Green extraction of chitin from hard spider crab shells

A green protocol to extract chitin from crab shells using water soluble ionic liquids (ILs) is here reported. Compared to conventional multistep acid-base extraction methods, this one-pot procedure achieves pulping of recalcitrant crustacean waste shells by employing ammonium acetate, ammonium formate and hydroxylammonium acetate as water-soluble, low-cost and easy to prepare ILs. An extensive parametric analysis of the pulping process has been carried out with different ILs, different ratios, temperature and time. The optimized protocol provides a high-quality chitin comparable, if not better, to commercial chitin. The best results were obtained at 150 °C with ammonium formate prepared in-situ from aqueous ammonia and formic acid: chitin was isolated in a 17 wt% yield (based on dried crab shells as starting biowaste), a degree of acetylation (DA) > 94 %, a crystallinity index of 39-46 %, a molecular weight up to 6.6 × 10⁵ g/mol and a polydispersity of ca 2.0.