No description available.

Améliorer la production en hydrogène dans les procédés de conversion des ressources renouvelables telles que la biomasse est un réel challenge dans le contexte de la production d’énergie propre et efficace. En effet, dans le procédé de conversion de la biomasse par vapogazéification, l’hydrogène est produit avec de quantités importantes de CO2, de CH4 et des molécules aromatiques lourdes, toxiques et complexes appelées goudrons. Ce travail s’intéresse à la production d’hydrogène par vaporeformage des goudrons avec capture in-situ de CO2 dans les procédés de vapogazéification de la biomasse. Nous proposons un système catalytique bifonctionnel de type Fe/CaO-Ca12Al14O33 dans lequel le fer est actif pour la production d’H2 tandis que la phase absorbante CaO-Ca12Al14O33 capture le CO2, ces deux processus se font simultanément dans un réacteur à lit fixe. Ce travail a permis de développer un système de type CaOCa12Al14O33/ olivine adapté pour la gazéification de la biomasse « Miscanthus » dans un réacteur à lit fluidisé. / Improve the hydrogen production from the conversion of renewable resources such as biomass is a real challenge in the context of the production of clean and efficient energy. In fact, during the biomass steam gasification, hydrogen is produced with significant amounts of CO2, CH4 and heavy, toxic and complex aromatic molecules called tars. This work focuses on the production of hydrogen by steam reforming of tar with in-situ CO2 capture. We propose a catalytic bi-functional material Fe/CaO-Ca12Al14O33 where iron favors the H2 production and simultaneously the CaO-Ca12Al14O33 capture CO2 in a fixed bed reactor. This work led also to the development of a CaOCa12Al14O33/ olivine system adapted for biomass gasification "Miscanthus" in a fluidized bed reactor.

No description available.

No description available.

No description available.

No description available.

No description available.

Palabras clave: materiales lignocelulósicos residuales, chopo, pino, paja de trigo, plantas anuales, abacá, sisal, yute, lino, Miscanthus sinensis, bagazo de caña de azúcar, henequén, pastas de cocción rápida sosa/AQ, pastas IRSP, carboximetilcelulosa, comportamiento reológico, grado de sustitución.El presente trabajo describe la preparación y caracterización de muestras de carboximetilcelulosa (CMC) a partir de diferentes materiales lignocelulósicos tanto residuales como no madereros, así como el estudio de la influencia de las condiciones de preparación de la materia de partida y sus características sobre las propiedades finales de las CMCs obtenidas. La producción de carboximetilcelulosa a partir de estos materiales supone una importante contribución ya que, en la mayoría de los casos, el derivado se obtiene a partir de linters de algodón y madera de pino y eucalipto. Las muestras de CMC fueron preparadas a partir de pastas procedentes de tres diferentes tipos de cocciones:  Pastas blanqueadas de pino, chopo y paja de trigo, provenientes de procesos de cocción con sosa/antraquinona con tiempos de residencia que abarcaban desde los convencionales de aproximadamente 90 min hasta tiempos de cocción rápidos del orden de 3 min. Pastas blanqueadas de Miscanthus sinensis, bagazo de caña de azúcar y henequén cocidas mediante el método IRSP (Impregnation Rapid Steam Explosion Process) Pastas papeleras comerciales y blanqueadas provenientes de procesos convencionales sosa/antraquinona de abacá, sisal, yute y lino La reacción de eterificación se llevó a cabo siguiendo el procedimiento Druvacell a escala laboratorio para la obtención de CMC con alto grado de pureza. Esta se realizó utilizando siempre las mismas condiciones de operación y relación cuantitativa de los materiales presentes. Los productos purificados fueron caracterizados en función de su grado de sustitución (DS), pureza, solubilidad, viscosidad intrínseca  de soluciones de CMC en NaCl 0.1M, peso molecular y comportamiento reológico de soluciones de CMC a diferentes concentraciones. Se encontró que el DS de las CMCs sintetizadas en el laboratorio dependen en gran medida de la morfología del material lignocelulósico del cual provienen. El método usado para la eterificación de las pastas, da como resultado DS cercanos a 1 después de una eterificación y alrededor de 2 si se aplica un segundo tratamiento de eterificación. Con excepción de las CMCs fabricadas a partir de Miscanthus sinensis y bagazo de caña de azúcar, se obtuvieron DS de 0.75 y 1.45 después de una y dos eterificaciones respectivamente. La pureza de todas las muestras de CMC superaba el 98%. Los valores del peso molecular y el comportamiento reológico de las soluciones de CMC están relacionados con la viscosidad de las pastas de partida. De esta manera, las pastas que tenían un valor menor de viscosidad generaban CMCs con un comportamiento reológico cercano al newtoniano y por el contrario las CMCs que fueron sintetizadas a partir de pastas con mayor viscosidad, presentaban comportamientos pseudoplásticos. Los resultados relacionados con la caracterización reológica de las muestras de CMC, muestran que es posible obtener derivados de celulosa de pastas no madereras con propiedades diferentes a las obtenidas por materiales comunes como la madera o linters de algodón. Estos nuevos materiales presentan un potencial importante para la producción de derivados de celulosa con características innovadoras para aplicaciones industriales específicas, especialmente la estabilidad de la viscosidad con la temperaturaEn general, los experimentos realizados mostraron la viabilidad de obtener CMCs similares a las comerciales partiendo de materiales no convencionales. Además, se confirma la posibilidad de producir derivados de celulosa a partir de pastas de cocción rápida y explosión con vapor, ampliándose de esta manera las opciones de estudio de otros derivados de celulosa de interés industrial. / Keywords: waste lignocellulosic materials, poplar, pine, wheat straw, annual plants, abaca, sisal, jute, linen, Miscanthus sinensis, sugar cane, henequen, fast soda/AQ pulps, IRSP pulps, carboxymethylcellulose, rheological behavior, degree of substitution.In this manuscript we describe the synthesis and characterization of carboxymethylcellulose (CMC) samples from different lignocellulosic residual and non-wood materials. We also describe how the condition of the raw materials affects the preparation and final properties of the CMCs produced. The production of carboxymethylcellulose from these materials is an important contribution because, currently, it is produced from cotton linters and pine and eucalyptus wood.The CMC samples were prepared from three kinds of cellulose pulps:  Soda/anthraquinone bleached pine, poplar and wheat straw pulps with cooking residence times ranging from 3 to 90 min. Steam exploded Miscanthus sinensis, sugar cane and henequen pulps cooked by IRSP (Impregnation Rapid Steam Explosion Process). Commercial bleached paper pulps cooked by the soda/anthraquinone process of abaca, sisal, jute and linen.High purity carboxymethylcellulose was obtained by the etherification Druvacell process on a laboratory scale, always under the same conditions and with the same chemical amounts.The final purified products were characterized in terms of their degree of substitution (DS), purity and solubility in concentrated NaOH, CMC intrinsic viscosity  in 0.1M NaCl solutions, molecular weight and rheological behavior of CMC samples at different concentrations.We found that the DS depended on the raw material morphology and properties and not on the cooking temperature of the pulp source. The method we used for the etherification reaction yielded CMCs whose degree of substitution was close to 1 after one etherification reaction, and around 2 when a second etherification reaction was performed at the same conditions. Miscanthus sinensis and sugar cane were the only exceptions because they yielded CMCs with a DS of around 0.75 and 1.45 after one and two etherification treatments. All CMC samples had purities of over 98%. The molecular weights and the rheological behavior of the CMC solutions were directly related to the viscosity of the pulps. Pulps of lower viscosity therefore produced CMCs whose rheological behavior was similar to Newtonian behavior. On the other hand, the pseudoplastic behavior was obtained from pulps of higher viscosity.The rheological characterization of the CMC samples shows the viability of obtaining carboxymethylcellulose from non-conventional materials whose characteristics are different from those obtained from common materials such as wood or cotton. These new materials have great potential for producing cellulose derivatives with novel characteristics like temperature stability that make them suitable for specific and tailor-made industrial applications. Overall, our results show that carboxymethylcelluloses can be obtained from non-conventional materials having similar characteristics to commercial CMC. We also confirm the production of CMC from rapid soda/AQ and IRSP pulps, being posible to extend this study for other cellulose derivatives of industrial interest.

La sfida nel 21esimo secolo è quella di fornire cibo e energia ad un mondo in continua crescita demografica e allo stesso tempo conservare l’ambiente. In questa tesi uno scenario alternativo di uso del suolo per la produzione di bioenergia è stato testato: le fasce tampone bioenergetiche. Considerate le problematiche ambientali legate al trilemma “cibo-energia-ambiente”, la struttura del Millennium Ecosystem Assessment sui servizi ecosistemici (SE) fornisce l’opportunità di esaminare l’impatto ambientale di questo nuovo scenario bioenergetico. In questa tesi ho mirato a determinare in che misura le colture bioenergetiche poliennali influenzino la fornitura multipla di SE quando coltivate come fasce tampone. Per raggiungere questo obiettivo, ho combinato una revisione sistematica della letteratura sui SE forniti da colture energetiche poliennali (CEP) con una prova sperimentale su fasce tampone bioenergetiche. Applicando una metodologia di attribuzione di punteggi agli impatti sui SE estratti dal materiale bibliografico raccolto, ho mostrato come coltivando le CEP lungo i margini dei campi coltivati esista una grande opportunità per sostenere la fornitura multipla di SE. La coltivazione delle CEP come fasce tampone adiacenti a campi agricoli può migliorare i SE di regolazione del clima, dell’acqua e della biodiversità, sostenere la salute del suolo e fornire biomassa dedicata alla produzione di bioenergia. Al contrario, la conversione di margini di campo di prati stabili ha mostrato un impatto netto negativo sulla fornitura multipla di SE. Tuttavia, due sono i principali svantaggi che sono stati individuati relativamente alla creazione e alla gestione delle fasce tampone bioenergetiche. Primo, diversi sono i fattori sito-specifici di tipo idro-pedologico lungo i margini dei campi che devono essere tenuti in considerazione poiché possono avere un impatto negativo sull’affrancamento delle colture e la loro produttività a medio-lungo termine. Secondo, riguardo la catena di approvvigionamento della biomassa, uno spazio di lavoro limitato per le macchine agricole è stato riconosciuto come principale inconveniente per le fasce tampone bioenergetiche rispetto alle CEP coltivate in pieno campo. Questo limite logistico di natura spaziale può inevitabilmente incrementare i tempi e le operazioni di taglio e raccolta della biomassa e quindi in ultima il consumo di combustili fossili. Grazie ad una prova sperimentale su fasce tampone bioenergetiche condotta in un terreno sabbioso-limoso con falda acquifera poco profonda contaminata da nitrati di origine agricola, si è dimostrato come fasce tampone coltivate con miscanto e salice siano in grado di intercettare e rimuovere i nitrati in falda (>60%) tanto quanto fasce tampone con specie avventizie. CEP come miscanto e salice, grazie ai loro apparati radicali profondi, hanno mostrato essere in grado di promuovere delle relazioni pianta-suolo-microorganismi lungo l’intero profilo del suolo utili ai fini ambientali delle fasce tampone bioenergetiche. Infatti, negli strati più profondi, una maggiore biomassa radicale ha portato le CEP a superare le specie avventizie in termini di rimozione biologica dei nitrati dal suolo e mitigazione potenziale dei gas serra. Inoltre, i risultati relativi alla produzione di biomassa e le asportazioni di N legata alla fase di raccolta hanno confermato ulteriormente come la coltivazione di CEP lungo i corsi d’acqua sia una strategia win-win: produzione di biomassa e protezione dell’ambiente. In conclusione, il potenziale rivelato dalle CEP in termini di fornitura multipla di SE suggerisce che la loro coltivazione, come elementi paesaggistici perenni in posizioni strategiche all'interno di paesaggio agricolo, è un'opzione promettente per promuovere l'intensificazione ecologicamente sostenibile degli agroecosistemi. / The 21st century will challenge agriculture to feed and fuel a growing world while conserving the environment. In this thesis an alternative bioenergy land use scenario to the conversion of marginal land has been tested: the bioenergy buffers. Given the environmental issues related to “food-energy-environment” trilemma, the Millennium Ecosystem Assessment framework on ES provides an opportunity to examine the environmental impacts of this new bioenergy land use scenario. In this thesis I aimed to determine to what extent do the perennial bioenergy crops affect the delivery of multiple ES when cultivated as bioenergy buffers. To reach this aim, I combined a systematic revision of literature on ES provided by perennial bioenergy crops with a field experiment on bioenergy buffers. Applying an impact scoring methodology to the effects on ES extracted from literature, I showed that, cultivating perennial bioenergy crops along field margins of former croplands offer a great opportunity to sustain the provision of multiple ES. The cultivation of perennial bioenergy crops on field margins can improve climate, biodiversity and water regulation services, sustain soil health and provide biomass for energetic purposes. On the contrary, grassland conversion showed a net negative impact on multiple ES provision. Nevertheless, I found two main shortcomings related to bioenergy buffers establishment and management. First, several site-specific factors along field margins must be taken into account, because they can affect crop establishment and buffers long-term productivity. Second, regarding to biomass supply chain, a limited working space for the farm machinery operations has been recognized as the main disadvantages of bioenergy buffers compared to large-scale bioenergy plantations. This spatial logistics constraint may inevitably increase harvest and collection operation times and fossil fuel consumption. Conducting a field experiment with bioenergy buffers in a nitrate-enriched shallow groundwater, I showed that miscanthus and willow buffers are able to efficiently intercept and remove from groundwater the incoming NO3-N as much as buffer strips with spontaneous species. Yet, due to their deep rooting systems, bioenergy buffers promote significant plant-microbial linkages along the soil profile. At deeper soil layers, a higher fine root biomass led perennial bioenergy crops to outperform patches of adventitious vegetation in terms of biological N removal from soil and belowground GHG mitigation potential. The results on biomass production and N removal via harvesting further confirmed that the cultivation of perennial bioenergy crops along watercourses is an effective win-win strategy: biomass production and protection of the environment. In conclusion, the revealed potential of perennial bioenergy crops on multiple ES provision implies that their cultivation as perennial landscape elements in strategic locations within landscape is a promising option to promote the ecological sustainable intensification of agroecosystems.

No description available.