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Gieleciak, Hena Farooqi CanmetENERGY, Natural Resources Canada One Oil Patch Drive, Devon, AB, T9G 1A8, Canada 1. Introduction Reducing the carbon footprint of industrial processes used to convert Canadian oil sands crudes into clean transportation fuels is a major challenge for upgraders, refiners and the R&D community. Co-processing biomass with petroleum/bitumen derived feedstocks may provide an alternative solution since the GHG emission from the production and processing of renewable biomass to produce biofuels is considered to be significantly lower than fuels derived solely from fossil fuel resources (Keesom et al., 2009; Sheehan et al., 1998). In addition, co-processing paraffinic biomass feeds and aromatic bitumen feeds may generate synergy to improve gasoline and diesel qualities. The detailed hydrocarbon characterization of petrochemical samples exemplifies one of the most challenging tasks currently faced by separation science. Accurate analytical separation and speciation are necessary to determine what compounds and/or isomers are unaltered and at what concentration levels they are present. For decades, one dimensional gas chromatography (1D-GC) equipped with various detectors had been the preferred technique for the detailed analysis of hydrocarbons, sulfur and nitrogen compounds in petroleum products. However, detailed separation cannot be obtained by using this conventional GC technique because of the lack of chromatographic resolution. The number of hydrocarbon isomers increases exponentially with the increase in the number of carbon atoms, which limits the speciation capability that can be provided by 1D-GC for samples with more than 9 carbon atoms (Vendeuvre et al., 2007). Comprehensive two-dimensional gas chromatography (GC×GC) offers a huge potential for examination of complex mixtures such as petroleum products due to its increased chromatographic resolving power. Moreover, this method has improved detection limits due to the focusing of analyte during the modulation process (Gieleciak et al., 2010; Adahchour et al., 2008; Adam et al., 2007; Hua et al., 2003; Blomberg et al., 1997). The hydroprocessing of vegetable oil and petroleum feedstock blends has been studied by several research groups (Templis et al., 2011; Šimáček and Kubička, 2010; Tóth et al., 2010; Bezergianni et al., 2009; Walendziewski et al., 2009; Watkins et al., 2009; Huber et al., 2007; Viljava et al., 2001; Furimsky, 2000; Wong and Hong, 1999). Most of the published studies have focused on hydroprocessing performance rather than detailed analysis of the diesel products that result from co-processing petroleum and biomass feedstocks. In this study, twenty diesel samples were obtained by co-hydroprocessing low-grade canola oil and bitumen derived heavy vacuum gas oil (HVGO) with different canola oil /HVGO blending ratios, 0/100, 5/95, 10/90, and 20/80 under various reaction conditions. The two-dimensional GC×GC methodology was used to characterize these samples and provide an accurate and simultaneous determination of the hydrocarbons derived from both canola oil and HVGO. 2.1 2. Experimental Feedstock description The feeds used in this study were blends of bitumen derived HVGO and low-grade raw

6 mm in diameter and 5 mm in averaged length) was used. a high-pressure phase separator. Mississauga.14 15 . 90/10.5 1.2 Diesel fractions The purpose of this study is to investigate the impact of bio-derived oils on the hydrocarbon composition. Mississauga. sulphur and nitrogen contents. 100 cm in length and 9 mm in diameter (ID). density. 2. was loaded in the reactor. The liquid product from the stabilizer went to a collector while the gases leaving the separator and the stabilizer were combined and directed to the vent. Prior to the planned runs. spinning band distillation was performed with the total liquid product (TLP). The reactor tube. Detection was performed . ON.17 18 . pressure. A total of 20 ml of catalyst. SK..4 Comprehensive two-dimensional gas chromatography (GC×GC) The diesel fractions were analyzed by two-dimensional gas chromatography (GC×GC). For all experiments gas/oil ratio was fixed at 8000 NL/L. from which a small slip-stream was analyzed by an online gas analyzer (HP5880 GC). Hydroprocessing parameters Temperature (°C) LHSV (h-1) Pressure (psig) 360 375 385 395 395 395 1.5 1. The operating conditions (Table 1) used for the experiments were typical for hydrotreating/mild hydrocracking and covered a relatively wide range of temperature. The reactor system A bench-scale reactor system was used for the experiments. the fresh catalyst was sulphided and then stabilized by processing the feed for about 170 hours to get relatively stable activity.0/2. For comparison. and liquid hourly space velocity.canola oil (Milligan Bio-Tech. A commercial NiMo/Al2O3 hydrotreating catalyst (extrudes of 1. with 20 ml of 0. To obtain the desired diesel fraction (200 – 343°C). Canada) equipped with liquid nitrogen-cooled quad-jet cryogenic modulator (Leco Instruments. 2003).10 11 . ON. pure HVGO was also tested under the similar operating conditions.0/2. 95/5. Slight catalyst deactivation was observed and monitored by conducting check-back runs periodically at the same operating conditions. The system consisted of a single tubular reactor. Hydrogen gas and liquid oil co-currently flowed upwards through the tubular reactor. The GC×GC experiments were performed on two separate Agilent 6890 instruments (Agilent Technologies. and 80/20. on the quality of diesel fractions obtained from co-processing of low-grade canola oil with HVGO.5 1. Case 1 2 3 4 5 6 2. and indirectly.5 1444 1444 1444 1444 1444 1155/1299/1589 Canola Oil (wt%) 0/5/10 0/5/10 0/5/10/20 0/5/10/20 5 5 2. and a product stabilizer. Canada) with 3 different mass blending ratios (HVGO/canola oil). Canada). was heated with a four-zone electric furnace. and hydrocarbon type composition using ASTM methods and other in-house developed methods (Chen et al.5 1. The feeds and the products were analyzed for simulated distillation (SimDis).20 Table 1.2 mm diluting glass beads.5 1.3 Sample ID 1-3 4-6 7 .

Co-hydroprocessing canola oil/HVGO mixture results in conversion of triglycerides to saturated hydrocarbons. In the ‘reversed’ mode the first column is polar and the second one is non-polar. simulating a real 1D-GC chromatogram.1 RTX-5.1 µL 300:1 / 0. peak information (position and area) after preprocessing with ChromaTOF software was further processed in MATLAB® software .1 DF:0. as shown in Figure 1b. Table 2. Comparing the 1D-GC and 2D-GC chromatograms it is easily to conclude that most likely two compounds co-eluting in the first separation can be separated in the second dimension.18 DF:0.5 m x 0.0 m x 0. 1. To enhance visual aspects of GC×GC chromatograms. 30 m x 0. constant flow. Figure 1 shows one of the most important features of GC×GC separation . 1. mostly heptadecane and octadecane and to less extent pentadecane and hexadecane. In the former case the first column is non-polar and the second one is polar.32 mm 1st column DF:0.GC×GC DB-PONA. is presented in the background of the 3D chromatograms. Inserts placed in the upper left corner of each map show three-dimensional view of GC×GC separation.20 mm VF17-MS.2 Secondary oven 20°C offset from main oven 20°C offset from main oven program Split ratio / Injection 200:1 / 0. Light gray color represents the baseline and dark gray/black color represents the most intense peaks in the sulfur chemiluminescence detector (SCD) operated in tandem with flame ionization detector (FID). The GC×GC systems were equipped both with ‘normal’ and ‘reversed’ column set combination. Signal intensity is illustrated by the color intensity. constant flow. Chromatographic conditions for ‘normal’ and ‘reversed’ GC×GC experiments Sample Description ‘normal’. 50 m x 0. 350 °C Detector adapter.2 mL/min He.GC×GC ‘reversed’. where compounds are arranged according to their chemical group and to their number of carbon atoms.1 µL size Carrier gas He. The features and operating conditions for both ‘normal’ and ‘reversed’ GC×GC setup are listed in Table 2. Results and Discussion 3.5 mL/min Modulator temperature 60°C offset from main oven 70°C offset from main oven FID.1 The GC×GC -FID hydrocarbon composition Figure 1 shows ‘normal’ GC×GC -FID chromatograms of the diesel fraction obtained with pure HVGO (a) and a mixture of 80% HVGO and 20% canola oil (b) under condition specified in Table 1 (Case 4). Peaks are displayed as spots in the retention plane described as the first dimension retention time on the x-axis and the second-dimension retention time shown on the y-axis.the structured nature of chromatograms. 300 °C with SCD FID.5 DF:0. The presence of ordered structures in GC×GC plots allows simple visual identification of the chromatograms. 1. 2. 800 °C Modulation period 6s 10 s 3.15 50°C (5) to 270°C (15) at 40°C (5) to 350°C (1) at Main oven program 2°C/min 2°C/min 2nd column Solgelwax. A summed signal on the second dimension.

Under the bubble plots. For example. This transformation allowed for presentation of ‘normal’. peaks found in chromatograms are presented in bubble plot form. ‘Normal’ GC×GC – FID chromatograms of diesel fractions obtained by co-hydroprocessing (Table 1. Release 2008b). In addition.(b) (MATLAB. Case 4) of HVGO (a).Figure 1. The simulated distillation by gas chromatography (ASTM 2887) reported for petroleum or petroleum/vegetable oil blends is normally used for determining the volatility behavior and processability of refinery streams. Figure 2 presents the upgraded version of GC×GC chromatogram of the diesel fraction from Figure 1b. 50. and 90%. The SimDis curve obtained from ASTM D2887 analysis was superimposed on the chromatogram as dashed magenta line.GC×GC-FID chromatograms in the ASTM D2887 distillation temperature domain. the SimDis profile (the magenta dotted line) presented in Figure 2 demonstrates that a significant amount of hydrocarbons have boiling points at around 305 °C and 320°C. respectively. respectively. The SimDis curves are usually characterized by several flat parts in their profile. and 80% HVGO and 20% canola oil blend. The first dimension time was converted into a temperature scale using a correlation established between boiling point of n-paraffins and their retention time. there are indications of n-paraffinic carbon number labeled in green color. The second separation is governed by polarity. which for these fuels means the number of aromatic rings. . in which the size of the bubble and its color are correlated to the compound concentration and relevant hydrocarbon type group. which correspond to n-heptadecane and n-octadecane. respectively. (right above the x-axis). This information can only obtained with GC×GC compositional data superimposed on SimDis results. The black dashed vertical lines on the graph show the SimDis cuts at 10.

For instance paraffins. all the diesel fractions mainly consist of n-paraffins. Averaged ‘normal’ and ‘reversed’ GC×GC hydrocarbon compositions for each case in Table 1 are presented in Figure 4. where the size of the bubbles and their color intensities are correlated to the total hydrocarbon class concentration. and relatively poor separation between aromatic hydrocarbons types in comparison to the ‘normal’ column setup. The hydrocarbon groups are also observed in the ‘reversed’ GC×GC chromatograms. some disadvantages are also present. are located at the top part of the chromatograms. Case 4) 80% HVGO and 20% canola oil blend. which are less polar than aromatics. indans/tetralins. improved separation between saturates and aromatics as well as paraffinic and cycloparaffinc hydrocarbon types. olefins/cycloparaffins and aromatics. Despite unquestionable advantages of using ‘reversed’ system. The use of the ‘reversed’ column setup leads to extended cross-border and thus. boiling point for the diesel fraction obtained by co-hydroprocessing (Table 1. In addition to the ‘normal’ column setup. As expected. 2013) to improve the separation between saturates. which allows more accurate integration for these hydrocarbon types.. Bubble plot (after post-processing Figure 1b) as a function of polarity vs. and potentially to increase capacity utilization. respectively. the proportions of these fractions change with different HVGO/canola oil ratios. As seen in Figure 4. Figures 3a and 3b present ‘reversed’ GC×GC-FID chromatograms of the diesel fractions obtained with pure HVGO. cycloparaffins. but in “reversed” order in comparison to that obtained with ‘normal’ column setup. . For instance. such as the loss of correlation between retention time and boiling point. under the conditions specified in Table 1 (Case 4).. cycloparaffins and indans/tetralins. the selected column combination (Table 1) provided good separation of individual compounds. The ‘reversed’ column setup has been shown (Vendeuvre et al. isoparaffins. 2005. alkylbenzenes. Seven hydrocarbon classes (n-paraffins. naphthalenes. and the 80% HVGO and 20% canola oil blend. diesel fuel samples were subjected to GC×GC experiment with ‘reversed’ column setup (see Table 2).T10 T50 T90 Figure 2. and acenaphthalenes/fluorenes) were identified and quantified using the FID detector. Cannella et al.

2010). Figure 4 reports only GC×GC bulk hydrocarbon class composition.5 wt% cycloparaffins. In addition to presented compositional changes in n-paraffinic region. cycloparaffins containing 17 and 18 carbon atoms appear to have . and 14. Figure 5 also depicts changes of decarboxylation selectivity for all cases in Table 1.g.6 wt% cycloparaffins.4 wt% n-paraffins (mostly n-C17 and n-C18).. and 25. Figure 5 shows the distribution of normal paraffins by carbon number (n-C14 – n-C19) for all the diesel fractions with the size of the squares and their color intensities representing the magnitude of concentration (wt%). In addition to those of n-paraffins (especially n-C16 – n-C18) the yields of other hydrocarbon classes generally decrease or. ‘Reversed’ GC×GC – FID chromatograms of diesel fractions obtained by hydroprocessing (Table 2. Case 4) of pure HVGO (a). with the increase in canola oil content in the feedstock. However. Most of the changes in hydrocarbon composition presented in Figure 4 seem to be caused by dilution effect of HVGO by canola oil. unlike the general trends discussed above.Figure 3.5 wt% indans/tetralins. at least are constant. The decarboxylation selectivity is defined as n-C17/(n-C17+n-C18)*100 (Huber et al. 27. for most of the hydrocarbon classes we are able to provide far more details. e. 40. and 80% HVGO and 20% canola oil blend (b) Sample 10 (obtained from 80% HVGO and 20% canola oil blend) consists of 40. hydrocarbon class distribution by carbon number (Figure 5). 2007) and reflects the relative hydrogen consumption during co-hydroprocessing canola oil and HVGO blends (Haldor Topsoe. However.9 wt% indans/tetralins whereas Sample 7 (obtained from pure HVGO) consists of 5 wt% n-paraffins. The numbers in horizontal axis of Figure 4 indicate the sample number.

Based on GC×GC-SCD results performed on all samples it can be concluded that from the present study. The first row shows the reaction conditions that are changing (eg. Generally with the increase in canola oil content in the feedstock.GC×GC hydrocarbon concentrations in wt%. 3. It clearly Illustrates (Figure 7a) that thiophenes (Th). Hydrodesulfurization conversion increases with increasing temperature. Interestingly. liquid hourly space velocity (LHSV). this paper is the first to show clear evidences of cycloisomerization of intermediate products produced through the hydroprocessing of fatty acids. sulfur content in the diesel fractions are not affected by the content of canola oil in the feed. and other hydrocarbon classes content decrease.2 Sulfur speciation using GC×GC-SCD system To investigate the impact of canola oil on hydrodesulfurization (HDS) GC×GC-SCD with normal column setup (cf. and pressure also affect the properties and compositions of the diesel samples as shown in Table 3. Increases for canola oil/HVGO ratios and temperature) whereas the second row presents major reaction conditions which are kept constant. but is not affected much by addition of canola oil (see Table 3). Figure 7a shows an example of two-dimensional chromatogram of sulfur species in diesel range samples. diesel yield. Although this observation has been reported in some published papers. This in turn can be attributed to cycloisomerization of intermediate products of hydroprocessed fatty acids. The details of each case are provided in Table 1. 3. Bubble plot of averaged ‘normal’ and ‘reversed’. The changes in temperature. canola oil does not affect the HDS performance. n-paraffins content and cetane index increase whereas the nitrogen content.3 Dependence of hydroprocessing performance on operating conditions Table 3 summarizes all the analytical findings obtained in this study in the form of increasing/decreasing compositional trends in hydroprocessing reaction conditions. wt % . benzothiophenes (BTh) and dibenzothiophenes (DBTh) form three bands almost parallel to one another. increased content in parallel to n-paraffins (see Figures 6a and 6b).Figure 4. density. Table 2) was used in all quantitative analysis. which are not discussed in detail in this paper. After hydrodesulfurization (Figures 7b and 7c) only dibenzothiophenes are left in the sample.

It provides complete quantitative characterization of these samples and. can be used to visually distinguish the compositional fingerprints of diesel fractions obtained from hydroprocessed HVGO/canola oil mixtures. The content of iso-paraffins remained relatively constant. Concluding Remarks A commercial hydroprocessing catalyst and typical industrial operating conditions were used in this study to investigate the properties and hydrocarbon type compositions of diesel fractions obtained from co-hydroprocessing of HVGO and canola oil. The GC×GC technique.Figure 5. Figure 6. These diesel samples were fully characterized by using standard ASTM methods and advanced two-dimensional gas chromatography (GC×GC). when used with advanced SimDis analysis. Zoom into saturates region of ‘reversed’ GC×GC – FID of diesel fractions obtained by hydroprocessing (Table 1. and 80% HVGO and 20% canola oil blend (b) 4. better modeling of reaction kinetics and thermodynamics in refinery processes can be conducted. Case 4) of pure HVGO (a). Characterization results showed that with the increase in canola oil content in the feed blends. The increase in the normal paraffins in the diesel samples was attributed to the hydrodeoxygenation and hydrodecarboxylation of triglycerides contained in the canola oil. n-Paraffinic product yields (colored squares) for cases 1-6 defined in Table 1 and correlation between hydroprocessing conditions and decarboxylation selectivity (blue dotted line). with one single analysis. the content of normal paraffins in the diesel fractions increased accordingly whereas the contents of aromatics and cycloparaffins decreased. .

Figure 7. boiling point distribution (or boiling curve). and composition and quality of the diesel products from co-hydroprocessing. The formation of normal heptadecane and normal octadecane resulted in changes in other physical and combustion properties of the diesel samples. diesel fractions obtained from pure HVGO hydrotreated at 365°C (620 ppm S) (b). This study uses advanced GCxGC techniques to provide detailed hydrocarbon characterization of diesel fractions from co-hydroprocessing canola oil and HVGO blends. . Examples of GC×GC-SCD chromatograms of sulfur class distribution in diesel range samples (3500 ppm sulfur ) (a). and cetane index/number. and at 395°C ( 65 ppm S) (c) Table 3. such as density. Therefore technical guidelines can be generated for implementing co-processing biomass and bitumen derived feedstocks to reduce carbon footprint (or GHG emission) while clean transportation fuels are produced from oil sands. These results are important for upgraders and refiners to understand how biomass derived feedstocks affect co-hydroprocessing performance. Dependence of hydroprocessing performance on operating conditions The normal paraffins in the diesel samples were mostly normal heptadecane (product of hydrodecarboxylation) and normal octadecane (product of hydrodeoxygenation) with trace amounts of other lighter/heavier normal paraffins.

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