Industrial ecology applied to ELV management. Material and energy recovery from ASR

This PhD thesis reports on car fluff management, recycling and recovery. Car fluff is the residual waste produced by car recycling operations, particularly from hulk shredding. Car fluff is known also as Automotive Shredder Residue (ASR) and it is made of plastics, rubbers, textiles, metals and other materials, and it is very heterogeneous both in its composition and in its particle size. In fact, fines may amount to about 50%, making difficult to sort out recyclable materials or exploit ASR heat value by energy recovery. This 3 years long study started with the definition of the Italian End-of-Life Vehicles (ELVs) recycling state of the art. A national recycling trial revealed Italian recycling rate to be around 81% in 2008, while European Community recycling target are set to 85% by 2015. Consequently, according to Industrial Ecology framework, a life cycle assessment (LCA) has been conducted revealing that sorting and recycling polymers and metals contained in car fluff, followed by recovering residual energy, is the route which has the best environmental perspective. This results led the second year investigation that involved pyrolysis trials on pretreated ASR fractions aimed at investigating which processes could be suitable for an industrial scale ASR treatment plant. Sieving followed by floatation reported good result in thermochemical conversion of polymers with polyolefins giving excellent conversion rate. This factor triggered ecodesign considerations. Ecodesign, together with LCA, is one of the Industrial Ecology pillars and it consists of design for recycling and design for disassembly, both aimed at the improvement of car components dismantling speed and the substitution of non recyclable material. Finally, during the last year, innovative plants and technologies for metals recovery from car fluff have been visited and tested worldwide in order to design a new car fluff treatment plant aimed at ASR energy and material recovery.

A chemical-loop approach for the generation of hydrogen by means of ethanol reforming

The work investigates the feasibility of a new process aimed at the production of hydrogen with inherent separation of carbon oxides. The process consists in a cycle in which, in the first step, a mixed metal oxide is reduced by ethanol (obtained from biomasses). The reduced metal is then contacted with steam in order to split the water and sequestrating the oxygen into the looping material’s structure. The oxides used to run this thermochemical cycle, also called “steam-iron process” are mixed ferrites in the spinel structure MeFe2O4 (Me = Fe, Co, Ni or Cu). To understand the reactions involved in the anaerobic reforming of ethanol, diffuse reflectance spectroscopy (DRIFTS) was used, coupled with the mass analysis of the effluent, to study the surface composition of the ferrites during the adsorption of ethanol and its transformations during the temperature program. This study was paired with the tests on a laboratory scale plant and the characterization through various techniques such as XRD, Mössbauer spectroscopy, elemental analysis... on the materials as synthesized and at different reduction degrees In the first step it was found that besides the generation of the expected CO, CO2 and H2O, the products of ethanol anaerobic oxidation, also a large amount of H2 and coke were produced. The latter is highly undesired, since it affects the second step, during which water is fed over the pre-reduced spinel at high temperature. The behavior of the different spinels was affected by the nature of the divalent metal cation; magnetite was the oxide showing the slower rate of reduction by ethanol, but on the other hand it was that one which could perform the entire cycle of the process more efficiently. Still the problem of coke formation remains the greater challenge to solve.