(211d) A Three-Step Catalytic Pathway for the Scalable Production of 1,5-Pentanediol from Biomass-Derived Tetrahydrofurfuryl Alcohol
- Conference: AIChE Annual Meeting
- Year: 2017
- Proceeding: 2017 Annual Meeting
- Group: Catalysis and Reaction Engineering Division
- Time: Monday, October 30, 2017 - 4:15pm-4:35pm
Dehydration of neat THFA in the vapor phase gave a >90% overall yield to DHP over a commercial Î³-Al2O3 catalyst, which is able to be completely regenerated upon calcination at 400Â°C. Hydration of the DHP results in the formation of the main hydration product, 2-HY-THP, and dimers formed via etherification. While 2-HY-THP yields were limited by solid polymer formation high temperatures (>130ËC), nearly quantitative yields to 1,5-PD precursors (2-HY-THP + dimers) were achieved at 50-130ËC in the absence of a catalyst. Solid acid catalysts such as HZSM5 increase hydration rates several orders of magnitude without any decrease in yields. Additionally, HZSM5 was demonstrated to be stable for ~70h in a continuous flow reactor at a 50wt% DHP loading in water.
Hydrogenation of the product formed in the hydration step over supported Ru catalysts gave >96% yields of 1,5-PD from 2-HY-THP and dimers. At low conversions, the 1,5-PD selectivity is <60% due to a shift in equilibrium towards the dimers; however, at higher conversions, dimers are hydrolyzed to their monomers, which are then hydrogenated to 1,5-PD at near quantitative yields. Ru/C was shown to be the most active and stable monometallic catalyst for 2-HY-THP hydrogenation to 1,5-PD. A technoeconomic analysis showed that the DHH pathway presented herein has a 6.6x lower production cost compared to the direct hydrogenolysis route.
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