COMPARATIVE HYDROCARBON ANALYSIS OF COSDENOL 180, RB SOLVENT 200B, AND CPCHEM NAPHTHALENE SAMPLES

Transcription

1 FINAL REPORT COMPARATIVE HYDROCARBON ANALYSIS OF COSDENOL 180, RB SOLVENT 200B, AND CPCHEM NAPHTHALENE SAMPLES R. Gieleciak, C. Fairbridge, C. Lay and D. Hager CanmetENERGY DEVON Work performed for: CanmetENERGY, Natural Resources Canada Fuels for Advanced Combustion Engines Working Group APRIL 2011 DIVISION REPORT DEVON INT Natural Resources Canada, Published by Coordinating Research Council, Inc. All rights reserved.

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 approached by the Coordinating Research Council (CRC) Fuels for Advanced Combustion Engines (FACE) Working Group and asked to provide advanced analytical characterization of a sample tagged as a CPChem Naphthalenes. This report provides 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: GC-FIMS (gas chromatography-field ionization mass spectrometry) and GCxGC (comprehensive two-dimensional gas chromatography) with both SCD/FID and TOFMS. A summary of the analyses is reported and the detailed analytical results are provided. In addition, comparative studies of previously analyzed samples, Cosdenol 180 and RB solvent 200, and a proposed new stream were performed. Diesel samples characterized in this report will be used for FACE research diesel fuel testing. This report is an extension of a report previously released on the CRC website:

4 iii CONTENTS DISCLAIMER... i EXECUTIVE SUMMARY... ii 1.0 INTRODUCTION EXPERIMENTAL SIMULATED DISTILLATION GAS CHROMATOGRAPHY FIELD IONIZATION MASS SPECTROMETRY (GC-FIMS) COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY (GC GC) RESULTS AND DISCUSSION SIMULATED DISTILLATION GC-FIMS COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY GC GC-SCD/FID GC GC-TOFMS/FID CONCLUSIONS ACKNOWLEDGEMENTS APPENDIX A: SIMDIS AST APPENDIX B: GC-FIMS APPENDIX C: GCxGC-SCD/FID GROUP TYPE ANALYSIS TABLES Table 1 Sample names, sample tags, and some known properties for samples analyzed in this report a)... 1 Table 2 Operating conditions for GC GC-FID/SCD analysis... 5 Table 3 Operating conditions for GC GC-TOFMS/FID analysis... 5 Table 4 GC-FIMS hydrocarbon type analysis... 7 Table 5 Operating conditions for GC GC-FID/SCD analysis

5 iv Table 6 Operating conditions for GC GC-TOFMS/FID analysis Table 7 Quantitative group type results of GC GC-FID separation Table A 1 Simulated distillation data Table B 1 GC-FIMS data for CPChem Naphthalene sample Table C 1 GCxGC SCD/FID hydrocarbon type analysis FIGURES Figure 1 Chromatagram illustrating alignment of subsequent simultaneous response of dual detectors TIC (orange) and FID (green)... 4 Figure 2 Simulated distillation curves for Cosdenol180, RB Solvent, and CPChem Naphthalenes streams (based on ASTM D2887 method)... 6 Figure 3 Graphic version of GC-FIMS data presented in Table 4. Details in text Figure 4 GC-FIMS hydrocarbon types by carbon number for Cosdenol 180 sample... 9 Figure 5 GC-FIMS hydrocarbon types by carbon number for RB Solvent 200B sample Figure 6 GC-FIMS hydrocarbon types by carbon number for CPChem Naphthalene sample Figure 7 GC-FIMS collective contour plot for Cosdenol 180, RB Solvent 200B, and CPChem Naphthalene samples Figure 8 Schematic example of compound class distribution using traditional column set combination. Meaning of symbols: a6 6 carbon aromatics, A5 5 carbon ring aliphatic, A6 6 carbon ring aliphatic Figure 9 Magnification of n-paraffinic, iso-paraffinic, and Monocycloparaffinic/olefinic regions Figure 10 Examples of compounds assigned to groups used in GC GC- FID typing... 15

6 v Figure 11 Graphic results of GC GC-FID speciation Figure 12 Example of column overloading by biphenyl compounds in RB Solvent sample Figure 13 GC GC-FID bubble plot chromatograms of Cosdenol 180 with selected classification groups Figure 14 GC GC-FID bubble plot chromatograms of RB Solvent 200B with selected classification groups Figure 15 GC GC-FID bubble plot chromatograms of CPChem Naphthalenes with selected classification groups Figure 16 Chromatograms of analyzed samples obtained by GC GC- SCD, with two sulfur classes found in the CPChem sample Figure 17 Examples of GC GC-TOFMS/FID chromatograms: (a) normal column combination (b) reversed column combination Figure 18 The GC GC-TOFMS/FID chromatograms with selected hydrocarbon group types: (a) Cosdenol 180, (b) RB Solvent 200B, (c) CPChem Naphthalenes. Region meanings: 1: Tetraethylbenzene, 2: 1,1 -diphenylethane, 3: C2-C3 1,1 - diphenylethanes, 4: dimethylbenzene, 5: C11-alkylbenzenes, 6: C2-C5 1,1 -diphenylethanes, 7: i+n-paraffines, 8: naphthalene, 9:methylnaphthalenes, 10: C2 alkylnaphthalenes, 11: C3-C5 alkylnaphthalenes Figure 19 Examples of mass spectra for selected species. On the left: diphenyl, acenaphthene and 2-ethenyl naphthalene Figure 20 Selected ion chromatograms (SIC) for analyzed samples. Columns (from left): Cosdenol 180, RB Solvent 200B, CRChem Naphthalenes. Rows (from top): selected ions: 57+71, , 133, and 91.The color scale is maintained in the same range for all the chromatograms Figure 21 Examples of mass spectra of selected multi-branch alkylbenzene isomers (on the left) and lower-branch alkylbenzenes (on the right)

7 vi Figure 22 Mass spectral filters applied to show C1 C4 alkyl-substituted naphthalenes in the analyzed samples Figure 23 Examples of mass spectra of selected isomers of naphthalenes: a) naphthalene, b) 1-methyl naphthalene, c) 1-propyl naphthalene, d) 2,3,6-trimethyl naphthalene, e) 1-butyl-naphthalene, and f) 2- methyl-1-propyl naphthalene Figure C 1 Two- and three-dimensional representations of GCxGC-FID chromatograms of analyzed samples... 39

8 1 1.0 INTRODUCTION This year CPChem is proposing to substitute a new naphthalenes source of aromatics to replace the heavy aromatics from the Cosdenol180 and RB Solvent 200 in FACE diesel fuels such as #7 and #8. This substitution was necessary to supply the FACE diesel fuels to Europe since previously proposed stream RBSolv200 did not have REACH Certification. A description of samples provided for analysis is presented in Table 1. Table 1 Sample names, sample tags, and some known properties for samples analyzed in this report a) Cosdenol 180 RB Solvent 200B CPChem Naphthalenes CanmetENERGY ID LCO CAS# Physical state liquid liquid liquid Flash point 82.2 C C 107 C Specific gravity (water = 1.00) Boiling/condensation point C 232 C C a) Taken from Material Safety Data Sheet 2.0 EXPERIMENTAL 2.1 SIMULATED DISTILLATION Firstly, simulated distillation analysis (ASTM D2887), which provides the boiling point distribution of petroleum products for the boiling range between C5 (35 C) and C44 (538 C), is performed on each sample. The distillation method is simulated by the use of gas chromatography (in this case, an Analytical Control Systems, Inc., Simulated Distillation Custom Analyzer based on the HP-6890 series gas chromatograph), whereby a nonpolar capillary column is used to elute the hydrocarbon components of the sample in order of increasing boiling point.

9 2 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 for 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 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 accurate measurements of the 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 Detailed Hydrocarbon Analysis (DHA, ASTM D6730) operated with a prefractionator to eliminate hydrocarbons that boil above 200 C (392 F).

10 3 2.3 COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY (GC GC) Comprehensive two-dimensional gas chromatography (GC GC) 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 out of the second column enter the detector. The main factors contributing to the 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 rapid (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 GC GC 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 a general hydrocarbon detector. All quantitative analysis provided in this report was based on the FID. 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 GC GC-TOFMS is equipped with an FID. After matching the TOFMS and FID signals, both qualitative and quantitative results can be obtained simultaneously. An example of such a chromatogram is shown in Figure 1.

11 4 Figure 1 Chromatagram illustrating alignment of subsequent simultaneous response of dual detectors TIC (orange) and FID (green) One of the main benefits of orthogonal GC GC 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 this report. The GC GC instruments were provided by Leco Instruments and utilized a cryogenically cooled modulator. The column features and the operating conditions for both GC GC-FID/SCD and GC GC-TOFMS/FID experiments are listed in Table 2 and Table 3, respectively. Detectors used in the analysis are as follows: FID, SCD (sulfur chemiluminescence detector), and TOFMS.

12 5 Table 2 Operating conditions for GC GC-FID/SCD analysis 1 st column Varian Factor 4 VF5-HT, 30 m x 0.32 mm DF: 0.1 Main oven program 50 C (1) to 350 C (0) at 3 C/min 2 nd column BPX-50, 1.0 m x 0.1 DF: 0.1 Secondary oven program 10 C offset from main oven Inlet temperature 350 C Injection size 1 L Split ratio 50:1 Carrier gas He, constant flow, 1.5 ml/min Modulator temperature 55 C offset from main oven Detector FID, 350 C with SCD adapter, 800 C Acquisition rate 100 Hz Modulation period 6 s Table 3 Operating conditions for GC GC-TOFMS/FID analysis 1 st column Varian factor 4 VF17-MS, 30 m x 0.32 mm DF: 0.1 Main oven program 50 C (0.2) to 330 C (9.8) at 3 C/min 2 nd column Varian factor 4 VF5-HT,1.5 m x 0.1 DF: 0.2 Secondary oven program 20 C offset from main oven Inlet temperature 350 C Injection size 0.2 L Split ratio 20:1 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 10 s Data handling, such as contour plotting, GC GC peak collection, retention time measurements, and peak volume calculations 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. The quantities of each compond are shown as a percentage of the total area of the quantified peaks. All quantitative analysis was based on FID output.

13 6 3.0 RESULTS AND DISCUSSION 3.1 SIMULATED DISTILLATION The simulated distillation analyses are 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 obtained during simulated distillation revealed similarities among analyzed samples. Clearly, Cosdenol 180 and RB Solvent 200B exhibit distillation curves that are higher than that of CPChem Naphthalenes. It was observed that the CPChem Naphthalenes are characterized by a milder, more regular simulated distillation curve run than the other samples. Both RB Solvent 200B and CPChem Naphthalenes have the same T10s. On the other hand, the T90s for Cosdenol and RB Solvent are the same, whereas T90 for CPChem Naphthalenes is about 25 C lower. Both RB Solvent 200B and Cosdenol 180 contain more heavier fractions boiling close to or above 400 C, whereas CPChem Naphthalenes distillation is finished below 350 C. Figure 2 Simulated distillation curves for Cosdenol180, RB Solvent, and CPChem Naphthalenes streams (based on ASTM D2887 method)

14 7 3.2 GC-FIMS The GC-FIMS hydrocarbon analysis for Cosdenol 180 and RB Solvent was reported previously and wasn t repeated for these samples for the purposes of this report. The GC-FIMS data for analyzed CPChem Naphthalenes as well as Cosdenol and RB solvent are presented in Table 4. The detailed GC-FIMS data for CPChem Naphthalenes sample is provided in tabulated form in Appendix B. Figure 3 illustrates the GC-FIMS results in Table 4. Table 4 GC-FIMS hydrocarbon type analysis Cosdenol 180 RB Solv 200B CPChem Naphthalenes HC Type / #C IBP-FBP IBP- FBP IBP-FBP Saturates i+ n-paraffins iso-paraffins 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

15 8 Figure 3 Graphic version of GC-FIMS data presented in Table 4. Details in text. The layout of consecutive bar plots on Figure 3 was created intentionally to show a zoom-in representation of hydrocarbon types found in analyzed samples. The

16 9 first bar plot shows a clear difference between the aromatic and saturate contents for the older streams (Cosdenol and RB Solvent) and CPChem Naphthalenes. However, in many cases such information is not sufficient. Following further subdivision of major hydrocarbon types into more detailed groups we can see true discrepancies between the analytes. The last plot in Figure 3 highlights the crucial differences between CPChem Naphthalenes and the other two samples. A more detailed comparison can be achieved by plotting GC-FIMS data in the form of the distribution of hydrocarbon types by carbon number. Such visual outputs for all streams are presented and explained in Figure 4 Figure 6. Figure 7 shows one contour plot with the same unified color scale for all samples. Figure 4 GC-FIMS hydrocarbon types by carbon number for Cosdenol 180 sample

17 10 Figure 5 GC-FIMS hydrocarbon types by carbon number for RB Solvent 200B sample Figure 6 GC-FIMS hydrocarbon types by carbon number for CPChem Naphthalenes sample

18 11 Cosdenol 180 RB Solvent 200B CPChem Naphthalenes Figure 7 GC-FIMS collective contour plot for Cosdenol 180, RB Solvent 200B, and CPChem Naphthalene samples 3.3 COMPREHENSIVE TWO-DIMENSIONAL GAS CHROMATOGRAPHY Two-dimensional gas chromatography was used for both quantitative and qualitative analyses. The following pages present the advanced characterization of aromatic samples in more detail and include two-dimensional chromatograms from both the GC GC-SCD/FID and GC GC-TOFMS/FID instruments. Recently, some parameters of the CanmetENERGY GC GC-SCD/FID instrument were changed. Details of changed operating conditions are listed in Table 5 and Table 6. For the sake of completeness, we repeated all the GC GC experiments for both Cosdenol 180 as well as RB Solvent using the new setup.

19 12 Table 5 Operating conditions for GC GC-FID/SCD analysis (the most important discrepancies between previously reported and recent column conditions are marked in red). 1 st column Varian factor 4 VF5-HT, 30 m x 0.32 mm DF: 0.1 Main oven program 50 C (1) to 350 C (0) at 3 C/min 2 nd column BPX-50, 1.0 m x 0.1 DF: 0.1 Secondary oven program 10 C offset from main oven Inlet temperature 350 C Injection size 1 L Split ratio 50:1 Carrier gas He, constant flow, 1.5 ml/min Modulator temperature 55 C offset from main oven Detector FID, 350 C with SCD adapter, 800 C Acquisition rate 100 Hz Modulation period 6 s Table 6 Operating conditions for GC GC-TOFMS/FID analysis (the most important discrepancies between previously reported and recent column conditions are marked in red). 1 st column Varian factor 4 VF17-MS, 30 m x 0.32 mm DF:0.1 Main oven program 50 C (0.2) to 330 C (9.8) at 3 C/min 2 nd column Varian Factor 4 VF5-HT,1.5 m x 0.1 DF:0.2 Secondary oven program 20 C offset from main oven Inlet temperature 350 C Injection size 0.2 L Split ratio 20:1 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 10 s GC GC-SCD/FID The CanmetENERGY GC GC-FID instrument is equipped with a traditional column set combination (see Table 5). 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

20 13 obtained. The separation on the second column is dependent on specific relationships between the stationary phase and the analytes. This setup provides a structured group separation. Classifications of hydrocarbon type regions were created and are shown in Figure 8 and Figure 9. The ordered structures enable rapid profiling and quantification. Selected representatives from compound classes are shown in Figure 10. All GC GC-FID results presented in this report were based on neat (undiluted) samples. The compound classes presented in Figure 8 and Figure 10 were used for reporting the results of group type separations for all analyzed samples. Table 7 gives information on group type content obtained after GC GC-FID analysis. The detailed tabulated quantitative and structural results are presented in Appendix C. Figure 11 presents results from Table 7 in graphic form. Table 7 Quantitative group type results of GC GC-FID separation Class Cosdenol 180 RB Solv 200B CPChem Naphthalenes n-paraffins iso-paraffins Monocycloparaffins a a6a5/a6a a6a a6a5a a6a6a a6a6a6a a6a6a6a LUMP

21 14 Figure 8 Schematic example of compound class distribution using traditional column set combination. Meaning of symbols: a6 6 carbon aromatics, A5 5 carbon ring aliphatic, A6 6 carbon ring aliphatic. Figure 9 Magnification of n-paraffinic, iso-paraffinic, and Monocycloparaffinic/olefinic regions

22 15 Figure 10 Examples of compounds assigned to groups used in GC GC-FID typing

23 16 Figure 11 Graphic results of GC GC-FID speciation Running neat (undiluted) samples creates some problems connected with column and/or detector overloading. The example presented on Figure 12 for RB Solvent 200B sample shows this situation. Such phenomena can result in significant shifting of the peak into different classification regions. It may be necessary to monitor such peaks and shift classification regions. On the other hand, samples can be diluted. However, running the GC after sample dilution can cause the loss of information about less-concentrated species in the sample.

24 17 Figure 12 Example of column overloading by biphenyl compounds in RB Solvent sample 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 temperature scale using a correlation established between boiling point of n-paraffins and their retention time. This exercise allowed for presentation of GC GC-FID maps in the boiling point domain. Additionally, component peaks found in chromatograms were presented in bubble plot form, where the size of the bubble is related to the component concentration. This type of visualization was used in a previous report for Cosdenol 180 and RB Solvent 200B. However, due to chromatographic condition changes we present new results in Figure 13, Figure 14, and Figure 15. Most of the hydrocarbon species fall into the diaromatic region of the chromatographic map (green bubbles). At this level of analysis, however, the exact natures of the chemical species are not clear. GC GC TOFMS and GC-FIMS experiments confirmed that the CPChem sample consists of alkylated naphthalenes. On the other hand, the diaromatic region in the Cosdenol 180 and RB Solvent samples consists mostly of biphenyls and/or diphenyl alkanes.

25 18 Figure 13 GC GC-FID bubble plot chromatograms of Cosdenol 180 with selected classification groups Figure 14 GC GC-FID bubble plot chromatograms of RB Solvent 200B with selected classification groups

26 19 Figure 15 GC GC-FID bubble plot chromatograms of CPChem Naphthalenes with selected classification groups Based on GC GC-SCD analysis we could detect different kinds of sulfur classes in analyzed samples. It can be seen from Figure 16 that there are significant differences in the sulfur contents of the streams. The first samples, Cosdenol 180 and RB Solvent 200, contain no sulfur or negligible amounts, whereas the CPChem Naphthalenes sample contains almost 400 ppm sulfur, distributed mostly between two groups, benzothiophenes and dibenzothiophenes.

27 20 Figure 16 Chromatograms of analyzed samples obtained by GC GC-SCD, with two sulfur classes found in the CPChem sample GC GC-TOFMS/FID The CanmetENERGY GC GC-TOFMS/FID instrument is equipped with a reversed column set combination (see Table 6), where first column is a long polar column and the second is a short nonpolar column. In this case, separation will be primarily governed by the specific interactions between analytes and the column s polar stationary phase. Figure 17 provides a quick reference illustrating distinctions between chromatograms obtained using the normal and reversed column setups.

28 21 Saturates Aromatics a) b) Figure 17 Examples of GC GC-TOFMS/FID chromatograms: (a) normal column combination (b) reversed column combination The previous report 1 contained a detailed description of GC GC-TOFMS results for Cosdenol 180 and RB Solvent 200B. However, in Figure 18 the GC GC- TOFMS/FID chromatograms for all samples are presented with key regions selected. The circled areas enable the reader to quickly determine important differences between all these samples. Images were digitally enhanced and the color scale was unified pdf

29 22 a) b) c) Figure 18 The GC GC-TOFMS/FID chromatograms with selected hydrocarbon group types: (a) Cosdenol 180, (b) RB Solvent 200B, (c) CPChem Naphthalenes. Region meanings: 1: Tetraethylbenzene, 2: 1,1 - diphenylethane, 3: C2-C3 1,1 -diphenylethanes, 4: dimethylbenzene, 5: C11- alkylbenzenes, 6: C2-C5 1,1 -diphenylethanes, 7: i+n-paraffines, 8: naphthalene, 9:methylnaphthalenes, 10: C2 alkylnaphthalenes, 11: C3-C5 alkylnaphthalenes The GC GC-TOFMS provides a large amount of structural information on compounds present in the sample. Species are usually identified by searching for matching spectra in the U.S. National Institute of Standards and Technology (NIST) mass spectral libraries. The main difficulty after library searching is connected with authentication of the results obtained. In many cases, accurate name attribution of a detected peak was impossible owing to the small quantity of analyte, the absence of an appropriate mass spectrum in the spectrometry library, or mass spectrum similarities between isomers. As an example, we had to assign hydrocarbon

30 23 compounds to peaks found in Cosdenol 180 and RB Solvent 200B, which were recognized after analysis as diphenyls. Figure 19 (on the left) shows mass spectra that look the same for three different chemical compounds (biphenyl, acenaphthene, 2- ethenyl naphthalene). Figure 19 Examples of mass spectra for selected species. On the left: diphenyl, acenaphthene and 2-ethenyl naphthalene. Total ion chromatography (TIC) provides information similar to that obtained using other GC detectors (see Figure 18). However, very often (but not always) we can obtain more structural, convenient, and easier-to-interpret results by extracting selected ion chromatograms (SIC). An example of such a methodology applied to samples in this report is presented in Figure 20. The first row of Figure 20 clearly shows paraffinic hydrocarbons in the CPChem Naphthalenes sample (selected ions: 57 and 71). The second row shows olefinic and/or naphthene species; the third row, multi-branch alkylbenzenes; and the last row (selected ion 91 as well as 105), lower-

31 24 branch alkylbenzenes, and straight-chain diphenylalkanes. Mass spectra used in differentiation of multi- or lower-branch alkylbenzenes are presented in Figure , 71 Cosdenol 180 RB solvent 200B CPChem 55, 69, Figure 20 Selected ion chromatograms (SIC) for analyzed samples. Columns (from left): Cosdenol 180, RB Solvent 200B, CRChem Naphthalenes. Rows (from top): selected ions: 57+71, , 133, and 91.The color scale is maintained in the same range for all the chromatograms.

32 25 Figure 21 Examples of mass spectra of selected multi-branch alkylbenzene isomers (on the left) and lower-branch alkylbenzenes (on the right). Figure 22 shows a sum of mass 128 and a set of monoisotopic masses 141, 155, 169, 183, 197 and 211. Such mass combination exemplifies m/z values that are characteristic of the naphthalene group (ion selection was based on retrospective analysis of mass spectra of isomers of alkyl naphthalenes presented in part in Figure 23). Therefore, we can now visually identify the position in the two-dimensional space that belongs to naphthalenes and distinguish them from biphenyls. Cosdenol 180 includes intense peaks for selected ions, but peak position as well as mass spectra for these peaks exclude them as naphthalenes. On the other hand, the selected ions chromatogram for RB Solvent in Figure 22 clearly indicates a low concentration of naphthalene compounds in the sample.

33 26 Figure 22 Mass spectral filters applied to show C1 C4 alkyl-substituted naphthalenes in the analyzed samples

34 27 Figure 23 Examples of mass spectra of selected isomers of naphthalenes: a) naphthalene, b) 1-methyl naphthalene, c) 1-propyl naphthalene, d) 2,3,6- trimethyl naphthalene, e) 1-butyl-naphthalene, and f) 2-methyl-1-propyl naphthalene

35 CONCLUSIONS This work provides advanced hydrocarbon characterization of the CPChem Naphthalenes stream and comparisons of the chemistries of a newly proposed fuel and older streams: Cosdenol 180 and RB Solvent 200B. The results presented in this report consist of data obtained using the following analytical techniques: GC-FIMS (gas chromatography field ionization mass spectrometry) and GC GC (comprehensive two-dimensional gas chromatography) with both SCD/FID and TOFMS. Detailed results including GC-FIMS and GCxGC-FID analyses are presented in the appendices. This report confirms that: - Both RB Solvent 200B and CPChem Naphthalenes have the same T10. On the other hand, the T90s for Cosdenol 180 and RB Solvent 200Bis the same, whereas the T90 for CPChem Naphthalenes is about 25 C lower. - There are significant differences in hydrocarbon contents of old and new streams. - Differences appear in the diaromatic region. The CPChem Naphthalenes sample consists mostly naphthalene while Cosdenol 180 and RB Solvent 200Bconsist mostly of diphenyls/biphenyls. - The saturates content (~27%) of CPChem Naphthalenes is high in comparison with the other two samples. - The CPChem Naphthalenes sample contains a meaningful concentration of organic sulfur, while Cosdenol 180 and RB Solvent 200Bcontain no sulfur at all. The diaromatics, in the form of naphthalenes like those in the newly proposed fuel source, provide good representation of the aromatic compounds found in commercial ULSDs. However, the concern is that these two groups of compounds (naphthalenes and diphenyls) could have considerably different physical properties or have different effects on engine combustion characteristics.

36 29 We can not speculate on that in this report. The autoignition temperature, for example, for naphthalene and biphenyl is close, 530 C and 570 C, respectively. 5.0 ACKNOWLEDGEMENTS The authors would like to acknowledge partial funding support from the Government of Canada s Interdepartmental Program of Energy Research and Development, PERD Petroleum Conversion for Cleaner Air.

37 30 APPENDIX A: SIMDIS AST 2887

38 31 Table A 1 Simulated distillation data ID LCO ID LCO Client ID COSDENOL 180 RB SOLVENT 200B CRChem NAPHTHALENES Client ID COSDENOL 180 RB SOLVENT 200B CRChem NAPHTHALENES ASTM D2887 Recovery Fraction Temperature Temperature Temperature ASTM D2887 Recovery Fraction Temperature Temperature Temperature (wt%) ( C) ( C) ( C) (wt%) ( C) ( C) ( C)

39

40 33 APPENDIX B: GC-FIMS

41 34 Table B 1 GC-FIMS data for CPChem Naphthalene sample

42 35 APPENDIX C: GCXGC-SCD/FID GROUP TYPE ANALYSIS

43 36 Table C 1 GCxGC SCD/FID hydrocarbon type analysis COSDENOL 180 RB SOLVENT 200B CRChem NAPHTHALENES Class Area Area (%) Area Area (%) Area Area (%) Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Cyc-C Monocycloparaffins (total) LUMP a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6-c a6 (total)

44 37 a6a5/a6a a6a5/a6a a6a5/a6a a6a5/a6a6 (total) a6a5a a6a5a a6a5a a6a5a a6a5a a6a5a a6a5a a6a5a6 (total) a6a6-c a6a6-c a6a6-c a6a6-c a6a6-c a6a6-c5-c a6a6-c a6a6 (total) a6a6a a6a6a a6a6a a6a6a a6a6a a6a6a6 (total) a6a6a6a a6a6a6a a6a6a6a a6a6a6a a6a6a6a a6a6a6a a6a6a6a a6a6a6a a6a6a6a5 (total) a6a6a6a ip-c ip-c ip-c ip-c ip-c ip-c ip-c ip-c ip-c ip-c ip-c ip-c

45 38 ip-c ip-c ip-c ip-c ip-c ip-c ip-c ip-c ip-c ip-c iso-paraffins (total) n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-c n-paraffins (total)

46 39 Figure C 1 Two- and three-dimensional representations of GCxGC-FID chromatograms of analyzed samples