Six ã-Al2O3 supported metallic nitride and carbide catalysts were chosen for a scouting test for the production of a diesel fuel cetane enhancer from canola oil. The six catalysts chosen for study were ã-Al2O3 supported molybdenum (Mo) carbide and nitride, tungsten (W) carbide and nitride, and vanadium (V) nitride and carbide. All six catalysts were prepared by the impregnation method and characterized using various techniques. The six catalysts were screened for their affinity for oxygen removal, fatty acid conversion, alkane/olefin selectivity, hydrogen consumption, and gas-by product production from oleic acid. The scouting test was carried out at a reaction temperature of 390°C, a LHSV of 0.46 hr-1, and elevated hydrogen partial pressures of greater than 7000 kPa, in a laboratory microreactor in an upflow configuration. The scouting test revealed that the two molybdenum catalysts performed the best with oxygen removal near 100% and alkane/olefin content of greater than 30%. <p>Next, the supported molybdenum carbide and nitride catalysts were compared against one another over a wider range of operating conditions. A temperature range of 380 390°C, a LHSV range of 0.64 1.28 hr-1, and a hydrogen partial pressure of 7100 kPa were used. Both catalysts had the same metal loading of 7.4 wt% molybdenum. The two catalysts were compared on the basis of oxygen removal, alkane/olefin selectivity, diesel fuel selectivity, and hydrogen consumption, while using both triolein and canola oil as the feed. It was found that the supported molybdenum nitride was the superior choice for this process, specifically when using the more complex canola oil feed. The supported molybdenum nitride catalyst delivered oxygen removal of greater than 85%, alkane/olefin selectivity of greater than 20%, and diesel fuel selectivity of greater than 40%, for all conditions studied. <p>Finally, a preliminary catalyst and process optimization was carried out on the chosen ã-Al2O3 supported molybdenum nitride catalyst. The catalyst optimization consisted of varying the metal loading of the catalyst from 7.4 wt% to 22.7 wt%. The catalysts were examined over a temperature range of 390 410°C, a LHSV range of 0.9 1.2 hr-1, and a hydrogen partial pressure of 8300 kPa, with canola oil as the chosen feed. It was found that the increase in molybdenum loading on the catalyst delivered an average increase in the alkane/olefin selectivity of 43.2% and an average increase in the diesel fuel selectivity of 5.3 %. The process optimization studied a temperature range of 390 410°C, a LHSV range of 0.6 1.2 hr-1, and a hydrogen partial pressure range of 7800 - 8900 kPa, with canola oil as the chosen feed. Within the limits of the design, it was found that the optimum operating conditions were 395°C, 1.05 hr-1, and 8270 kPa. At these conditions the predicted yields of alkane/olefin products and diesel fuel are 47.3 and 50.5 g/100g liquid fed, respectively.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:SSU.etd-09152008-100149 |
| Date | 17 September 2008 |
| Creators | Sulimma, Hardi Lee |
| Contributors | Scott, Robert, Pugsley, Todd, Monnier, Jacques, Dalai, Ajay K., Wang, Hui |
| Publisher | University of Saskatchewan |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://library.usask.ca/theses/available/etd-09152008-100149/ |
| Rights | unrestricted, I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to University of Saskatchewan or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report. |
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