Progress 05/01/08 to 12/31/08
Outputs
OUTPUTS: Eleven catalysts were prepared. With scale-up and commercialization in mind, several methods were developed with the goal of ensuring elemental uniformity from batch to batch while maintaining high surface area and large pore volume/diameter. Catalysts prepared were characterized by surface area analysis, phase analysis, elemental and morphological analysis. The preferred catalyst was Y42-06 with a surface area of 49 m^2/g, a pore volume of 0.3059 cc/g and a pore diameter of 172 angstrom. Catalysts were tested in the reactor with a pre-reformer bed placed upstream. At 600 degC, the performance with the pre-reformer is slightly better with more H2 and CO and less liquid byproducts formed. At 800 degC, even more H2 and CO are produced, and the H2/CO ratio is near the theoretical of 1.35. The liquid production decreases at 800 degC as well. However, long-term tests without a pre-reformer showed excellent gas product vs. liquid byproduct production according to mass balance calculations based on C, so a pre-reformer was deemed unnecessary. Eight crude glycerol solutions were prepared with varying amounts of water, methanol, and KOH. These solutions mimic the crude glycerol that is collected after biodiesel production. Some solutions would result after the methanol is reclaimed for reuse in the transesterification process. Water and methanol levels have little effect on the syngas production. Solutions with varying amounts of KOH were prepared. K+ ions have a negative effect on the performance of the reforming catalyst. Crude glycerol feedstock, with significant amounts of K+ present, clogged the reactor in the cool zone upstream of the catalyst bed with a substance that was high in char and tar. During Phase I research, we were able to investigate the effects of the pH on the catalyst activity and several attempts were made to remove K+ ions from the glycerol feedstock. Long-term tests were able to satisfy two project goals: 1) catalyst performance will be assessed by comparing synthesis gas vs. liquid byproduct production levels, with >95% selectivity required and 2) pre-reformer and catalyst combinations will be stable reforming crude glycerol for >1000 hours with <1% weekly deactivation rate. Using a C Mass Balance calculation, a Y42 catalyst showed 100% carbon conversion to gaseous carbon species (CO, CH4, and CO2) with minimal decline in activity for 1000 hours. In collaboration with Pacific Biodiesel, we determined which syngas product (hydrogen, methanol, Fischer-Tropsch diesel, etc.) would maximize biodiesel production profits. Hydrogen has the lowest capital and operating costs combined with the highest product market value. However, on-site use of methanol for the transesterification process gives weight to producing methanol from glycerol. Phase I calculations show that the value of hydrogen produced exceeds the $140/ton price of crude glycerol stated in the Phase I proposal. However, crude glycerol prices are experiencing large fluctuations and many analysts predict that if biodiesel production increases to match current potential capacity, crude glycerol may lose all value. PARTICIPANTS: Sara L. Rolfe, Senior Scientist, was Primary Investigator and her role in this program was to provide research direction, the majority of the data evaluation and wrote all reports. Dr. Joel Thompson, Senior Chemist, provided solutions for K+ mitigation. Dr. David Anderson, Chief Engineer, provided scale-up analysis and hydrogen cost analysis. Alana C. Rolfe, Research Technician, performed bench scale testing of catalyst powders. William Smith and Lee Litvin of Pacific Biodiesel Technologies provided crude glycerol (at no cost) to Eltron for use in experiments as well as technical information about crude glycerol. TARGET AUDIENCES: Biodiesel Producers PROJECT MODIFICATIONS: Not relevant to this project.
Impacts
A key element to the economics of the biodiesel market involves the reuse and resale of the production waste product, glycerol. Eltron's Cycloforming process converts the glycerol into syngas, creating significant advantages for the Biodiesel Producer. Syngas can be used to generate electricity and in the production of methanol, synthetic diesel fuel and many other products. Long-term tests were able to satisfy two project goals: 1) catalyst performance will be assessed by comparing synthesis gas vs. liquid byproduct production levels, with >95% selectivity required and 2) pre-reformer and catalyst combinations will be stable reforming crude glycerol for >1000 hours with <1% weekly deactivation rate. Using a C Mass Balance calculation, a Y42 catalyst showed 100% carbon conversion to gaseous carbon species (CO, CH4, and CO2) with minimal decline in activity for 1000 hours. The Cycloforming process produces syngas with nearly 100% selectivity. This process uses the crude glycerol without need for separation or purification, resulting in reduced capital and energy costs. Eltron's Cycloforming technology is also unique in that it requires no oxygen separation equipment, as is needed with other gasification systems. This not only cuts the overall operating cost, but also results in a higher-value gas product (more syngas with less methane and nitrogen). Cycloforming promotes better long-term reactor performance; the technology produces 100% gas products instead of producing tars and liquid products which commonly clog reactor systems. Another advantage of Eltron's technology is that it offers the flexibility to incorporate other feedstocks such as waste algal biomass, waste agricultural biomass, etc. Solutions with varying amounts of KOH were prepared. K+ ions have a negative effect on the performance of the reforming catalyst. Crude glycerol feedstock, with significant amounts of K+ present, clogged the reactor in the cool zone upstream of the catalyst bed with a substance that was high in char and tar. During Phase I research, we were able to investigate the effects of the pH on the catalyst activity and several attempts were made to remove K+ ions from the glycerol feedstock. Further work to reduce K+ levels is necessary. Syngas is a mixture of hydrogen and carbon monoxide that can be used to produce methanol, synthetic diesel fuel, electricity and many other products. Hydrogen has the lowest capital and operating costs combined with the highest product market value. However, on-site use of methanol for the transesterification process gives weight to producing methanol from glycerol. Phase I calculations show that the value of hydrogen produced exceeds the $140/ton price of crude glycerol stated in the Phase I proposal. However, crude glycerol prices are experiencing large fluctuations and many analysts predict that if biodiesel production increases to match current potential capacity, crude glycerol may lose all value. Biodiesel Producers will instantly see the benefit of converting waste glycerol to other high-value, profitable products.
Publications
- No publications reported this period
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