Comparative Hydrocarbon Analysis of Cosdenol 180, RB Solvent ...

FINAL REPORT 

PROTECTED BUSINESS INFORMATION 

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 2011-044-INT 

© Natural Resources Canada, 2011. Published by Coordinating Research Council, Inc. All rights reserved.

CanmetENERGY–Devon 

DISCLAIMER 

i PROTECTED BUSINESS INFORMATION 

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.


ii PROTECTED BUSINESS INFORMATION 

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: http://www.crcao.org/news/FACE/index.html.


iii PROTECTED BUSINESS INFORMATION 

CONTENTS 

DISCLAIMER ..................................................................................................................... i 

EXECUTIVE SUMMARY ................................................................................................ ii 

1.0 INTRODUCTION .................................................................................................. 1 

2.0 EXPERIMENTAL.................................................................................................. 1 

2.1 SIMULATED DISTILLATION............................................................................. 1 

2.2 GAS CHROMATOGRAPHY–FIELD IONIZATION MASS 

SPECTROMETRY (GC-FIMS) ............................................................................. 2 

2.3 COMPREHENSIVE TWO-DIMENSIONAL GAS 

CHROMATOGRAPHY (GC×GC) ........................................................................ 3 

3.0 RESULTS AND DISCUSSION............................................................................. 6 

3.1 SIMULATED DISTILLATION............................................................................. 6 

3.2 GC-FIMS ................................................................................................................ 7 


CHROMATOGRAPHY ....................................................................................... 11 

3.3.1 GC×GC-SCD/FID ................................................................................................ 12 

3.3.2 GC×GC-TOFMS/FID........................................................................................... 20 

4.0 CONCLUSIONS................................................................................................... 28 

5.0 ACKNOWLEDGEMENTS.................................................................................. 29 

APPENDIX A: SIMDIS AST 2887................................................................................. 30 

APPENDIX B: GC-FIMS................................................................................................ 33 

APPENDIX C: GCxGC-SCD/FID GROUP TYPE ANALYSIS.................................... 35 

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. ..................................... 12


iv PROTECTED BUSINESS INFORMATION 

Table 6 – Operating conditions for GC×GC-TOFMS/FID analysis................................. 12 

Table 7 – Quantitative group type results of GC×GC-FID separation ............................. 13 

Table A 1 – Simulated distillation data............................................................................. 31 

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

Table C 1 – GCxGC –SCD/FID hydrocarbon type analysis ............................................ 36 

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. ..................................................................................................................... 8 

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.......................................................................................................... 10 

Figure 6 – GC-FIMS hydrocarbon types by carbon number for CPChem 

Naphthalene sample.............................................................................................. 10 

Figure 7 – GC-FIMS collective contour plot for Cosdenol 180, RB Solvent 

200B, and CPChem Naphthalene samples............................................................ 11 

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................................................................................................................. 14 

Figure 9 – Magnification of n-Paraffinic, iso-Paraffinic, and 

Monocycloparaffinic/olefinic regions................................................................... 14 

Figure 10 – Examples of compounds assigned to groups used in GC×GC- 

FID typing............................................................................................................. 15


v PROTECTED BUSINESS INFORMATION 

Figure 11 – Graphic results of GC×GC-FID speciation ................................................... 16 

Figure 12 – Example of column overloading by biphenyl compounds in 

RB Solvent sample................................................................................................ 17 

Figure 13 – GC×GC-FID bubble plot chromatograms of Cosdenol 180 

with selected classification groups........................................................................ 18 

Figure 14 – GC×GC-FID bubble plot chromatograms of RB Solvent 200B 

with selected classification groups........................................................................ 18 

Figure 15 – GC×GC-FID bubble plot chromatograms of CPChem 

Naphthalenes with selected classification groups................................................. 19 

Figure 16 – Chromatograms of analyzed samples obtained by GC×GC- 

SCD, with two sulfur classes found in the CPChem sample ................................ 20 

Figure 17 – Examples of GC×GC-TOFMS/FID chromatograms: (a) 

‘normal’ column combination (b) ‘reversed’ column combination...................... 21 

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.................................................................................................. 22 

Figure 19 – Examples of mass spectra for selected species. On the left: 

diphenyl, acenaphthene and 2-ethenyl naphthalene.............................................. 23 

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, 55+69+97, 

133, and 91.The color scale is maintained in the same range for all 

the chromatograms................................................................................................ 24 

Figure 21 – Examples of mass spectra of selected multi-branch 

alkylbenzene isomers (on the left) and lower-branch alkylbenzenes 

(on the right). ........................................................................................................ 25


vi PROTECTED BUSINESS INFORMATION 

Figure 22 – Mass spectral filters applied to show C1–C4 alkyl-substituted 

naphthalenes in the analyzed samples................................................................... 26 

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................................................................................ 27 

Figure C 1 – Two- and three-dimensional representations of GCxGC-FID 

chromatograms of analyzed samples .................................................................... 39

1.0 INTRODUCTION 

1 


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 10-1042 10-1043 LCO 

CAS# 64742-94-5 147952-37-2 64741-59-9 

Physical state liquid liquid liquid 

Flash point 82.2°C 136.1°C 107°C 

Specific gravity (water = 1.00) 0.98 0.978 0.92 

Boiling/condensation point 236-318°C 232°C 162-364°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. 

CanmetENERGY–Devon

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). 



CHROMATOGRAPHY (GC×GC) 

3 


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. 


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. 


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 50C (1) to 350C (0) at 3C/min 

2 nd column BPX-50, 1.0 m x 0.1 DF: 0.1 

Secondary oven program 10C offset from main oven 

Inlet temperature 350C 

Injection size 1 L 

Split ratio 50:1 

Carrier gas He, constant flow, 1.5 mL/min 

Modulator temperature 55C 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 50C (0.2) to 330C (9.8) at 3C/min 

2 nd column Varian factor 4 VF5-HT,1.5 m x 0.1 DF: 0.2 



Injection size 0.2 L 




Detector TOFMS and FID 



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. 


3.0 RESULTS AND DISCUSSION 

3.1 SIMULATED DISTILLATION 

6 


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) 


3.2 GC-FIMS 

7 


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 

HC Type / #C IBP-FBP 

RB Solv CPChem 

200B 

IBP- 

Naphthalenes 

FBP IBP-FBP 

Saturates 0.37 0 26.87 

i+ n-Paraffins 0 0 13.44 

iso-Paraffins 0 0 10.01 

n-Paraffins 0 0 3.43 

Cycloparaffins 0.37 0 13.43 

Monocycloparaffins 0.37 0 5.94 

Dicycloparaffins 0 0 4.13 

Polycycloparaffins 0 0 3.36 

Aromatics 99.63 100 73.13 

Monoaromatics 32.73 35.98 13.75 

Benzenes 20.57 35.08 4.09 

Indanes/tetralins 4.81 0.74 6.52 

Indenes/benzocycloalkane 7.35 0.15 3.13 

Diaromatics 63.2 63.72 57.90 

Naphthalenes 2.01 4.29 51.10 

Acenaphthenes/biphenyls 56.1 59.43 4.48 

Acenaphthalenes/fluorenes 5.09 0 2.32 

Triaromatics 2.94 0.3 1.30 

Phenanthrenes/anthracenes 0.78 0.3 1.30 

Cyclopentanophenanthrenes 2.17 0 0.01 

Tetraaromatics 0.24 0 0.02 

Pyrenes/fluoranthenes 0.24 0 0.02 

Chrysenes/benzoanthracenes 0 0 0.00 

Aromatic sulfur 0.52 0 0.16 

Benzothiophenes 0.16 0 0.08 

Dibenzothiophenes 0.35 0 0.08 

Naphthobenzothiophenes 0.02 0 0.00 


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 


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 


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 


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 


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. 


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 50C (1) to 350C (0) at 3C/min 

2 nd column BPX-50, 1.0 m x 0.1 DF: 0.1 



Injection size 1 L 




Detector FID, 350°C with SCD adapter, 800°C 



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 50C (0.2) to 330C (9.8) at 3C/min 

2 nd column Varian Factor 4 VF5-HT,1.5 m x 0.1 DF:0.2 



Injection size 0.2L 




Detector TOFMS and FID 



3.3.1 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 


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 

Cosdenol RB Solv CPChem 

Class 


200B Naphthalenes 

n-Paraffins 0.61 0.03 6.31 

iso-Paraffins 0.01 0.02 8.29 

Monocycloparaffins 0.14 0.04 4.18 

a6 13.73 33.26 5.92 

a6A5/a6A6 12.69 7.85 5.01 

a6a6 67.78 57.19 61.91 

a6A5a6 3.10 0.92 7.60 

a6a6a6 1.68 0.64 0.77 

a6a6a6a5 0.23 0.06 0.00 

a6a6a6a6 0.03 0.00 0.00 

LUMP 0.00 0.00 0.00 


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 


15 


Figure 10 – Examples of compounds assigned to groups used in GC×GC-FID typing 


Figure 11 – Graphic results of GC×GC-FID speciation 

16 


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. 


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. 


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 


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. 


20 


Figure 16 – Chromatograms of analyzed samples obtained by GC×GC-SCD, with 

two sulfur classes found in the CPChem sample 

3.3.2 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. 



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. 

1 

http://www.crcao.org/news/FACE/HC%20Characterization%20of%20FACE%20Fairbridge201 

0.pdf

22 


a) b) 

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: C11alkylbenzenes, 

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 


c)

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, 2ethenyl 

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- 


24 


branch alkylbenzenes, and straight-chain diphenylalkanes. Mass spectra used in 

differentiation of multi- or lower-branch alkylbenzenes are presented in Figure 21. 

Cosdenol 180 

57, 71 

55, 69, 97 

133 

91 

RB solvent 200B CPChem 

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, 55+69+97, 133, and 91.The color scale is 

maintained in the same range for all the chromatograms. 


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. 


26 


Figure 22 – Mass spectral filters applied to show C1–C4 alkyl-substituted 

naphthalenes in the analyzed samples 


27 


Figure 23 – Examples of mass spectra of selected isomers of naphthalenes: a) 

naphthalene, b) 1-methyl naphthalene, c) 1-propyl naphthalene, d) 2,3,6trimethyl 

naphthalene, e) 1-butyl-naphthalene, and f) 2-methyl-1-propyl 

naphthalene 


4.0 CONCLUSIONS 

28 


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. 


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 1.1.3. Petroleum Conversion for Cleaner Air. 



30 

APPENDIX A: SIMDIS AST 2887 

PROTECTED BUSINESS INFORMATION

Table A 1 – Simulated distillation data 

31 


ID 100001041 100001044 LCO ID 100001041 100001044 LCO 

Client ID 

ASTM 

D2887 

Recovery 

Fraction 

COSDENOL 


RB 

SOLVENT 

200B 

CRChem 

NAPHTHALENES Client ID 

Temperature Temperature Temperature 

ASTM D2887 

Recovery 

Fraction 

COSDENOL 


RB 

SOLVENT 

200B 

CRChem 

NAPHTHALENES 

Temperature Temperature Temperature 

(wt%) (°C) (°C) (°C) (wt%) (°C) (°C) (°C) 

0.5 219 142.4 147.2 51 279.4 297.2 270.2 

1 222.4 142.4 170 52 280 297.2 271.4 

2 230.8 143.2 192.4 53 280.8 297.8 272.2 

3 239.6 172.2 207.6 54 282 298.4 272.8 

4 240.4 205 216.2 55 285.4 299.8 272.8 

5 241.8 210.4 227.8 56 289.4 300.4 273.4 

6 245.2 213.6 233.2 57 293.2 301.8 274 

7 249.2 219 233.8 58 294.6 302.4 274.8 

8 252.6 223.8 233.8 59 295.2 303 275.4 

9 254 228 234.6 60 295.2 303 276 

10 254.8 231.4 234.6 61 295.8 303.6 276.8 

11 254.8 234.2 236.6 62 295.8 304.4 277.4 

12 255.4 237.6 237.2 63 295.8 304.4 277.4 

13 255.4 242.4 237.2 64 295.8 305 278 

14 256 249.2 240.6 65 296.6 305.6 279.4 

15 256 256.8 244.8 66 296.6 307.6 280 

16 256 258 248 67 296.6 308.8 280.6 

17 257.4 262 250.8 68 297.2 310 281.2 

18 258.8 268 252.2 69 297.8 312 282 

19 263.4 272 252.8 70 299.8 312.6 282.6 

20 266 274 253.6 71 300.4 313.2 283.2 

21 268 275.4 254.2 72 300.4 313.2 284.6 

22 268.8 276.8 254.8 73 301 314 285.8 

23 268.8 278 254.8 74 301 314 287.2 

24 269.4 279.4 255.6 75 301.8 314.6 287.8 

25 269.4 280.8 255.6 76 302.4 315.2 287.8 

26 270 281.4 255.6 77 304.4 315.8 288.4 

27 270 282.8 256.2 78 305.6 316.6 289 

28 270 284 256.2 79 307.6 317.2 289.8 

29 270 284.8 256.8 80 308.8 317.8 290.4 

30 270 286 257.6 81 310.8 318.6 291.6 

31 270.8 286.8 257.6 82 312.6 320 292.4 

32 270.8 287.4 258.2 83 315.2 320.6 293.6 

33 270.8 288 258.2 84 316.6 321.4 295.6 

34 270.8 288.8 258.8 85 317.2 321.4 296.8 

35 270.8 289.4 258.8 86 320 322 298.8 

36 271.4 289.4 258.8 87 321.4 322 300.6 


32 


37 271.4 290 258.8 88 322.6 322 302 

38 271.4 290 259.6 89 325.4 322.6 303.2 

39 271.4 290.6 259.6 90 327.6 322.6 303.8 

40 271.4 291.4 259.6 91 330.2 324 304.4 

41 271.4 292 259.6 92 333 324.8 305.8 

42 271.4 292.6 260.8 93 335.8 325.4 307.6 

43 272 293.2 261.6 94 339.8 326.8 309.6 

44 272 294 262.2 95 346.6 328.2 312.8 

45 272 295.2 262.2 96 351.8 328.8 315.2 

46 272 295.2 263.6 97 360.4 333 318 

47 273.4 295.8 264.2 98 376.2 346 322.8 

48 275.4 296.6 265.6 99 397.8 369.6 330.2 

49 277.4 296.6 267.6 99.5 412.2 389.4 337 

50 278 296.6 268.8 



33 

APPENDIX B: GC-FIMS 


Table B 1 – GC-FIMS data for CPChem Naphthalene sample 


34 


35 


APPENDIX C: GCXGC-SCD/FID GROUP TYPE ANALYSIS 


Table C 1 – GCxGC –SCD/FID hydrocarbon type analysis 

36 

COSDENOL 180 RB SOLVENT 200B 


CRChem 

NAPHTHALENES 

Area 

Area 

Area 

Class Area (%) Area (%) Area (%) 

Cyc-C10 2630 0.00 3863 0.00 14715 0.00 

Cyc-C11 4629 0.00 10232 0.00 37307 0.01 

Cyc-C12 41853 0.01 10605 0.00 493258 0.08 

Cyc-C13 296941 0.04 93926 0.01 1359730 0.21 

Cyc-C14 512879 0.07 1452 0.00 3070597 0.47 

Cyc-C15 99883 0.01 53532 0.01 6675286 1.02 

Cyc-C16 10648 0.00 8121 0.00 5271918 0.81 

Cyc-C17 4581 0.00 6376 0.00 5175330 0.79 

Cyc-C18 10941 0.00 1472 0.00 3360283 0.52 

Cyc-C19 2322 0.00 566 0.00 1460671 0.22 

Cyc-C20 1869 0.00 103 0.00 304061 0.05 

Cyc-C21 0 0.00 0 0.00 32994 0.01 

Cyc-C22 0 0.00 110 0.00 1339 0.00 

Cyc-C23 0 0.00 1751 0.00 387 0.00 

Cyc-C24 0 0.00 77 0.00 0 0.00 

Cyc-C25 0 0.00 10409 0.00 0 0.00 

Cyc-C26 0 0.00 11588 0.00 0 0.00 

Cyc-C27 0 0.00 9630 0.00 0 0.00 

Cyc-C28 0 0.00 9360 0.00 0 0.00 

Cyc-C29 0 0.00 7110 0.00 0 0.00 

Cyc-C30 0 0.00 5144 0.00 0 0.00 

Cyc-C31 

Monocycloparaffins 

0 0.00 794 0.00 0 0.00 

(total) 989176 0.14 246219 0.04 27257878 4.18 

LUMP 22044 0.00 15020 0.00 10671 0.00 

a6-C1 50579 0.01 28375 0.00 326876 0.05 

a6-C2 209329 0.03 18442982 2.76 1877277 0.29 

a6-C3 4609 0.00 1345167 0.20 4565915 0.70 

a6-C4 601159 0.09 3901900 0.58 5574508 0.85 

a6-C5 268174 0.04 19274120 2.89 4495525 0.69 

a6-C6 13388999 1.93 20589533 3.08 5786895 0.89 

a6-C7 71373826 10.28 14452513 2.16 6902450 1.06 

a6-C8 6332174 0.91 8762788 1.31 4866007 0.75 

a6-C9 2598310 0.37 63613504 9.53 2258053 0.35 

a6-C10 369723 0.05 71445454 10.70 1055589 0.16 

a6-C11 85587 0.01 219563 0.03 714657 0.11 

a6-C12 0 0.00 494 0.00 213838 0.03 

a6-C13 0 0.00 78 0.00 0 0.00 

a6-C14 0 0.00 288 0.00 0 0.00 

a6-C15 0 0.00 40714 0.01 0 0.00 

a6-C16 0 0.00 1774 0.00 0 0.00 

a6 (total) 95282468 13.73 222119247 33.26 38637591 5.92 


37 


a6A5/a6A6-1 38119952 5.49 25356196 3.80 25200580 3.86 

a6A5/a6A6-2 49945512 7.19 26974746 4.04 7503313 1.15 

a6A5/a6A6-3 0 0.00 70199 0.01 0 0.00 

a6A5/a6A6 (total) 88065464 12.69 52401141 7.85 32703894 5.01 

a6A5a6-1 28 0.00 32 0.00 0 0.00 

a6A5a6-2 2319 0.00 7690 0.00 1959487 0.30 

a6A5a6-3 733756 0.11 130072 0.02 17852640 2.74 

a6A5a6-4 491113 0.07 4591 0.00 19852246 3.04 

a6A5a6-5 5402642 0.78 47679 0.01 8420561 1.29 

a6A5a6-6 13933122 2.01 5879639 0.88 1482472 0.23 

a6A5a6-7 972979 0.14 93000 0.01 0 0.00 

a6A5a6 (total) 21535958 3.10 6162703 0.92 49567406 7.60 

a6a6-C0 2039 0.00 643700 0.10 2773679 0.43 

a6a6-C1 483188 0.07 4042520 0.61 46239851 7.09 

a6a6-C2 3697499 0.53 10674035 1.60 162065502 24.85 

a6a6-C3 201226798 28.99 18494963 2.77 121819665 18.68 

a6a6-C4 94742234 13.65 78875999 11.81 51606560 7.91 

a6a6-C5-C14 170237522 24.52 268920281 40.27 19279971 2.96 

a6a6-C15+ 112554 0.02 285428 0.04 0 0.00 

a6a6 (total) 470501834 67.78 381936927 57.19 403785227 61.91 

a6a6a6-1 30551 0.00 31026 0.00 3001479 0.46 

a6a6a6-2 306985 0.04 177600 0.03 1677542 0.26 

a6a6a6-3 625300 0.09 933529 0.14 337865 0.05 

a6a6a6-4 1113702 0.16 1529115 0.23 19418 0.00 

a6a6a6-5 9553818 1.38 1618015 0.24 0 0.00 

a6a6a6 (total) 11630356 1.68 4289285 0.64 5036303 0.77 

a6a6a6a5-1 0 0.00 61 0.00 0 0.00 

a6a6a6a5-2 20 0.00 22 0.00 0 0.00 

a6a6a6a5-3 98302 0.01 6550 0.00 1400 0.00 

a6a6a6a5-4 177108 0.03 32094 0.00 0 0.00 

a6a6a6a5-5 412067 0.06 46859 0.01 0 0.00 

a6a6a6a5-6 258707 0.04 150809 0.02 0 0.00 

a6a6a6a5-7 441461 0.06 93004 0.01 0 0.00 

a6a6a6a5-8 208756 0.03 57349 0.01 0 0.00 

a6a6a6a5 (total) 1596421 0.23 386747 0.06 1400 0.00 

a6a6a6a6 241765 0.03 4151 0.00 0 0.00 

iP-C7 0 0.00 11674 0.00 193366 0.03 

iP-C8 45188 0.01 6244 0.00 369914 0.06 

iP-C9 12381 0.00 1366 0.00 677395 0.10 

iP-C10 5955 0.00 39775 0.01 1036975 0.16 

iP-C11 3458 0.00 7479 0.00 1164127 0.18 

iP-C12 5933 0.00 165 0.00 1539904 0.24 

iP-C13 1925 0.00 713 0.00 1809764 0.28 

iP-C14 443 0.00 1785 0.00 8851369 1.36 

iP-C15 56 0.00 237 0.00 13162047 2.02 

iP-C16 867 0.00 5393 0.00 10838251 1.66 

iP-C17 409 0.00 510 0.00 7164292 1.10 

iP-C18 2766 0.00 3260 0.00 4533738 0.70 


38 


iP-C19 9725 0.00 1834 0.00 2052548 0.31 

iP-C20 1705 0.00 575 0.00 581223 0.09 

iP-C21 1435 0.00 422 0.00 78086 0.01 

iP-C22 30 0.00 3603 0.00 10648 0.00 

iP-C23 0 0.00 7046 0.00 3938 0.00 

iP-C24 0 0.00 9636 0.00 935 0.00 

iP-C26 0 0.00 2347 0.00 0 0.00 

iP-C27 0 0.00 1805 0.00 0 0.00 

iP-C28 0 0.00 1788 0.00 0 0.00 

iP-C30 0 0.00 505 0.00 0 0.00 

iso-Paraffins (total) 92274 0.01 108162 0.02 54068520 8.29 

n-C5 650971 0.09 10883 0.00 88577 0.01 

n-C6 3550992 0.51 10673 0.00 591133 0.09 

n-C8 0 0.00 838 0.00 115118 0.02 

n-C9 0 0.00 118364 0.02 256917 0.04 

n-C7 0 0.00 5241 0.00 54632 0.01 

n-C10 521 0.00 4663 0.00 143099 0.02 

n-C11 0 0.00 263 0.00 227959 0.03 

n-C12 350 0.00 2312 0.00 76622 0.01 

n-C13 441 0.00 1418 0.00 1147242 0.18 

n-C14 92 0.00 1318 0.00 6721253 1.03 

n-C15 625 0.00 1056 0.00 9247804 1.42 

n-C16 944 0.00 1472 0.00 8934301 1.37 

n-C17 1923 0.00 1301 0.00 7204100 1.10 

n-C18 6275 0.00 1520 0.00 4464225 0.68 

n-C19 1462 0.00 456 0.00 1497537 0.23 

n-C20 882 0.00 598 0.00 330514 0.05 

n-C21 419 0.00 1148 0.00 44646 0.01 

n-C22 208 0.00 1408 0.00 853 0.00 

n-C23 252 0.00 2945 0.00 383 0.00 

n-C24 0 0.00 3966 0.00 0 0.00 

n-C25 0 0.00 2634 0.00 0 0.00 

n-C26 0 0.00 4864 0.00 0 0.00 

n-C27 0 0.00 2676 0.00 0 0.00 

n-C28 0 0.00 2956 0.00 0 0.00 

n-C29 0 0.00 1775 0.00 0 0.00 

n-C30 0 0.00 899 0.00 0 0.00 

n-Paraffins (total) 4216357 0.61 187646 0.03 41146914 6.31 



39 


Figure C 1 – Two- and three-dimensional representations of GCxGC-FID 

chromatograms of analyzed samples

Comparative Hydrocarbon Analysis of Cosdenol 180, RB Solvent ...

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