In the framework of the industry of secondary aluminum, the chemical neutralization of highly reactive materials that come from the pre-treatment screening processes of scraps (beverage cans and domestic appliances) was investigated through experiments in aqueous alkaline solutions. Metallic aluminum-rich by-products are classified, according to EU law, as dangerous waste, as they can potentially develop flammable gases capable of forming explosive mixtures with air. In this way they cannot be disposed of in landfills for non-hazardous wastes if chemical neutralization is not planned and performed beforehand. In this way, these experiments were mainly aimed at unraveling the oxidation rate and at quantifying the production of hydrogen-rich gases from the reactions of the metallic aluminum-rich by-products in a water-rich alkaline (liquid or vapor) environment. Reactions were carried out in a stainless-steel batch mini-reactor with metering and sampling valves, with the resulting gases analyzed by gas-chromatography (GC). The experimental setup was planned to avoid the following issues: (i) the corrosion of the reactor by the alkaline solution and (ii) the permeability of the system to hydrogen (i.e., possible leaks of H2), related to the fast kinetics and short duration of the reactions (which may hinder a pile-up-effect) between the solid by-products and the liquid. The procedure was defined by a controlled interaction process between metals and liquid, using NaOH to increase reaction rates. The experimental runs performed in the mini-reactor proved to be effective for eliminating the reactive metallic aluminum, reaching a maximum hydrogen production of 96% of the total gases produced in the experiments. The relations between gas generation (up to 55 bar of H2 in the experiments, which lasted for four days) and each specific parameter variation are discussed. All the obtained results can be transferred and applied to (i) the possible industrialization of the method for the chemical neutralization of these dangerous by-products, increasing sustainability and workplace safety, (ii) the use of the resulting hydrogen as a source of energy for the furnaces of the secondary aluminum industry itself, and (iii) new technological materials (e.g., “foamed geopolymers”), by using hydrogen as a foaming agent, coupled with aluminosilicate materials, during geopolymeric reactions.