Sustainable Hydrogen from Bio-Oil - Catalytic Steam Reforming of Acetic Acid as a Model Oxygenate

Studies were conducted with acetic acid (HAc) as model oxygenate for the design of active and stable catalysts for steam reforming of bio-oil. Pt/ZrO2 catalysts were prepared by wet impregnation technique. The Pt/ZrO2 catalysts showed high activities at initial time on stream, but lost its activity for steam reforming (H2 production) rapidly. During HAc/H2O reaction over Pt/ZrO2, conversion was close to 100% and constant for 3 hr, however, yields of products changed with time. In the beginning (5 min), H2 and CO2 were the main products, CH4 and CO were observed in small quantities. During HAc/H2O reaction over ZrO2 (without Pt), HAc conversion was close to 90%. The conversion of HAc and yields of the products were constant for 3 hr. However, no steam reforming activity (H2 and CO) was observed, and only acetone and CO2 were observed as products. Both Pt/ZrO2 and ZrO2 were very active for HAc conversion. However, H2 and CO, i.e., steam reforming products, were produced only over Pt/ZrO2 and not over ZrO2. ZrO2 showed acetone yields similar to those observed over Pt/ZrO2 after 25 min time on stream. The presence of acetone in the product mixture and formation of deposits on ZrO2 indicated a role for acetone in catalyst deactivation

Catalyst deactivation during steam reforming of acetic acid over Pt/ZrO2.

Steam reforming of acetic acid as a model compound present in bio-oil over Pt/ZrO2 catalysts has been investigated. Pt/ZrO2 yields steam reforming products (i.e., H2, CO, CO2) to the amounts predicted by thermodynamic equilibrium; however, conversion and yields dropped rapidly with time on course. The deactivation was due to blockage of active sites by coke/oligomer formed. This report clarifies cause of the deactivation during steam reforming of acetic acid. It was found that many products can be formed from acetic acid on ZrO2, such as acetone. The experimental results confirmed that aldol condensation of acetone took place on ZrO2 to give larger compounds which can easily become deposits to block active sites for steam reforming. In order to develop durable catalysts for steam reforming of bio-oil, support should be designed to enhance activation of water, minimize dehydration reactions and thus oligomer formation