Oxidative Reforming of Biodiesel Over Molybdenum (IV) Oxide Jessica Whalen, Oscar Marin Flores, Su Ha The Gene and Linda Voiland School of Chemical Engineering and Bioengineering Washington State University INTRODUCTION XRD: Commercial MoO2 No Pretreatment 10 8 6 H2 yield Intensity Energy consumption continues to skyrocket worldwide. Biodiesel is a renewable fuel source that has become more popular due to its high energy output, making it a good candidate as potential feedstock in solid oxide fuel cells. Petroleum based fuels become scarcer daily, and biodiesel provides renewable energy. This fuel is created from the reaction of alcohol with vegetable oils and can therefore be made from a diverse number of sources from waste frying oil to algae. 4 2 0 24 34 44 2 Theta 54 64 Particle Size Distribution Commercial molybdenum dioxide was used for all tests. Catalytic partial oxidation was carried out in a fixed bed tubular (quartz) reactor. Typically, 0.5 grams of sample were used for each run. Tests were performed with the O2/C ratio = 0.5, WHSV = 1 h 1, at 8500 C and atmospheric pressure unless otherwise noted. All syngas information was taken from a gas chromatograph. XRD information was gathered as part of the characterization process. A Horiba LA950V2 machine provided particle size distribution information. SEM and EDX images were taken to better understand how the catalyst changed after testing. The BET surface area was measured using a Micromeritics ChemiSorb 2720. Intensity 0 1000 2000 3000 Diameter (µm) 4000 RESULTS AND DISCUSSION Effect of WHSV H2 yield 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% The WHSV was increased every 2 hours in increments of 1.0 beginning with WHSV = 1 h 1. The best conversion occurs at WHSV = 1 h 1. H2 yield CO yield Conversion 0 2 4 6 Time (h) 8 10 24 34 44 2 Theta 54 64 100% 80% 60% H2 yield 40% CO yield 20% Conversion 0 CHARACTERIZATION OF THE CATALYST 2 4 6 8 10 The O2/C ratio was increased every 2 hours in increments of .1 beginning with O2/C=0.5. The best conversion occurs at O2/C=0.5. Time (h) 100% Reaction temperature was lowered every 2 hours in increments of 500 C, beginning at 8500 C. The most effective temperature was 8500 C . H2 yield H2 yield 80% CO yield 60% Conversion 40% 20% 0% 4 6 Time (h) More efficient technology for energy production is important. The prospect of solid oxide fuel cells using biodiesel and molybdenum dioxide shows great promise and must be studied further. Though alone molybdenum dioxide is stable for 19 hours, more can be done to increase the length of stability and productivity of the catalyst. The addition of components such as nickel may improve performance. Further study is in progress to see how nickel will alter catalyst performance. This work was supported by the National Science Foundation’s REU program under grant number EEC-0754370. Effect of Temperature Change 2 Maximum hydrogen yield and conversion were achieved at 8500 C and atmospheric pressure with WHSV = 1 h 1, and O2/C=0.5. Long term tests with similar conditions allowed the catalyst to continue producing stable results with 50 percent hydrogen yield after 19 hours. EDX images showed little coking, so the decline of the catalyst cannot be attributed to coking problems. XRD of the spent sample shows evidence of sintering, which lead to the lowering of the already low surface area, eventually causing the decline of the catalyst. ACKNOWLEDGEMENTS BET surface area = 3.9 m2/g 0 CONCLUSIONS FUTURE WORK Effect of O2/C Change 0% SEM images of commercial MoO2 XRD: MoO2 Sample after long term test 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0 SEM images and XRD of commercial MoO2 after long term test H2 yield METHODS 25 20 15 10 5 0 Percentage Researchers have found molybdenum dioxide displays excellent behavior as catalytic material for the oxidative reforming of both isooctane [1] and dodecane [2]. Isooctane yielded 78% H2 100% carbon conversion while dodecane had 99.21% H2 yield. High conversion and yield percentages with isooctane and dodecane make molybdenum a good candidate as an effective catalyst for biodiesel. Few papers have been published on the topic of catalytic partial oxidation with molybdenum dioxide. Further research must be done to fully understand its potential for use in solid oxide fuel cells. This cutting edge area of research continues to be important as energy consumption increases worldwide. Combining two promising components, biodiesel and molybdenum dioxide, may prove useful for solid oxide fuel cells. 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% After finding ideal WHSV, O2/C ratio, and temperatures for the reaction, a long term test was performed at 8500 C and H2 yield atmospheric pressure CO yield Conversion with WHSV = 1 h 1, and O2/C=0.5. The 0 2 4 6 8 1012141618202224 catalyst was stable for Time (h) 19 hours. Long Term Test 8 10 REFERENCES [1]. O. Marin Flores and S. Ha, Appl. Cata. A Gen. 352 (2009), p. 124- 132. [2]. O. Marin Flores, T. Turba, J. Breit, M. Grant Norton, and S. Ha, Appl. Cata. A Gen. 381 (2010), p. 18-25.