The production of municipal solid waste has continued to grow in recent years. In Italy, municipal solid waste production reaches about 29 million tons per year. The organic fraction of municipal solid waste (OFMSW), which accounts for 30-40% of the total waste, usually undergoes biological treatments such as anaerobic digestion or composting, or is incinerated or landfilled. Biological treatments are considered not economically viable due to the long processing time (20-30 days), while incineration and landfilling are considered as low cost but polluting processes. In contrast, Hydrothermal Carbonization (HTC) is a cost-effective process to treat organic waste especially for the shorter processing time (0.5-8 h) and the possibility to treat directly wet heterogeneous materials. This thesis aims to investigate the potential use of HTC to upgrade OFMSW and other biomasses to biofuels or valuable byproducts. Chapter 1 gives an overview on the state of the art of HTC technology applied to organic wastes, focusing both on mechanisms and on the characteristics of reaction products. Chapter 2 investigates the potential use of HTC to upgrade the organic fraction of municipal solid waste (OFMSW) into biofuel and byproducts. The impact of process conditions (process time, temperature and solid load) on the formation, chemical and energy properties of hydrochar was deeply investigated. To analyze the behavior of hydrochar as a solid biofuel, the combustion (oxidation) of hydrochar and the co-firing (co-oxidation) of hydrochars and coals was also investigated. The results show that, especially at HTC harsher conditions, hydrochar is a “coal-like” material, that can be used as a valuable solid biofuel. The results evidenced that hydrochar is composed of primary char and secondary char. Primary char (non-extractable with organic solvents) has characteristics similar to coal and could be recovered for combustion, while secondary char is an amorphous and more volatile solid, easily extracted with organic solvents, which found possible application as a source of biochemicals and liquid bio-fuel. Chapter 3 investigates the use of HTC as a promising pre-treatment to enhance the biomethane potential during anaerobic digestion of OFMSW. Anaerobic digestion experiments were carried out using the HTC process liquid and the entire HTC reaction mixtures. Results proved that, when compared to the raw OFMSW, the use of HTC liquid and HTC mixture into AD lead to an increase of biomethane production of up to 37% and 363% by volume, respectively. Chapter 4 reports an HTC kinetics study and a kinetic model, which accounted for reactions leading to the production of primary and secondary char, as well as the liquid and gas phases. The model was optimized using experimental data performed on a lignocellulosic feedstock (olive trimmings) and validated on two other types of biomasses (grape marc and Opuntia Ficus Indica) and was used as a reliable tool to predict the carbon distribution among HTC products. In this chapter an in-depth analysis was also carried out to understand the evolution of feedstock characteristics during the heat-up transient phase before reaching the HTC set-point temperature. The results show that during heat up, the feedstock carbonized to a considerable extent at 220-250 °C. Tests clearly show evidence of the transition between thermal hydrolysis and HTC. Chapter 5 presents a study conducted to evaluate the economic feasibility and the detailed energy and cost analyses of a hypothetical HTC plant transforming wet biomass into pelletized dry hydrochar. To achieve these goals, a model was developed on the basis of experimental results obtained previously on two other organic materials (grape marc and off-specification compost). The results show that, when operating the HTC plant with grape marc at the optimal HTC conditions (T=220 °C, t=1 h, dry biomass to water ratio=0.19), the production cost of hydrochar were determined to be 157 €/ton, competitive with the price of wood pellets (150-200 €/ton). This makes HTC a promising process for a large development at the industrial scale.

To achieve a sustainable use of energy we must increase our use of renewable energysources, biogas if one such source. One of the greatest potentials for biogas are in theagricultural sector and the Energy Agency calculates that 25% of the available manurecan be used for biogas production. The purpose of this thesis is to contribute withknowledge of co-digestion of manure and how this affects the methane potential andhow co-digestion affects the contents of NH4 in the sludge. The report includes a literature study to understand the digestion process and its partsand allows interpretation of data. The report includes analysis of data from HalmstadUniversitys experiment of anaerobic digestion and an additional digestion. The resultsobtained in this study shows that the effect of co-digestion varies depending on manure.Horse and chicken manure and beef and pig manure gives a positive effect to the codigestion.

La digestion anaérobie en voie sèche représente une opportunité de développement de la méthanisation sur le territoire français au vu des gisements agricoles disponibles sur le territoire. Toutefois, l’importance des verrous scientifiques et technologiques de par leur nombre et leur complexité rend cette technologie non mature et peu développée sur le territoire français. Dans ces travaux de thèse, il a été étudié dans un premier axe la mise au point de la détermination de la demande chimique en oxygène (DCO) pour des substrats solides avec un kit commercial rendant celle-ci utilisable sans dilution des déchets et utilisant une faible quantité de réactifs. Cette méthode est un outil de suivi des installations. Un deuxième axe d’étude qui s’est attaché à l’étude de la phase d’acidification, verrou majeur de la méthanisation phase sèche, a démontré l’impact de la conservation et de l’origine des inocula sur leur capacité à gérer une phase d’acidification en présence de déchets facilement hydrolysables. L’inoculum est un paramètre majeur de la méthanisation voie sèche et est pourtant peu étudié. Un troisième axe de cette thèse concerne l’étude des transferts hydriques sur des substrats d’origine agricole par une méthodologie de traçage et de modélisation via le modèle à deux régions d’eau mobile et immobile. L’évolution des transferts hydriques a été étudiée au cours de la digestion anaérobie de fumier bovin en digesteur 60 L montrant une diminution de la perméabilité du massif après le deuxième pic de production de méthane. Par conséquent, tout l’inoculum recirculé passe par les côtés et non au sein du massif solide. Deux fréquences de recirculation ont été testées permettant d’obtenir une amélioration de la production de méthane d’environ 20 %. La caractérisation des transferts hydriques obtenus pour ces deux modalités sont identiques après 32 jours de dégradation anaérobie. Le gain de méthane obtenu se fait donc jusqu’au deuxième pic de production de biogaz par la recirculation. Les bilans hydriques et massiques effectués sur ces digesteurs 60 L démontrent que 36 % de la matière organique sont retrouvés dans le digestat montrant un procédé non optimisé. Le quatrième axe d’étude a été de comprendre et d’étudier la dynamique des populations méthanogènes au sein de digesteurs de méthanisation voie sèche de 60 L selon deux configurations. Des expérimentations modulant l’immersion du massif solide ont conduit à obtenir une amélioration de 13 % de production de méthane pour la condition favorisant l’immersion. Cette augmentation de production de méthane est induite par une plus forte quantité de Methanosarcinaceae. La dynamique des populations méthanogènes a été étudiée dans la phase solide et liquide au cours de la digestion anaérobie montrant un transfert microbien de la phase liquide à solide pour un ordre des bactéries hydrogénotrophes, une hiérarchie de ces « hydrogénotrophes » dans le milieu et un fort développement des « acétotrophes » dans le milieu solide servant de support. Dans un cinquième axe, la mise en oeuvre de la tomographie électrique sur un digesteur de 30 m3 a permis de valider son utilisation pour localiser la phase liquide, les zones de potentiels méthane et les zones dégradées dans un container en fonction des protocoles de remplissage et de vidange du digesteur. Cette méthode est disponible pour localiser les zones mortes et donc pour optimiser le procédé de méthanisation en voie sèche type batch. A travers ces expérimentations menées à différentes échelles et avec différentes problématiques, des méthodologies ont été adaptées pour la compréhension des mécanismes et le suivi du procédé de méthanisation par voie sèche. / The dry anaerobic digestion (AD) process is an opportunity to develop the methanization in France. Agricultural waste is abundant in France. However, many scientific and technical locks are complex and must be solved to develop the dry anaerobic digestion process in France. In this work, the chemical oxygen demand (COD) method was adapted for solid waste no implying waste dilution or a high quantity of reagent. This COD method was available to monitor and manage the dry AD process. The study of acidification phase, a major lock of the dry AD process, showed that the storage condition and the origin of inoculum influence the capacity to manage this phase. The inoculum is a major parameter of the dry AD process. But, the inoculum is few studied.On another part of experiments concerned the water transfers studied on agricultural waste with a tracing method. The modeling of the elution curves to determine the diffusion and the convective transfers was made with a model with two Mobile-Immobile regions. The evolution of water transfers was studied during the AD cycle showing a decrease about the permeability of solid phase after the second peak of methane production. Thus, the inoculum passes on the board of solid phase. Two recirculations were tested allowing to obtain an improvement the methane production about 20 % after the AD cycle. The water transfers of these two recirculations modalities were identical after the AD cycle. The improvement of methane production occurred after the second peak of the methane production. Water and mass balances made showing that 36 % of organic matter was find in the digestat. Consequently, the process was not optimized. Others experiments modulating the immerged part of solid phase showed an improvement of the methane production about 13 % with the increasing of immerged part. This methane improvement was induced by the development of Methanosarcinaceae. The methanogens dynamics were studied in the liquid and solid phases during the AD process showing (i) a population transfer between the liquid phase to the solid phase, (ii) a hierarchy of hydrogenotrophs methanogens in the media, and (iii) a strong development of acetotrophs methanogens in the solid phase. In the final part, the electrical tomography was implemented in a dry AD batch at full scale (30 m3). This method was adapted to localize the liquid phase, the zones of methane potential and the degraded zones according to filling and the emptying protocols. This method can detect the “dead” zones of process in dry AD process.Though, experiments carried out at different scales and with different problematic and several methodologies were adapted to understand the dry AD process. Moreover, the optimization of dry AD process was finding to increase the methane production.