Lithium aluminate flotation by pH- and light-switchable collectors based on the natural product punicine.

Derivatives of the natural product punicine [1-(2',5'-dihydroxyphenyl)pyridinium chloride] were developed as switchable collectors for the flotation of lithium-containing engineered artifical minerals (EnAMs). These EnAMs are e.g. formed by pyrometallurgical processing of end-of-life lithium-ion batteries. Depending on the pH value and the lighting conditions, punicines exist in water as cations, two different electrostatically neutral mesomeric betaines, anionic tripoles, radical cations or radical anions. The radical species form by photochemically induced disproportionation reactions. We prepared punicine derivatives introducing alkyl chains in the pyridinium moiety (4-methyl, 4-ethyl, 4-octyl and 4-undecanyl) to install hydrophobic groups and examined the recovery rates of the flotation of lithium aluminate (LiAlO2). We varied the lighting conditions (darkness, daylight, LED irradiation at λ = 390-400 nm) and the pH value, the collector's and frother's concentration, and the flotation time. With our collectors, recovery rates of lithium aluminate up to 90% were accomplished when the flotation was conducted in Hallimond tubes exposed to daylight at pH 11 in water.

Polyether-tethered imidazole-2-thiones, imidazole-2-selenones and imidazolium salts as collectors for the flotation of lithium aluminate and spodumene.

Imidazolium salts were prepared which possess 2-ethoxyethyl pivalate or 2-(2-ethoxyethoxy)ethyl pivalate groups as amphiphilic side chains with oxygen donors as well as n-butyl substituents as hydrophobic groups. The N-heterocyclic carbenes of the salts, characterized by 7Li and 13C NMR spectroscopy as well as by Rh and Ir complex formation, were used as starting materials for the preparation of the corresponding imidazole-2-thiones and imidazole-2-selenones. Flotation experiments in Hallimond tubes under variation of the air flow, pH, concentration and flotation time were performed. The title compounds proved to be suitable collectors for the flotation of lithium aluminate and spodumene for lithium recovery. Recovery rates up to 88.9% were obtained when the imidazole-2-thione was used as collector.

Novel nicotinoid structures for covalent modification of wood: an environmentally friendly way for its protection against insects.

Timber is constantly exposed to environmental influences under outdoor conditions which limits its lifetime and usability. In order to counteract the damaging processes caused by insects, we have developed a novel and more environmentally friendly method to protect wood materials via covalent modification by organic insecticides. Starting with an important class of synthetic insecticides which are derived from the natural insecticide nicotine, various new carboxylic acid derivatives of imidacloprid were made accessible. These activated neonicotinoids were utilized for the chemical modification of wood hydroxy groups. In contrast to conventional wood preservation methods in which biocides are only physically bound to the surface for a limited time, the covalent fixation of the preservative guarantees a permanent effect against wood pests, demonstrated in standardized biological tests. Additionally, the environmental interaction caused by non-bound neonicotinoids is significantly reduced, since both, a smaller application rate is required and leaching of the active ingredient is prevented. By minimizing the pest infestation, the lifetime of the material increases while preserving the natural appearance of the material.