La production de biochars et hydrochars permet de former des amendements enrichis en carbone aromatique, potentiellement plus récalcitrant contre les dégradations dans le sol, tout en produisant massivement des énergies renouvelables. Ces amendements ont pour objectif d’augmenter la quantité de matières organiques des sols (MOS), ainsi que leur fertilité. Néanmoins, due à la diversité des biomasses pouvant être utilisé et des procédés de production, des incompréhensions existent sur le potentiel de ces matériaux à stocker du C dans le sol, à court et à long terme. De plus, des méthodes permettant d’évaluer rapidement la stabilité à long terme de ces matériaux restent à mettre au point, afin de permettre aux utilisateurs de statuer de la qualité de ces nouveaux amendements. Ces travaux ont consisté à évaluer la stabilité de biochars et hydrochars, biologiquement par des incubations de sols, et chimiquement par des oxydations à l’acide dichromate. Les biochars ont montré un haut niveau de stabilité biologique et chimique, permettant de stocker une quantité importante de carbone à l’échelle du siècle. De façon contrastée, les hydrochars se sont caractérisés par une stabilité beaucoup plus faible que les biochars, ne permettant probablement pas de séquestrer massivement du carbone au-delà de la décennie. L’hydrochar a induit un priming effect positif (stimulation), alors que le biochar a induit un priming effect négatif (protection). L’altération physique des deux matériaux a conduit à une augmentation de la stabilité et à une diminution du priming effect, mettant en lumière l’importance des paramètres environnementaux dans les stratégies de séquestration de carbone du sol. Les sols d’anciennes charbonnières ont été utilisés comme modèle d’étude à long terme de l’effet d’un apport de biochar après plusieurs siècles. Leur analyse a mis en évidence que l’apport de biochar améliore durablement les propriétés physicochimiques du sol, telle que la teneur en argile, la capacité d’échange cationique (CEC), la quantité de carbone soluble, et les teneurs en azote et phosphore. Toutefois, après plusieurs siècles d’un amendement de biochar, les communautés microbiennes ne présentaient pas d’adaptation spécifique à la dégradation d’un nouvel apport de biochar. Dans ce modèle, l’apport de résidus de plante a entrainé un priming effect négatif. Ainsi, l’apport de biochar, en générant des conditions particulières, permet le maintient de communautés de microorganismes avec la capacité de réorienter leur métabolisme, afin de dégrader spécifiquement de nouveaux substrats plus facilement minéralisables. D’autres travaux seront nécessaires afin d’évaluer la stabilité des biochars dans le système sol-plante. / Biochars and hydrochars production can form amendments enriched in aromatic carbon, potentially recalcitrant against microbial degradation, while massively producing renewable energy. These amendments are aimed to increase soil organic matter (SOM) quantity, and soil fertility. However, due to the diversity of their feedstock and production processes, misunderstandings exist on the potential of these materials to store C in soil at short and long term. In addition, methods to rapidly evaluate the long-term stability of these materials remain to be developed, in order to allow users to determine the quality of these new amendments. This work was consisted for assessing the stability of biochar and hydrochars, biologically by soil incubations, and chemically by oxidation with acid dichromate. The biochar showed a high level of biological and chemical stability, allowing to storage a large amount of carbon throughout the century. In opposite, the hydrochars might not allow sequestering massively carbon beyond the decade, due to its lower biological and chemical stability. The hydrochars induced a positive priming effect (stimulation) while biochar induced a negative priming effect (protection). Physical weathering of both materials led to an increase of stability and a decrease of the priming effect, highlighting the importance of environmental factors in evaluation of strategies for sequestering carbon. Charcoal kiln soils were used as a model for long-term study of the input of biochar in soil after several centuries. Their analysis showed that the contribution of biochar sustainably improves the physicochemical properties of the soil, such as clay content, cation exchange capacity (CEC), amount of nitrogen, phosphorus, and soluble carbon. However, after several centuries of biochar amendment, microbial communities showed no specific adaptation to the degradation of a new biochar input. In this soil model, the input of plant residues resulted in a negative priming effect. Thus, the contribution of biochar in generating specific conditions, allows the maintenance of microbial communities with the ability to switch of substrates, for a new source of substrates more easily degradable. Further works are needed to assess the stability of biochar in soil-plant system.

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Margretelunds reningsverk i Åkersberga står såsom andra svenska avloppsreningsverk inför nya utmaningar i samband med anpassningen till ett mer hållbart och cirkulärt samhälle. För att bidra till en bra lokal miljö med få transporter och minimerad lukt, uppnå en hög grad av fosforåtervinning, samt reducera organiska och icke-organiska föreningar i slammet ska Roslagsvattenb i samarbete med IVL Svenska Miljöinstitutet utvärdera C-Greens OxyPower HTC-teknik. HTC-tekniken är hydrotermisk karbonisering (HTC) kombinerat med våtoxidation av HTC- vatten. Det våta slammet tas om hand på reningsverket och omvandlas till en fast kolanrikad produkt så kallad HTC-biokol eller hydrokol. HTC-processen innebär uppvärmning av det våta slammet (180–260°C) under högt tryck och syrefria förhållande med vatten närvarande. Hydrokolet som bildas kan uppgraderas till bränsle, jordförbättringsmedel eller aktiverat kol.  I detta arbete studerades potentialen att använda hydrokol som jordförbättringsmedel genom att undersöka biokolets fysikaliska- och kemiska egenskaper. Hydrokol jämfördes med biokol från pyrolys som också är en förkolningsprocess av biomassa vid höga temperaturer (300–650 °C) under syrefria förhållande dock utan närvaro av vatten.  Baserat på resultatet från publicerade studier, har hydrokol potentialen att ersätta eller komplettera mineralgödsel. Hydrokol förbättrar markens bördighet och produktivitet genom att t.ex. öka den totala växttillväxten, förbättrar mineraliseringen av näringsämnen och tillgängligheten av fosfor, samt ger en långsam frisättning av näringsämnen. / Margretelund's treatment plant in Åkersberga, like other Swedish sewage treatment plants, faces new challenges in connection with the adaptation to a more sustainable and circular society. In order to contribute to a good local environment with few transports and minimized odors, achieve a high degree of phosphorus recovery, and reduce organic and inorganic pollutants in the sludge, Roslagsvatten, in collaboration with the IVL Swedish Environmental Institute, will evaluate C-Green's OxyPower HTC-technology.  The HTC-technology is hydrothermal carbonization (HTC) combined with wet oxidation of HTC-water. The wet sludge is taken care of at the treatment plant and converted into a fast carbon-enriched product called HTC-biochar or hydrochar. The HTC-process involves heating the wet sludge (180–260°C) under high pressure and oxygen-free conditions with water present. The hydrochar that is formed can be upgraded to fuel, soil improver or activated carbon.  In this work, the potential of using hydrochar as a soil improver is studied by examining the biochar's physical and chemical properties. Hydrochar was compared with biochar from pyrolysis, which is also a charring process of biomass at high temperatures (300–650 °C) under oxygen-free conditions but without the presence of water.  Based on the results of published studies, hydrochar has the potential to replace or supplement mineral fertilizers. Hydrochar improves soil fertility and productivity by e.g. increase overall plant growth, improve nutrient mineralization and phosphorus availability, and provide a slow release of nutrients.

Increasing population across the globe paved the way for rapid growth in industrialization. Pharmaceuticals, automotive, textiles, agriculture, electronics, electrical and many other industries discharge different types of heavy metals, dyes and organic contaminants into ground water. These discharges are released into lakes and rivers without prior treatment causing huge environmental impact to the environment. Among different remediation techniques, adsorption was considered the most promising method because of its low-cost and high efficiency. Biomass is considered as the most practical and renewable source for production of bio products and biofuels. Biomass is also used for carbon sequestration and as an essential element to produce hydrochar and biochar which are considered as the 21st century black gold. Hydrochar and biochar can be used as an excellent low-cost adsorbent for the removal of heavy metals, dyes and organic contaminants from water. This dissertation work focuses on, firstly, development of novel oxone treated hydrochar as an adsorbent for the efficient removal of Pb(II) and Methylene Blue (MB) from aqueous solutions. Secondly, preparing novel ozone oxidized hydrochar treated with polyethyleneimine for removal of Remzol Brilliant Blue (RBB) and Remzol Reactive Black (RRB) dyes from aqueous solutions. Thirdly, producing high-performance CO2 activated biochar as an adsorbent for efficient removal of Aniline from aqueous solution. All prepared hydrochar and biochar adsorbents were characterized by SEM, TGA, FTIR, Elemental analysis, conductometric titration, and N2 adsorption-desorption isothermal analyses (BET and BJH). The adsorption capacities were determined by Atomic absorption spectrometry (AAS) and Ultraviolet–visible spectroscopy (UV-VIS) respectively. The adsorption capacity of each prepared biochar or hydrochar was determined and both kinetic and isothermal studies were performed. The optimal preparation conditions and adsorption parameters were determined for each adsorbent.

La carbonisation hydrothermale (HTC) est un procédé de conversion en énergie de la biomasse dans l’eau sous critique (180-250°C) à faibles pressions (10-40 bars). Ce procédé conduit à la production d’un matériau solide carboné appelé "hydro-char". L’objectif de ce travail est d’optimiser le procédé HTC par l’étude des performances de l’hydro-char comme source d’énergie. La biomasse étudiée est un résidu d’extraction d’huile d’olive dénommé grignons d’olive constitués de peau, de pulpe et de noyau (taux d’humidité de 70%). Ces grignons d’origine marocaine ont été préalablement séchés (GOS). Au cours de l’HTC, la biomasse est décomposée via des réactions de déshydratation et de décarboxylation. Les hydro-chars sont moins humides et plus riches en carbone que les GOS. Aussi, ils s’appauvrissent en cendres en les transférant dans la phase liquide. Les hydro-chars ont un PCS plus élevé que celui de la tourbe et de lignite. Les résultats montrent que le rendement et les propriétés de l’hydro-char dépendent surtout de la température du procédé. Pour mieux analyser l’effet des conditions opératoires, l’approche des plans d’expériences a été appliquée pour optimiser et modéliser le procédé HTC. Grâce au plan de Doehlert, on peut relier les propriétés de l’hydro-char avec son rendement massique et son comportement thermique de combustion. La représentation des surfaces de réponses a permis de définir les zones de production d’hydro-char avec ses propriétés permettant d’orienter l’élaboration de l’hydro-char pour répondre aux critères d’une application prédéfinie. Le liquide issu de l’HTC des GOS montre une sensibilité à la variation des conditions opératoires. Le carbone soluble dans ce liquide lui donne un pouvoir polluant. Pour le diminuer, deux procédés de traitement ont été testés: l’évaporation et l’oxydation en voie humide. Les résultats ont montré que la quantité d’eau utilisée pour le traitement est le facteur le plus influent sur le bilan énergétique du procédé HTC. / Hydrothermal carbonization (HTC) allows pre-treating humid biomass in subcritical water (180-250°C) and at low pressures (10-40 bars) in the absence of air. This process produces a carbonaceous solid material called "hydro-char". The main aim of this work is to optimize the HTC process by studying the potential of hydro-char to produce energy. The studied biomass is a by-product of the olive oil industry called olive pomace containing water, residual oil, olive skin, olive pulp, and olive stones (with 70% moisture content). The moroccan olive pomace was first air-dried (DOP) and characterized. During the HTC process, the biomass is decomposed via dehydration and decarboxylation reactions. The obtained hydro-char has much less moisture and higher carbon contents than that of untreated DOP. Also, the hydro-char becomes poor in ashes by transferring them into the liquid phase. Hydro-chars have a higher HHV than that of peat and lignite. The results show that hydro-char mass yield and its properties depend on the process temperature especially. For a better analysis of the effect of operating conditions, a Design of Experiments Response Surface Methodology (DoE/RSM) approach was applied to optimize the HTC process. The DoE/RSM allows identifying a relationship between hydro-char properties and its mass yield and thermal combustion behavior. Response-surface plots show defined areas of production of hydro-char which allows tailoring hydro-char elaboration to a specific application. The process liquid from the HTC treatment of DOP shows a sensibility to operating conditions. The soluble carbon in the HTC liquid increases its polluting power and to decrease it two treatment process have been tested: evaporation and wet oxidation. Finally, the results show that the amount of water used for the hydrothermal treatment is the most influential factor on the energy balance of the HTC process.

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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.

Hydrothermal carbonisation (HTC) could form the basis for rendering human faecal wastes safe whilst at the same time generating a carbon-rich material (hydrochar) and providing prospects for the recovery of energy. The work presented here has an objective of the search for optimal conditions for the HTC conversion of human faecal waste. Primary sewage sludge (PSS) and synthetic faeces (SF), of various moisture contents, were used as feedstocks to investigate the kinetics of decomposition of solids during HTC over a range of reaction times and temperatures. Decomposition was found to follow first-order kinetics, and the corresponding activation energies were obtained. Temperature was of primary importance to influence solid decomposition. Higher temperatures resulted in higher solids conversion to hydrochar. The energy contents of the hydrochars from PSS carbonised at 140 200oC for 4 h ranged from 21.5 to 23.1 MJ kg 1. Moisture content was found to affect the HTC process and feedstocks, with higher initial moisture contents resulted in lower hydrochar yields. The effect of reaction conditions on the characteristics of the hydrochar, liquid and gas products from HTC of faecal material, and the conditions leading to optimal hydrochar characteristics were investigated using a Response Surface Methodology (RSM). Models were developed here which could aid in the identification of reaction conditions to tailor such products for specific end uses. The results showed that the amount of carbon retained in hydrochars decreased as temperature and time increased, with carbon retentions of 64 77% at 140 and 160oC, and 50 62% at 180 and 200oC. Increasing temperature and reaction time increased the energy content of the hydrochar from 17 19 MJ kg 1 but reduced its energy yield from 88 to 68%. HTC at 200oC for 240 min resulted in hydrochars suitable for fuel, while carbonation at 160oC for 60 min produced hydrochars appropriate for carbon storage when applied to the soil. Theoretical estimates of methane yields resulting from subsequent anaerobic digestion (AD) of the liquid by-products are presented, with the highest yields obtained following carbonisation at 180oC for 30 min. In general, HTC at 180oC for 60 min and 200oC for 30 min resulted in hydrochars having optimal characteristics, and also for obtaining optimal methane yields. Maillard reaction products were identified in the liquid fractions following carbonisations at the higher temperatures. It was also found that the TOC, COD and BOD of the liquid products following HTC increased as the reaction temperature and time were increased and that these would require further treatment before being discharged. The results indicated that the gaseous phase following HTC contained carbon dioxide, nitrogen dioxide, nitric oxide, ammonia, and hydrogen sulphide indicating that additional treatment would be required before discharge to the atmosphere. In order to identify the optimum conditions leading to greater filterability of slurry resulted from HTC, the effects of reaction temperature and time on the filterability of PSS and SF slurries were investigated and optimised using RSM. It was shown that filterability improved as the reaction temperature and time at which the solids were carbonised was increased, with the best filtration results being achieved at the highest temperature (200°C) and longest treatment time (240 min) employed here. The specific cake resistance to filtration of the carbonised slurries was found to vary between 5.43 x 1012 and 2.05 x 1010 m kg 1 for cold filtration of PSS, 1.11 x 1012 and 3.49 x 1010 m kg 1 for cold filtration of SF, and 3.01 x 1012 and 3.86 x 1010 m kg 1 for hot filtration of SF, and decreased with increasing reaction temperature and time for carbonisation. There was no significant difference in specific resistance between cold and hot filtration of SF. The RSM models employed here were found to yield predictions that were close to the experimental results obtained, and should prove useful in designing and optimising HTC filtration systems for generating solids for a wide variety of end uses. Mass and energy balances of a semi-continuous HTC of faecal waste at 200oC and a reaction time of 30 min were conducted and based on recovering steam from the process as well energy from the solid fuel (hydrochar) and methane from digestion of the liquid by-product. The effect of the feedstock solids content and the quantity of feed on the mass and energy balances were investigated. Preheating the feed to 100oC using heat recovered from the process was found to significantly reduce the energy input to the reactor by about 59%, and decreased the heat loss from the reactor by between 50 60%. For feedstocks containing 15 25% solids (for all feed rates), energy recycled from the flashing off of steam and combustion of the hydrochar would be sufficient for preheating the feed, operating the reactor and drying the wet hydrochar without the need for any external sources of energy. Alternatively, for a feedstock containing 25% solids for all feed rates, energy recycled for the flashing off of steam and combustion of the methane provides sufficient energy to operate the entire process with an excess energy of about 19 21%, which could be used for other purposes.