Abiotic hydrogen production in fresh and altered MSWI-residues: texture and microstructure investigation

Long-term hydrogen generation was observed in a Bavarian mono-landfill for municipal solid waste incineration (MSWI) residues. Hydration reactions of non-noble metals, especially aluminum, predominantly produce hydrogen at alkaline reaction conditions. Microscopic investigations show that aluminum metal may occur in different forms: as larger single grains, as small particles embedded in a vitrified matrix or less frequently in blowholes together with metallic silica. Four types of corrosion texture were observed, indicating different reaction mechanisms: aluminum hydroxide rims caused by hydration reactions at alkaline reaction conditions (reaction type 1) and multiphase rims with ettringite and hydrocalumite due to the reaction of aluminum hydroxide with sulfate and chloride ions which are solved in the pore water (reaction type 2). Galvanic corrosion textures due to the electric potential difference between aluminum and embedded intermetallic Fe- or Cu-rich exsolution phases lead to two further corrosion textures: Strong hydration effects of aluminum except a border of aluminum remnant directly beside the Fe- or Cu-rich segregations were only observed in fresh samples (reaction type 3). The reaction type 4 shows a network of Al-hydroxide veins occurring along the embedded intermetallic Fe- or Cu-rich exsolution segregation pattern within the metallic aluminum grain. Metal particles enclosed in vitrified particles offers the potential for future corrosion processes. The occurrence of corrosion types 1, 2 and 3 in fresh bottom ashes indicates that these reaction mechanisms predominate during the first reaction period in the presence of chlorine in an alkaline solution. Corrosion type 4, however, was additionally observed in aged samples. Here aluminum acts as sacrificed anode implying electrochemical reaction due to electrolytic pore water. Chloride in the system keeps the reaction alive as Al-hydroxide is solved which normally builds a protection shield around the aluminum metal particles. Due to field observations and experimental results we have reasonable indications that after an initial strong formation of hydrogen the reaction time for hydrogen production in the landfill is lengthened for several decades by the presence of chloride in the alkaline pore water.