in the chromatogram. The second series (Figures F1b F4b) shows twodimensional chromatograms together with classification regions. The third series of pictures (Figures F1c F4c) shows three-dimensional views of GCxGC separation. Table 3 gives detailed quantitative and structural information of group type GCxGC-FID analysis. Figure 12 presents the results from Table 4 in visual form. Table 4 Quantitative group type results of GCxGC-FID separation Cosdenol 104 Atosol 115 Cosdenol 180 RB Solvent 200B N-paraffins Isoparaffins olefins/cycloparaf a6 a) a6a a6a6a a6a6a6c a6c5/a6c6/a6c a6c5a a) Explanation of symbolic tags oin Figure 11.

26 17 Figure 12 Graphic results of GCxGC-FID speciation Peak areas obtained after preprocessing with ChromaTOF software were transferred into MATLAB and subjected to further processing. The first-dimension retention time was converted into a boiling point using a correlation established between the boiling point of n-paraffins and their retention time. This exercise allowed for presentation of GCxGC-FID maps in the boiling point domain. Additionally, component peaks found in the chromatograms were presented in bubble plot form where the size of the bubble is related to the component concentration. This type of visualization is presented in Figure 13 and Figure 14. The Cosdenol 104 and Atosol 115 bubble plots were deliberately placed together in Figure 3.12 to facilitate quick comparison). The same arrangement was applied to the other pair of samples, namely Cosdenol 180 and RB Solvent 200B in Figure 3.13.

27 18 a) b) Figure 13 GCxGC-FID bubble plot chromatograms of (a) Cosdenol 104 and (b) Atosol 115 with selected groups. The lighter streams (Cosdenol 104 and Atosol 115) are mostly composed of substituted benzene ring compounds. The old source Cosdenol contains more diaromatic compounds (a6a6) than the proposed source Atosol 115. A close look at

28 19 Figure F1 and Figure F2 (in Appendix F) and the bubble plot (Figure 13 ) reveals that the a6a6 group compounds are naphthalene and 1- and 2-methylnaphthalene. a) b) Figure 14 GCxGC-FID bubble plot chromatograms of (a) Cosdenol 180 and (b) RB Solvent 200B with selected groups The heavier streams (Cosdenol 180 and RB Solvent 200B) are mostly composed of substituted monoaromatic compounds and a6a6 compounds. As shown

29 20 in Figure 11, the a6a6 group could be biphenyl, naphthalene, or 1,1 -diphenylethane derivatives. However, further GCxGC-TOFMS analysis showed that this group of compounds is mostly composed of diphenyl alkanes. Additionally, maps showing differences between GCxGC-FID chromatograms were prepared (see Figure 15 and Figure 16). Such representation allows for fast recognition of regions of deviation between samples. Cosdenol 114 Atosol 115 Atosol Cosdenol 114 a) b) Figure 15 Differentiation plots for (a) Cosdenol 104 & Atosol 115 and (b) Atosol 115 & Cosdenol 104 Cosdenol 180 RB Solvent 200B RB Solvent 200B - Cosdenol 180 a) b) Figure 16 Differentiation plots for (a) Cosdenol 180 & RB Solvent 200B and (b) RB Solvent 200B & Cosdenol 180

30 21 In addition to the discrete characterization described above, GCxGC-FID has also the capability to provide continuous information in the form of SimDis curves. To achieve this, the first-dimension retention time has to be converted to a boiling point using a relationship established with n-paraffins. Figure 17a and Figure 18a show the SimDis curves obtained for both the lighter and heavier samples. These derived SimDis curves are very similar to ASTM D2887 SimDis curves (see Figure 2). In addition to SimDis characterization of total liquid product, it is possible to draw SimDis curves specific to each chemical group found during the classification process (see Figure 17b and Figure 18b). a) b) 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 a) b) 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

31 GCXGC-TOFMS/FID The CanmetENERGY GCxGC-TOFMS/FID instrument is equipped with a reversed column set combination (see Table 2), where the first column is a long polar column and the second one is a short nonpolar column. In this case, separation is primarily governed by the specific interactions between the analytes and the column s polar stationary phase. The reversed-polarity column setup is being investigated by CanmetENERGY to improve the separation between saturates, olefins, cycloparaffins, and aromatics, and potentially to increase utilization of capacity. However, during our experiments with the reversed-polarity column set we noticed certain disadvantages, including loss of correlation between retention time and boiling point, and poorer separation of aromatic hydrocarbons compared to a normal column setup. The discussed separation conditions reported earlier in Table 2 are presented in Figure 19b together with the class boundary between aromatics and saturates on the chromatogram. Saturates Aromatics a) b) Figure 19 GCxGC-TOFMS/FID chromatograms of example sample: (a) normal column combination (b) reversed column combination With the installation of a purged two-way splitter, it was possible to precisely synchronize the CanmetENERGY GCxGC-TOFMS with the flame ionization

32 23 detector to greatly enhance the reliability of both the quantitative and qualitative results. Table 5 presents crude results of GCxGC-TOFMS/FID analysis. Unlike the earlier GCxGC-FID results, GCxGC-TOFMS analysis is restricted to a smaller number of compound group types. In the near future we are planning to extend the reported results by splitting the aromatic group into a few subgroups (di-, triaromatics). Table 5 Results of GCxGC-TOFMS/FID speciation Cosdenol 104 Atosol 115 Cosdenol 180 RB Solvent 200B aromatics cyclo-paraffins iso-paraffins n-paraffins For GCxGC-TOFMS/FID chromatograms, both 2D and 3D views obtained from the analysis of all four aromatic samples are shown in Appendix G (Figures G1 G4). Retention time in the first dimension is shown on the x-axis, and retention time in the second dimension is shown on the y-axis. Signal intensity (FID signal) is illustrated on a color scale where blue represents the baseline and red represents the most intense peaks in the chromatogram. Each two-dimensional chromatogram includes the classification regions used in quantitative analysis. The GCxGC-TOFMS provides a huge amount of structural information on compounds present in the sample. Usually, species are identified by searching for matching spectra in the U.S. National Institute of Standards and Technology (NIST) mass spectral libraries. The main difficulty following a library search is associated with authentication of the results obtained. In many cases, accurate name attribution for a detected peak was impossible because of the low concentration of the analyte, the lack of an appropriate mass spectrum in the spectrometry library, or mass spectrum similarities between isomers. For example, Figure 20 presents the chromatogram of RB Solvent 200B. The red circle on the GCxGC map shows the aromatic region with a representative mass spectrum from this region. Information

33 24 included in the mass spectrum i.e., molecular ion M+ and a few peaks associated with the spectrum suggested that the group of peaks in the red oval belong to C11 benzene derivatives. Peak True - sample " _40resamplex2", peak 278, at 1290, sec, sec Characteristic ion for 4 substituted benzene rings M+ equal 232 means that it is benzene ring substituted with eleven carbones Figure 20 Example of identification of compounds in selected region for RB Solvent 200B During retrospective analysis, the authors of this report noticed that the total ion current chromatograms had a very characteristic, flat peak shape, which could point to a detector overloading phenomenon. This could have affected the process of identifying the proper specific compound; however, it had no effect on quantitative results received from the FID detector. Therefore, all the samples were diluted (1/50 in dichloromethane and GCxGC-TOFMS analysis was repeated. Figure 21 and Figure 22 illustrate the results of hydrocarbon speciation for aromatic streams. Each chromatogram presented here contains either the compound name or the compound class name. All the compounds or class regions were based on individual mass spectra analysis. Figure 25 shows the structures of compounds used in the comparative analysis prepared for aromatic streams. The bar plots in Figure 23 and Figure 24 illustrate the concentrations of individual compounds/groups of compounds for the samples.

34 25 a) b) 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 >)

35 26 a) b) 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 >)

36 27 FID Peak Area (%) C2 1,1'-DIPHENYLETHANE (36) C4 -NAPHTHALENE (33) 1,2-DIMETHYLINDANE (26) DIMETHYLNAPHTHALENE (32) ,2-DIMETHYLBENZENE (2) 2-METHYLNAPHTHALENE (31) (1-METHYLBUTYL)BENZENE (17) 1-METHYLINDAN (25) 1-METHYL-2-ISOPROPYLBENZENE (14) ISOPROPYLBENZENE (7) 1,3-DIMETHYL-5-ISOPROPYLBENZENE (18) 1-METHYLNAPHTHALENE (30) NAPHTHALENE (29) 1-METHYL-4-(1-METHYLETHYL)BENZENE (12) 1,3-DIMETHYLBENZENE (3) TERT-PENTYLBENZENE (19) 2,3-DIHYDRO-INDENE (24) 1-ETHYL-3,4-DIMETHYLBENZENE (11) PROPYLBENZENE (8) TERT-BUTYLBENZENE (16) 1-ETHYL-2,6-DIMETHYLBENZENE (10) 1-ETHYL-2,3-DIMETHYLBENZENE (9) 1-ETHYL-4-METHYLBENZENE (5) M-METHYLPROPYLBENZENE (15) 1-ETHYL-2-METHYLBENZENE (4) 1,2,3-TRIMETHYLBENZENE (6) Cosdenol 104 Atosol 115 Figure 23 Comparison of detailed GCxGC-TOFMS hydrocarbon type analyses for Cosdenol 104 and Atosol 115

37 28 FID Peak Area (%) 2-METHYLNAPHTHALENE (31) 1-ETHYL-2,6-DIMETHYLBENZENE (10) 1-METHYLNAPHTHALENE (30) ,2-DIMETHYLINDANE (26) (1-METHYLBUTYL)BENZENE (17) DIMETHYLNAPHTHALENE (32) 1,3-DIMETHYL-5-ISOPROPYLBENZENE (18) 1,3,5-TRIETHYLBENZENE (21) DIPHENYLMETHAN (34) 2-METHYLCYCLOHEXYLBENZENE (28) TERT-PENTYLBENZENE (19) 1,2,4-TRIETHYLBENZENE (20) CYCLOHEXYLBENZENE (27) 1,2-DIMETHYLBENZENE (2) C2 1,1'-DIPHENYLETHANE (36) C4 -NAPHTHALENE (33) 1,2,4,5-TETRAETHYLBENZENE (22) C11 BENZENE (23) 1,1'-DIPHENYLETHANE (35) C3 1,1'-DIPHENYLETHANE (37) Cosdenol 180 RB Solvent 200B C4 1,1'-DIPHENYLETHANE (38) Figure 24 Comparison of detailed GCxGC-TOFMS hydrocarbon type analyses for Cosdenol 180 and RB Solvent 200B

38 29 Figure 25 Examples of compounds used in GCxGC-TOFMS/FID comparative analysis

39 30 In addition to material presented thus far, maps were prepared showing differences between GCxGC-TOFMS/FID chromatograms (see Figure 26 and Figure 27) similar to those reported earlier for GCxGC-FID (Figure 15 and Figure 16). Such representation allows for rapid recognition of regions of deviation between samples. Cosdenol 114 Atosol 115 Atosol Cosdenol 114 a) b) Figure 26 Differentiation plots for (a) Cosdenol 104 & Atosol 115 and (b) Atosol 115 & Cosdenol 104 Cosdenol 180 RB Solvent 200B RB Solvent 200B - Cosdenol 180 a) b) Figure 27 Differentiation plots for (a) Cosdenol 180 & RB Solvent 200B and (b) RB Solvent 200B & Cosdenol 180

40 ACKNOWLEDGEMENTS The authors would like to acknowledge partial funding from the Government of Canada s Interdepartmental Program of Energy Research and Development, PERD Petroleum Conversion for Cleaner Air.

41 32 APPENDIX A: SIMDIS ASTM D2887

42 33 Table A1 SimDis table Client ID COSDENOL 104 COSDENOL 180 RB SOLV 200B ATOSOL 115 ASTM D2887 Recovery Fraction Temperature Temperature Temperature Temperature (wt%) ( C) ( C) ( C) ( C)

43 34 Client ID COSDENOL 104 COSDENOL 180 RB SOLV 200B ATOSOL 115 ASTM D2887 Recovery Fraction Temperature Temperature Temperature Temperature (wt%) ( C) ( C) ( C) ( C)

44 35 Client ID COSDENOL 104 COSDENOL 180 RB SOLV 200B ATOSOL 115 ASTM D2887 Recovery Fraction Temperature Temperature Temperature Temperature (wt%) ( C) ( C) ( C) ( C) Carbon (wt%) Hydrogen (wt%)

45 36 APPENDIX B: PIONA DATA

46 37 Table B1 PIONA data for COSDENOL 104 REPORT IN WEIGHT % NORMALIZED Saturated Unsaturated C-num Napht Paraffins Napht Paraffins Arom Totals Iso Norm Iso Norm Totals Recovery <200 C Fraction From SIMDIS (ASTM 2887): % REPORT IN WEIGHT % Saturated Unsaturated C-num Napht Paraffins Napht Paraffins Arom Totals Iso Norm Iso Norm Totals

47 38 Table B2 PIONA data for ATOSOL 115 REPORT IN WEIGHT % NORMALIZED Saturated Unsaturated C-num Napht Paraffins Napht Paraffins Arom Totals Iso Norm Iso Norm Totals Recovery <200 C Fraction From SIMDIS (ASTM 2887): % REPORT IN WEIGHT % Saturated Unsaturated C-num Napht Paraffins Napht Paraffins Arom Totals Iso Norm Iso Norm Totals No PIONA data for COSDENOL180 because its initial boiling point is > 200 C. No PIONA data for RB Solvent 200B because its initial boiling point is >200 C.

48 39 APPENDIX C: DHA DATA

49 40 Table C1 DHA analysis by boiling point and by carbon number for COSDENOL 104 Recovery <200C Fraction From SIMDIS (ASTM 2887): % DHA By BP C Sum of By Bp Totals By CNo Start BP - (ibp) End BP (ibp) Simdist %off n-paraffins Isoparaffins Olefins Naphthenes Aromatics Unknown Total DHA by C-Num C-num n- Paraffins Isoparaffins Olefins Naphthenes Aromatics Unknown Totals Totals

50 41 Table C2 DHA analysis by boiling point and by carbon number for ATOSOL 115 Recovery <200 C Fraction From SIMDIS (ASTM 2887): % DHA By BP C Start BP - (ibp) End BP (ibp) Simdist %off n-paraffins Isoparaffins Olefins Naphthenes Aromatics Unknown Total DHA By BP C Start BP Sum of Totals By End BP by Bp CNo Simdist %off n-paraffins Isoparaffins Olefins Naphthenes Aromatics Unknown Total DHA by C-Num C-num n- Paraffins Isoparaffins Olefins Naphthenes Aromatics Unknown Totals Totals

51 42 No DHA data for COSDENOL180 because its initial boiling point is > 200 C. No DHA data for RB Solvent 200B because its initial boiling point is > 200 C.

52 43 APPENDIX D: SPE-GC-MS AND PIONA DATA

53 44 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) COSDENOL 105 ATOSOL 115 Method PIONA SPE/GC-MS Total PIONA SPE/GC-MS Total IBP- IBP- Boiling range IBP-200 o C 200 o C-FBP FBP IBP-200 o C 200 o C-FBP FBP SATURATES Total paraffins Isoparaffins n-paraffins Cycloparaffins Monocycloparaffins Dicycloparaffins Tricycloparaffins Rings cycloparaffins Rings cycloparaffins Rings cycloparaffins AROMATICS Monoaromatics Alkylbenzenes Benzocycloalkanes Benzodicycloalkanes Diaromatics Naphthalenes Naphthocycloalkanes Fluorenes Triaromatics Phenanthrenes Phenanthrocycloalkanes Tetraaromatics Pyrenes/Benzofluorenes Chrysenes Pentaaromatics Benzpyrenes/Perylenes Dibenzanthracenes Unidentified CnH2n-32/CnH2n CnH2n-36/CnH2n-26S CnH2n-38/CnH2n-28S CnH2n-40/CnH2n-30S CnH2n-42/CnH2n-32S CnH2n-44/CnH2n-34S Aromatic Sulfur Benzothiophenes Dibenzothiophenes Benzonaphthothiophenes OLEFINS TOTAL

54 45 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) COSDENOL RB SOLV B Method SPE/GC-MS SPE/GC-MS Boiling range IBP-FBP IBP-FBP SATURATES Total paraffins Isoparaffins n-paraffins Cycloparaffins Monocycloparaffins Dicycloparaffins Tricycloparaffins Rings cycloparaffins Rings cycloparaffins Rings cycloparaffins AROMATICS Monoaromatics Alkylbenzenes Benzocycloalkanes Benzodicycloalkanes Diaromatics Naphthalenes Naphthocycloalkanes Fluorenes Triaromatics Phenanthrenes Phenanthrocycloalkanes Tetraaromatics Pyrenes/Benzofluorenes Chrysenes Pentaaromatics Benzpyrenes/Perylenes Dibenzanthracenes Unidentified CnH2n-32/CnH2n CnH2n-36/CnH2n-26S CnH2n-38/CnH2n-28S CnH2n-40/CnH2n-30S CnH2n-42/CnH2n-32S CnH2n-44/CnH2n-34S Aromatic Sulfur Benzothiophenes Dibenzothiophenes Benzonaphthothiophenes OLEFINS TOTAL

55 46 APPENDIX E: GC-FIMS

56 CanmetENERGY Devon Table E1 GC-FIMS + PIONA data for COSDENOL 104 DILUTED TOTAL NEAT TOTAL HC Type / #C C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 Sum IBP-FBP Sum IBP-FBP Saturates Paraffins Isoparaffins N-paraffins Cycloparaffins Monocycloparaffins Dicycloparaffins Polycycloparaffins Aromatics Monoaromatics Benzenes Indanes/tetralins Indenes/benzocycloalkane Diaromatics Naphthalenes Acenaphthenes/biphenyls Acenaphthalenes/fluorenes Triaromatics Phenanthrenes/anthracenes Cyclopentanophenanthrenes Tetraaromatics Pyrenes/fluoranthenes Chrysenes/benzoanthracenes Aromatic Sulfur Benzothiophenes Dibenzothiophenes Naphthobenzothiophenes Total No GC-FIMS data for ATOSOL 115 because its initial boiling point is < 200 C. 47

57 CanmetENERGY Devon Table E2 GC-FIMS data for COSDENOL 180 TOTAL TOTAL HC Type / #C C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 IBP-FBP IBP-FBP Saturates Paraffins Isoparaffins N-paraffins Cycloparaffins Monocycloparaffins Dicycloparaffins Polycycloparaffins Aromatics Monoaromatics Benzenes Indanes/tetralins Indenes/benzocycloalkane Diaromatics Naphthalenes Acenaphthenes/biphenyls Acenaphthalenes/fluorenes Triaromatics Phenanthrenes/anthracenes Cyclopentanophenanthrenes Tetraaromatics Pyrenes/fluoranthenes Chrysenes/benzoanthracenes Aromatic Sulfur Benzothiophenes Dibenzothiophenes Naphthobenzothiophenes Total

58 CanmetENERGY Devon Table E3 GC-FIMS data for RB SOLVENT 200B TOTAL TOTAL HC Type / #C C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 IBP-FBP IBP-FBP Saturates Paraffins Isoparaffins N-paraffins Cycloparaffins Monocycloparaffins Dicycloparaffins Polycycloparaffins Aromatics Monoaromatics Benzenes Indanes/tetralins Indenes/benzocycloalkane Diaromatics Naphthalenes Acenaphthenes/biphenyls Acenaphthalenes/fluorenes Triaromatics Phenanthrenes/anthracenes Cyclopentanophenanthrenes Tetraaromatics Pyrenes/fluoranthenes Chrysenes/benzoanthracenes Aromatic Sulfur Benzothiophenes Dibenzothiophenes Naphthobenzothiophenes Total

59 CanmetENERGY Devon Hydrocarbon Content (mass%) GC-FIMS and PIONA for COSDENOL Olefins Acenaphthalenes/fluorenes Acenaphthenes/biphenyls Naphthalenes Indenes (benzocycloalkane) Indans/tetralins Benzenes Iso- + N-Paraffins C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 Carbon Number Figure E1 GC-FIMS and PIONA for COSDENOL

60 CanmetENERGY Devon Hydrocarbon Content (mass%) GC-FIMS and PIONA for ATOSOL Olefins Acenaphthalenes/fluorenes Acenaphthenes/biphenyls Naphthalenes Indenes (benzocycloalkane) Indans/tetralins Benzenes Iso- + N-Paraffins C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 Carbon Number Figure E2 GC-FIM and PIONA for ATOSOL

61 CanmetENERGY Devon Hydrocarbon Content (mas%) GC-FIMS and PIONA for COSDENOL Olefins Acenaphthalenes/fluorenes Acenaphthenes/biphenyls Naphthalenes Indenes (benzocycloalkane) Indans/tetralins Benzenes Iso- + N-Paraffins C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 Carbon Number Figure E3 GC-FIMS and PIONA for COSDENOL

62 CanmetENERGY Devon Hydrocarbon Content (mas%) GC-FIMS and PIONA for RB SOLV 200B Olefins Acenaphthalenes/fluorenes Acenaphthenes/biphenyls Naphthalenes Indenes (benzocycloalkane) Indans/tetralins Benzenes Iso- + N-Paraffins C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 Carbon Number Figure E4 GC-FIMS and PIONA for RB SOLV 200B 53

63 54 APPENDIX F: GCXGC FID

64 55 a) b) c) Figure F1 GCxGC-FID chromatograms of Cosdenol 104: (a) 2D view, (b) 3D view, (c) 2D view together with classification regions

65 56 a) b) c) Figure F2 GCxGC-FID chromatograms of Atosol 115: (a) 2D view, (b) 3D view, (c) 2D view together with classification regions

66 57 a) b) c) Figure F3 GCxGC-FID chromatograms of Cosdenol 180: (a) 2D view, (b) 3D view, (c) 2D view together with classification regions

67 58 a) b) c) Figure F4 GCxGC-FID chromatograms of RB Solvent 200B: (a) 2D view, (b) 3D view, (c) 2D view together with classification regions

68 59 APPENDIX G: GCXGC TOFMS/FID

69 60 a) b) Figure G1 GCxGC-TOFMS/FID chromatograms of Cosdenol 104: (a) 2D view together with classification regions, (b) 3D view

70 61 a) b) Figure G2 GCxGC-TOFMS/FID chromatograms of Atosol 115: (a) 2D view together with classification regions, (b) 3D view

71 62 a) b) Figure G3 GCxGC-TOFMS/FID chromatograms of Cosdenol 180: (a) 2D view together with classification regions, (b) 3D view

72 63 a) Figure G4 GCxGC-TOFMS/FID chromatograms of RB Solvent 200B: (a) 2D view together with classification regions, (b) 3D view b)