Hydrogen production from bioethanol reforming in supercritical water

Hydrogen production by reforming and oxidative reforming of ethanol in supercritical water (SCW) at the intermediate temperature range of 500–600 °C and pressure of 25 MPa were investigated at different ethanol concentrations or water to ethanol ratios (3, 20 and 30), with the absence and the presence of oxygen (oxygen to ethanol ratio between 0 and 0.156). Hydrogen was the main product accompanied with relatively low amounts of carbon dioxide, methane and carbon monoxide. Some liquid products, such as acetaldehyde and, occasionally, methanol were present. The ethanol conversion and hydrogen yield and selectivity increased substantially as the water to ethanol ratio and the reaction temperature increased. Ethanol was almost completely reformed and mainly converted to hydrogen giving a H2/CO ratio of 2.6 at 550 °C and water to ethanol ratio of 30 without carbon formation. Coke deposition was favored at low water to ethanol ratio, especially at high temperatures (≥550 °C). The hydrogen yield improved as the ethanol was partially oxidized by the oxygen added into the feed at oxygen to ethanol ratios <0.071. It was evidenced that the metal components in Inconel 625 reactor wall reduced by a hydrogen stream acted as a catalyst promoting hydrocarbon reforming as well as water–gas-shift reactions while dehydrogenation of ethanol forming acetaldehyde can proceed homogeneously under the SCW condition. However, at high oxygen to ethanol ratio, the reactor wall was gradually deactivated after being exposed to the oxidant in the feed. The loss of the catalytic activity of the reactor surface was mainly due to the metal oxide formation resulting in reduction of catalytic activity of the reactor wall and reforming of carbon species was no longer promoted.