Academic literature on the topic 'Butyl levulinate'

Commercially available Purolite CT151 demonstrated to be an efficient acid catalyst for the synthesis of alkyl levulinates via alcoholysis of furfuryl alcohol (FA) at mild temperatures (80–120 °C) and short reaction time (5 h). Reaction conditions were first optimized for the synthesis of ethyl levulinate and then tested for the preparation of methyl-, propyl-, isopropyl-, butyl, sec-butyl- and allyl levulinate. Preliminary scale-up tests were carried out for most of the alkyl levulinates (starting from 5.0 g of FA) and the resulting products were isolated as pure by distillation in good yields (up to 63%). Furthermore, recycling experiments, conducted for the preparation of ethyl levulinate, showed that both the Purolite CT151 and the exceeding ethanol can be recovered and reused for four consecutive runs without any noticeable loss in the catalyst activity.

This work developed an efficient route to produce fuel bioadditive alkyl levulinates. Special attention was paid to butyl levulinate, which is a bioadditive with an adequate carbon chain size to be blended with liquid fuels such as diesel or gasoline. In this process, levulinic acid was esterified with butyl alcohol using cheap and commercially affordable metal nitrates as catalysts, producing bioadditives at more competitive costs. Iron (III) nitrate was the most active and selective catalyst toward butyl levulinate among the salts evaluated. In solvent-free conditions, with a low molar ratio and catalyst load (1:6 acid to alcohol, 3 mol% of Fe (NO3)3), conversion and selectivity greater than 90% after an 8 h reaction was achieved. A comparison of the iron (III) nitrate with other metal salts demonstrated that its superior performance can be assigned to the highest Lewis acidity of Fe3+ cations. Measurements of pH allow the conclusion that a cation with high Lewis acidity led to a greater H+ release, which results in a higher conversion. Butyl levulinate and pseudobuty levulinate were always the primary and secondary products, respectively. The consecutive character of reactions between butyl alcohol and levulinic acid (formation of the pseudobutyl levulinate and its conversion to butyl levulinate) was verified by assessing the reactions at different temperatures and conversion rates. A variation in Fe(NO3)3 catalyst load impacted the conversion much more than reaction selectivity. The same effect was verified when the reactions were carried out at different temperatures. The reactivity of alcohols with different structures depended more on steric hindrance on the hydroxyl group than the size of the carbon chain. A positive aspect of this work is the use of a commercial iron nitrate salt as the catalyst, which has advantages over traditional mineral acids such as sulfuric and hydrochloric acids. This solid catalyst is not corrosive and avoids neutralization steps after reactions, minimizing the generation of residues and effluents.

SO42−/SnO2-ZrO2catalyst, organic acids, inorganic acids and sulfates have been applied for the alcoholysis of sugars to butyl levulinate using n-buthanol as solvent and reactant. The combined effect of solid acid and H2SO4showed a high catalytic activity for the selective conversion of cellulose to butyl levulinate at 200 °C, whereas the glucose yielded around 40 mol% butyl levulinate. The oxalic acid and CuSO4also showed great activity towards the cellulose alcoholysis.

In recent years, functionalized metal oxides have been gaining popularity for biomass conversion to fuels and chemicals due to the global energy crisis. This study reports a novel catalyst based on noble metal immobilization on functionalized zirconia that has been successfully used in the production of biofuel alkyl levulinates (ALs) from lignocellulosic biomass-derived levulinic acid (LA) under vapor-phase. The wet impregnation method was used to immobilize Pt-metal nanoparticles on zirconia-based supports (silicotungstic acid zirconia, STA-ZrO2; sulfated zirconia, S-ZrO2; and tetragonal zirconia, t-ZrO2). A variety of physicochemical techniques were used to characterize the prepared catalysts, and these were tested under atmospheric pressure in continuous flow esterification of LA. The order of catalytic activity followed when ethyl levulinate was produced from levulinic acid via esterification: Pt/STA-ZrO2 ≫ Pt/S-ZrO2 ≫ Pt/t-ZrO2. Moreover, it was found that ALs synthesis from LA with different alcohols utilizing Pt/STA-ZrO2 catalyst followed the order ethyl levulinate ≫ methyl levulinate ≫ propyl levulinate≫ butyl levulinate. This work outlines an excellent approach to designing efficient catalysts for biofuels and value-added compounds made from biomass.

The present investigation represents a concrete example of complete valorization of Eucalyptus nitens biomass, in the framework of the circular economy. Autohydrolyzed-delignified Eucalyptus nitens was employed as a cheap cellulose-rich feedstock in the direct alcoholysis to n-butyl levulinate, adopting n-butanol as green reagent/reaction medium, very dilute sulfuric acid as a homogeneous catalyst, and different heating systems. The effect of the main reaction parameters to give n-butyl levulinate was investigated to check the feasibility of this reaction and identify the coarse ranges of the main operating variables of greater relevance. High n-butyl levulinate molar yields (35–40 mol%) were achieved under microwave and traditional heating, even using a very high biomass loading (20 wt%), an eligible aspect from the perspective of the high gravity approach. The possibility of reprocessing the reaction mixture deriving from the optimized experiment by the addition of fresh biomass was evaluated, achieving the maximum n-butyl levulinate concentration of about 85 g/L after only one microwave reprocessing of the mother liquor, the highest value hitherto reported starting from real biomass. The alcoholysis reaction was further optimized by Response Surface Methodology, setting a Face-Centered Central Composite Design, which was experimentally validated at the optimal operating conditions for the n-butyl levulinate production. Finally, a preliminary study of diesel engine performances and emissions for a model mixture with analogous composition to that produced from the butanolysis reaction was performed, confirming its potential application as an additive for diesel fuel, without separation of each component.

γ-valerolactone can be a game-changer in the chemical industry because it could substitute fossil feedstocks in different fields. Its production is from the hydrogenation of levulinic acid or alkyl levulinates and can present some risk of thermal runaway. To the best of our knowledge, no studies evaluate the thermal stability of this production in a continuous reactor. We simulated the thermal behavior of the hydrogenation of butyl levulinate over Ru/C in a continuous stirred-tank reactor and performed a sensitivity analysis. The kinetic and thermodynamic constants from Wang et al.’s articles were used. We found that the risk of thermal stability is low for this chemical system.

Addition of 10 vol% biomass-based methyl levulinate (ML), ethyl levulinate (EL), butyl levulinate (BL), gamma-valerolactone (GVL), dimethyl carbonate (DimC), and diethyl carbonate (DieC) in gasoline were selected as blended fuels. Physical-chemical properties of six different blends of biofuels and gasoline, including miscibility, octane number, distillation, vapor pressure, unwashed gum content, solvent washed gum content, copper corrosiveness, water content, mechanical admixtures, and lower heating value was evaluated according to the China National Standards. Blended fuels were then evaluated on the performance and emissions of a gasoline test engine without any modification. The results showed that all biomass-based fuels at 10 vol% have good miscibility in gasoline at temperatures of –30 to 30 °C. Experiments were performed at 4500 rpm engine speed at different engine loads (from 10% to 100% in 10% intervals). Results showed slightly lower engine power at different loads with the blended fuels than those from gasoline fuelled engine. However, the brake specific fuel consumption (BSFC) with the blended fuels was slightly higher than that from gasoline. Emission of carbon monoxide (CO), total unburned hydrocarbon (THC) and oxides of nitrogen (NOx) was reduced significantly from the blended fuels compared to gasoline while carbon dioxide (CO2) emission was slightly higher than that from gasoline. The data suggests that 10 vol% addition of biomass-based levulinates and carbonates fuels to gasoline is suitable for use in gasoline engines.

Hydrolysis and butanolysis of lignocellulosic biomass are efficient routes to produce two valuable bio-based platform chemicals, levulinic acid and n-butyl levulinate, which find increasing applications in the field of biofuels and for the synthesis of intermediates for chemical and pharmaceutical industries, food additives, surfactants, solvents and polymers. In this research, the acid-catalyzed hydrolysis of the waste residue of Cynara cardunculus L. (cardoon), remaining after seed removal for oil exploitation, was investigated. The cardoon residue was employed as-received and after a steam-explosion treatment which causes an enrichment in cellulose. The effects of the main reaction parameters, such as catalyst type and loading, reaction time, temperature and heating methodology, on the hydrolysis process were assessed. Levulinic acid molar yields up to about 50 mol % with levulinic acid concentrations of 62.1 g/L were reached. Moreover, the one-pot butanolysis of the steam-exploded cardoon with the bio-alcohol n-butanol was investigated, demonstrating the direct production of n-butyl levulinate with good yield, up to 42.5 mol %. These results demonstrate that such residual biomass represent a promising feedstock for the sustainable production of levulinic acid and n-butyl levulinate, opening the way to the complete exploitation of this crop.

To enhance the yield of alkyl levulinates, a mixed-acid catalyst system consisting of CrCl3 and H3PO4 was investigated for the transformation of furfuryl alcohol (FA). The CrCl3−H3PO4 system exhibited a positive synergistic catalytic activity for the synthesis of alkyl levulinates, which was especially obvious for n-butyl levulinate (BL) synthesis. The strongest synergic effect of mixed-acid system for BL production was achieved at the CrCl3 molar ratio of 0.3 (based on total moles of CrCl3 and H3PO4). Furthermore, the mixed-acid systems consisting of Cr-salts combined with H3PO4 and its salts in catalyzing FA conversion to BL were evaluated, and the evolution process of FA to produce BL was explored in the presence of CrCl3−H3PO4, sole CrCl3, and sole H3PO4. A possible synergistic catalytic pathway of CrCl3 combined with H3PO4 was proposed. Finally, the key process variables were examined. Under optimal conditions, a high BL yield of 95% was achieved from 99% FA conversion catalyzed by the synergy of CrCl3 and H3PO4.

Nowadays fossil fuels such as coal, petroleum, and natural gas provide more than three quarters of the world`s energy. They are also used to produce the most common transportation fuels. In addition over 96% of chemicals containing carbon, used in our society, derive from petroleum. Among all the possibilities, biomass, such as wood waste, aquatic plant, agricultural crops, municipal and animal wastes, has been recognized as the most promising candidate to replace the fossil resources. Biomass, especially lignocellulose type, represents a renewable, plentiful and cheap material for the industrial production, not only in the energy field but also as feedstock for the manufacture of chemicals, solvent and materials, expecting also environmental benefits. In this context, alkyls levulinates are a class of compounds that are widely studied, primarily as additives for diesel but also for their use as aromas, fragrances and green solvents. This work proposes the study of the reaction between fructose and 1-butanol to produce butyl levulinate using as catalyst ionic acid-exchange resins. In particular the determination of the behavior of the catalyst, according to the reaction conditions used such as feed composition and temperature, and therefore the achievement of a greater selectivity to butyl levulinate and lower production of by-products such as formic acid, butyl formate and humins. Results shows that decreasing the amount of water the selectivity to the main product, butyl levulinate, increases and the formation of by-products such as humins, formic acid and butyl formate decreases. In addition, rising the temperature, the reaction rate increases, leading to higher selectivity to butyl levulinate and the reduction of by-products. The best conditions to obtain the selectivity to butyl levulinate up to 59%, is working at 130°C, with no water, Ratio Fru/BuOH (mol/mol) equal to 0,0165 and Rcat(wt/wt) equal to 0.016.

Questo lavoro è incentrato sullo studio sperimentale e modellistico della produzione di gamma-valerolattone (GVL) mediante l'idrogenazione di n-butil levulinato tramite un processo di idrogenazione catalitica. Il sistema di reazione consta di due fasi consecutive: l'idrogenazione del substrato (nBL) all'intermedio idrossilato (BHP) seguita dalla chiusura ad anello dell'intermedio (cioè la lattonizzazione) al fine di produrre il prodotto finale (GVL). Due diversi solventi (cioè GVL stesso e n-butanolo) sono stati testati per determinare quale fosse il più adatto per condurre gli esperimenti atti a valutare la cinetica del processo. Pertanto, gli esperimenti cinetici sono stati eseguiti utilizzando un reattore batch in condizioni isotermiche ed isobare, cambiando le variabili di processo come la temperatura di reazione, la quantità di catalizzatore e la concentrazione iniziale del substrato al fine di analizzare la loro influenza sulla conversione del substrato e sulla resa del prodotto. I dati sperimentali raccolti sono stati utilizzati per perseguire la stima dei parametri e la discriminazione del modello. Secondo lo studio sperimentale, il solvente più adatto per condurre il processo, che non influisse negativamente sia sulla conversione del substrato che sulla resa del prodotto, è risultato essere il GVL. Inoltre, condurre gli esperimenti cinetici sia ad alta temperatura, elevata quantità di catalizzatore e alta concentrazione iniziale è risultato favorire entrambe le reazioni consecutive dal punto di vista cinetico. Infine, lo studio di modellazione cinetica ha ottenuto come risultato che il modello più adatto a predire i dati sperimentali e a descrivere il meccanismo cinetico sia della reazione di idrogenazione che della reazione di lattonizzazione sia quello che adotta Eley Rideal come modello per definire la velocità della prima reazione, mentre la legge di potenza per definire la velocità della seconda reazione.

Dans le contexte du secteur de l’aviation, qui pose des défis importants en raison de la complexité et des normes strictes en matière de carburant, notre proposition de recherche revêt une pertinence particulière. Nous visons à développer une approche intégrée qui valorise pleinement la biomasse lignocellulosique en carburéacteurs, contribuant ainsi au développement durable de la société. La biomasse lignocellulosique est une ressource renouvelable qui peut être utilisée comme matière première pour produire des matériaux et des produits chimiques de grande valeur, tels que le kérosène. Ce type de valorisation de la biomasse comprend de nombreuses étapes de transformation, pour lesquelles la cinétique et le risque thermique de la réaction chimique ne sont pas forcément connus. Ce travail se concentre sur un composé spécifique : le lévulinate de butyle (BL). Ce composé peut être obtenu à partir de la biomasse lignocellulosique et peut être transformé en gamma-valérolactone (GVL) par hydrogénation. Le GVL est une molécule de plateforme vitale qui peut servir de matière première pour produire des substituts aux combustibles fossiles comme l’essence, le diesel et les carburéacteurs. Les principaux objectifs de cette recherche sont les suivants : 1) Développer un modèle cinétique robuste et fiable pour l’hydrogénation BL afin de produire du GVL. Ici, nous cherchons à développer expérimentalement un modèle cinétique dans différents modes de fonctionnement thermiques, c’est-à-dire isotherme, isopéribolique et adiabatique. Ce type de modèle permet non seulement de prédire la cinétique et le débit de chaleur correspondant, mais aussi d’évaluer le risque thermique lié à la réaction chimique. Les expériences de développement de ce modèle cinétique ont été réalisées dans le réacteur calorimétrique Mettler-Toledo RC1. 2) La valorisation complète de la biomasse lignocellulosique vise l’échelle industrielle. Par conséquent, la production continue de GVL à partir de BL doit être évaluée. En ce sens, nous avons étudié la stabilité thermique de la production continue de GVL à partir de BL dans un réacteur CSTR (réacteur à cuve agitée continue). 3) L’un des aspects intrigants de notre recherche est l’utilisation potentielle du lévulinate de butyle (BL) comme additif pour carburants. Nous avons mené une évaluation approfondie de l’adéquation du BL en tant qu’additif de kérosène, dans le but de comprendre comment son ajout affecte le rendement de combustion et les limites de fonctionnement dans une chambre de combustion de turbine à gaz. Les résultats obtenus concernant le modèle cinétique ont montré que les modèles non compétitifs de Langmuir-Hinshelwood prédisent les données expérimentales de concentration et de température pour l’hydrogénation des BL avec une bonne précision. L’analyse du risque thermique, liée à l’hydrogénation BL, a montré que l’énergie libérée lors de la réaction est relativement faible, ΔH_{hyd} = -35.28 kJ/mol +/- 1.00 kJ/mol, et par la suite l’étude de stabilité thermique a montré que pour des valeurs de Ua > 1500 W/m³/K dans un réacteur continu, le risque d’instabilités thermiques est faible. L’évaluation du BL en tant qu’additif de kérosène a montré que l’ajout de 20 % de BL dans le kérosène ne modifie pas de manière significative les propriétés physiques, ni l’efficacité de la combustion, ni les limites de fonctionnement dans les conditions de fonctionnement prises en compte lors de l’évaluation de la combustion
In the context of the aviation sector, which poses significant challenges due to the complexity and stringent standards of fuel, our research proposal gains particular relevance. We aim to develop an integrated approach that fully valorizes lignocellulosic biomass into jet fuels, thereby contributing to the sustainable development of society. Lignocellulosic biomass is a renewable resource that can be used as feedstock to produce high-value materials and chemicals, such as jet fuel. This type of biomass valorization includes many transformation steps, for which the kinetics and the thermal risk of the chemical reaction are not necessarily known. This work focuses on a specific compound: butyl levulinate (BL). This compound can be obtained from lignocellulosic biomass and can be transformed into gamma-valerolactone (GVL) via hydrogenation. The GVL is a vital platform molecule that can serve as a feedstock to produce substitutes for fossil fuels like gasoline, diesel, and jet fuels. The main objectives of this research are: 1) To develop a robust and reliable kinetic model for BL hydrogenation to produce GVL. Here, we seek to develop a kinetic model experimentally in different thermal modes of operation, i.e., isothermal, isoperibolic, and adiabatic. This model type not only predicts kinetics and the corresponding heat-flow rate but also allows the assessment of the thermal risk related to the chemical reaction. The experiments for developing this kinetic model were performed in the calorimeter reactor Mettler-Toledo RC1. 2) The complete valorization of lignocellulosic biomass targets the industrial scale. Therefore, the continuous production of GVL from BL should be assessed. In that sense, we studied the thermal stability of the continuous production of GVL from BL in a CSTR reactor (continuous stirred tank reactor). 3) One of the intriguing aspects of our research is the potential use of butyl levulinate (BL) as a fuels additive. We have conducted a thorough assessment of the suitability of BL as a kerosene additive, aiming to understand how its addition affects the combustion efficiency and operating limits in a gas turbine combustion chamber. The results obtained concerning the kinetic model showed that the Non-Competitive Langmuir-Hinshelwood models predict the experimental data of concentration and temperature for BL hydrogenation with good accuracy. The thermal risk analysis, linked to BL hydrogenation, showed that the energy released during the reaction is relatively low, ΔH_{hyd} = -35.28 kJ/mol +/- 1.00 kJ/mol, and subsequently the thermal stability study showed that for values of Ua > 1500 W/m³/K in a continuous reactor, the risk of thermal instabilities is low. The evaluation of BL as a kerosene additive showed that adding up to 20% of BL into Kerosene does not significantly change the physical properties, neither the combustion efficiency nor the operating limits in the operating conditions considered during the combustion assessment
En el contexto del sector de la aviación, que plantea importantes retos debido a la complejidad y a los estrictos estándares de combustible, nuestra propuesta de investigación cobra especial relevancia. Nuestro objetivo es desarrollar un enfoque integrado que valorice plenamente labiomasa lignocelulósica en combustibles para aviones, contribuyendo así al desarrollo sostenible de la sociedad. La biomasa lignocelulósica es un recurso renovable que se puede utilizar como materia prima para producir materiales y productos químicos de alto valor, como el combustible para aviones. Este tipo de valorización de la biomasa incluye muchas etapas de transformación, para las cuales no necesariamente se conoce la cinética y el riesgo térmico de la reacción química. Este trabajo se centra en un compuesto específico: el levulinato de butilo (BL). Este compuesto se puede obtener a partir de biomasa lignocelulósica y se puede transformar en gamma-valerolactona (GVL) mediante hidrogenación. El GVL es una molécula plataforma vital que puede servir como materia prima para producir sustitutos de combustibles fósiles como la gasolina, el diésel y los combustibles para aviones. Los principales objetivos de esta investigación son: 1. Desarrollar un modelo cinético robusto y fiable para la hidrogenación de BL para producir GVL. Aquí, buscamos desarrollar un modelo cinético experimentalmente en diferentesmodos de operación térmica, es decir, isotérmico, isoperibólico y adiabático. Este tipo de modelo no solo predice la cinética y el flujo de calor correspondiente, sino que también permite evaluar el riesgo térmico relacionado con la reacción química. Los experimentos para el desarrollo de este modelo cinético se realizaron en el reactor calorímetro Mettler-Toledo RC1. 2. La valorización completa de la biomasa lignocelulósica se dirige a la escala industrial. Por lo tanto, debe evaluarse la producción continua de GVL a partir de BL. En ese sentido, estudiamos la estabilidad térmica de la producción continua de GVL a partir de BL en un reactor CSTR (reactor continuo de tanque agitado). 3. Uno de los aspectos intrigantes de nuestra investigación es el potencial uso del levulinato de butilo (BL) como aditivo de combustibles. Hemos llevado a cabo una evaluación exhaustiva de la idoneidad del BL como aditivo de queroseno, con el objetivo de comprender cómo su adición afecta la eficiencia de la combustión y los límites de funcionamiento en una cámara de combustión de turbina de gas. Los resultados obtenidos en relación con el modelo cinético mostraron que los modelos no competitivos de Langmuir-Hinshelwood predicen los datos experimentales de concentración y temperatura para la hidrogenación de BL con buena precisión. El análisis de riesgo térmico, vinculado a la hidrogenación BL, mostró que la energía liberada durante la reacción es relativamente baja, ΔH_{hyd} = -35.28 kJ/mol +/- 1.00 kJ/mol, y posteriormente el estudio de estabilidad térmica mostró que para valores de Ua > 1500 W/m ³/K en un reactor continuo, el riesgo de inestabilidades térmicas es bajo. La evaluación del BL como aditivo de queroseno mostró que la adición de hasta un 20% de BL al queroseno no cambia significativamente las propiedades físicas, ni la eficiencia de la combustión ni los límites de funcionamiento en las condiciones de funcionamiento consideradas durante la evaluación de la combustión

L'objectif de ce travail était d'étudier en profondeur la synthèse catalytique de lévulinates de butyle à partir de biomasse, d'abord en utilisant les isomères de butanol, puis les isomères de butène comme agents d'estérification. Généralement obtenus par estérification de l'acide lévulinique, les esters lévuliniques et notamment les lévulinates de butyle présentent des propriétés physiques et chimiques faisant d'eux de potentiels additifs de carburant, molécules plateformes, solvants ou encore additifs pour l'industrie alimentaire ou pharmaceutique. En convertissant sélectivement la cellulose en lévulinates de butyle, aucune étape de synthèse et de purification d'intermédiaires réactionnels n'a été nécessaire. Dans les isomères de butanol, la conversion de la cellulose en lévulinates avec H2SO4 a permis d'obtenir à 200°C respectivement 50 et 14% d'esters dans les alcools primaires et secondaire. L'utilisation de zircone sulfatée et de phosphotungstate de césium a abouti à la formation de 15% d'esters dans les alcools primaires, et de 3% dans l'alcool secondaire. L'utilisation d'oléfines comme substituant aux alcools fut étudiée en présence d'acide sulfurique. Avec le n-butène, l'estérification de l'acide lévulinique a donné 55% de lévulinate de sec-butyle à 100°C et en absence de solvant. A partir de cellulose, un rendement de 19% a été obtenu à 100°C dans l'iso-octane. Avec l'iso-butène, 50% de lévulinate de tert-butyle ont été obtenus à partir de l'acide lévulinique, sans solvant et à 25°C. En présence d'Amberlyst-15, 80% de rendement ont pu être obtenus, avec une réutilisation jusqu'à 6 fois du catalyseur sans désactivation notable
The objective of this work was to study in details the catalytic synthesis of butyl levulinates from biomass, first by using butanol isomers, then butene isomers as esterifying agents. Usually obtained by esterification of levulinic acid, levulinic esters including butyl levulinates possess physical and chemical properties making them potential fuel additives, platform molecules, solvents or additives for the food or pharmaceutical industry. By selectively converting cellulose into butyl levulinates, no step of synthesis and purification of reaction intermediates was necessary. In butanol isomers, the conversion of cellulose to levulinates with H2SO4 gave at 200°C, respectively 50 and 14 % of esters in the primary and secondary alcohols. The use of sulfated zirconia and cesium phosphotungstate led to 15% of esters from primary alcohols, and 3% from secondary alcohol. The use of olefins as alcohol substituents was studied in the presence of sulfuric acid. With n-butene, the esterification of levulinic acid gave 55% of sec-butyl levulinate at 100°C and in the absence of solvent. From cellulose, 19% yield was obtained at 100°C in iso-octane. With iso-butene, 50% of tert-butyl levulinate was obtained from levulinic acid, without solvent and at 25°C. In the presence of Amberlyst-15, 80% yield was obtained, with a reuse up to 6 times of the catalyst without significant deactivation

Le monde, et en particulier l'Europe, fait face aux effets du changement climatique dus à sa longue dépendance aux combustibles fossiles en reconnaissant la nécessité vitale de s'orienter vers des ressources énergétiques renouvelables. Parmi les énergies renouvelables, la biomasse alimente non seulement la production de bioénergie, mais constitue également une source vitale de biocarbone, utilisé pour créer des molécules à haute valeur ajoutée, en remplacement des produits d'origine fossile. Les lévulinates d'alkyle, dérivés de la biomasse, se distinguent particulièrement par leur potentiel en tant que bio-additifs et biocarburants. La solvolyse acide des sucres hexagonaux de la biomasse semble être une voie de production prometteuse et rentable. Le potentiel du lévulinate d'alkyle s'étend à sa conversion en γ-valérolactone (GVL), un biosolvant prometteur, généralement obtenu par hydrogénation avec hydrogène moléculaire. En plus d'être un réactif clé, l'hydrogène est également un vecteur énergétique prometteur, facilitant l'intégration des sources d'énergie renouvelables sur le marché. Les systèmes de stockage d'énergie à base d'hydrogène soutiennent cette intégration et favorisent la transformation industrielle "verte". Cette thèse porte sur l'étude technologique et l'évaluation de la durabilité d'un système de biotransformation, intégrant la valorisation de la biomasse lignocellulosique, la production d'énergie et la génération d'hydrogène. L'étude comprend des investigations expérimentales, optimisant les technologies pour la production de lévulinate de butyle et son hydrogénation en GVL, ainsi que la simulation et l'évaluation de la durabilité de l'ensemble du procédé. Afin de répondre à la question de la durabilité, la recherche présente une première section axée sur l'étude expérimentale de la technologie optimale pour la production de lévulinate de butyle. La solvolyse de l'hexose Fructose en lévulinate de butyle a été étudiée en termes de conditions optimales de procédé et de modélisation cinétique. Sélectionné le catalyseur hétérogène, l'effet du solvant a été étudié, montrant les avantages de l'utilisation du GVL comme co-solvant, avec le butanol, sur la cinétique de conversion et de dissolution du fructose. Dans ces conditions, la solvolyse en lévulinate de butyle a été étudiée d'un point de vue cinétique, d'abord en proposant un modèle pour la solvolyse du 5-HMF, un intermédiaire dans la voie du fructose, puis en étendant la modélisation à partir du fructose lui-même. Un modèle cinétique robuste, décrivant le mécanisme réactionnel de la solvolyse, a été défini et validé, en particulier dans des conditions de concentration élevée en fructose, et en incluant dans la modélisation la cinétique de dissolution et de dégradation du fructose. Dans la deuxième partie de la recherche, la perspective technologique a été étendue à l'hydrogénation du lévulinate de butyle en GVL. À partir d'une phase de conception, le schéma global du procédé de transformation du fructose en GVL a été défini, simulé et optimisé sur la base du concept d'intensification du procédé. Le procédé a ensuite été intégré dans une étude de cas réelle en Normandie, France, en adaptant l'analyse à la disponibilité locale de la biomasse lignocellulosique et de l'énergie éolienne. L'étude définit une méthodologie pour la conception et l'intégration du système d'approvisionnement en énergie, en évaluant différents scénarios. L'évaluation de la durabilité, basée sur des indicateurs de performance couvrant les dimensions économiques, environnementales et sociales, aboutit à un indice global de durabilité. Les résultats montrent que les scénarios intégrant le système de GVL, l'énergie éolienne et le stockage de l'énergie sous forme d'hydrogène sont prometteurs, car ils démontrent une rentabilité économique élevée et un impact environnemental réduit. Enfin, des analyses de sensibilité valident la robustesse et la fiabilité de la méthodologie
The world is facing the impacts of climate change due to its long dependence on fossil fuels, and specifically Europe, which is facing an energy crisis, has recognized the fragility of its fossil fuel-dependent energy system and has moved strongly towards renewable energy resources. Among renewables, biomass not only powers bio-energy production but also serves as a vital source of bio-carbon, used to create high-value molecules, replacing fossil-based products. Alkyl levulinates, derived from biomass, particularly stand out for their potential as bio-additives and bio-fuels. Acid solvolysis of hexose sugars from biomass appears to be a promising and cost-effective production route, which requires further investigation not yet found in the literature. The potential of alkyl levulinate extends to its conversion into γ-valerolactone (GVL), a promising bio-solvent, commonly obtained by hydrogenation through molecular-hydrogen. Besides being a key reagent, hydrogen is also a promising energy carrier, facilitating the integration of renewable energy sources into the market. Hydrogen energy storage systems support this integration, promoting 'green' industrial transformation. This thesis focuses on technological investigation and sustainability assessment of a potential biorefinery system, integrating lignocellulosic biomass valorization, energy production, and hydrogen generation. The study encompasses experimental investigations, optimizing technologies for the production of butyl levulinate and its subsequent hydrogenation to GVL. Sustainability considerations are fundamental to the process configuration, aligning with the global shift towards renewable and carbon bio-resources. In order to answer the question of sustainability, the research presents a first section focused on the experimental investigation of the optimal technology for the production of butyl levulinate. The solvolysis of the biomass-derived hexose Fructose to butyl levulinate was investigated, in terms of optimal process conditions and kinetic modelling. Selected an effective heterogeneous catalyst, the effect of the solvent was investigated, showing the benefits of using GVL as co-solvent, together with butanol, on the conversion and dissolution kinetics of fructose. In these conditions, the solvolysis to butyl levulinate was studied in depth from a kinetic point of view, first by proposing a model for the solvolysis of 5-HMF, an intermediate in the fructose pathway, and then extending the modelling from fructose itself. A robust kinetic model, describing the reaction mechanism of solvolysis, was defined and validated, particularly under conditions of high initial fructose concentration (applying the concept of High-gravity), and including in the modelling the kinetics of dissolution, and degradation of fructose, under acidic conditions.In the second part of the research, the technological perspective was extended to the hydrogenation of butyl levulinate to GVL. Starting from a conceptual design phase, the overall fructose-to-GVL process scheme was defined, simulated, and optimized on the basis of the process intensification concept. In the third part, the process was then dropped into a real case study in Normandy, France, adapting the analysis to the local availability of lignocellulosic biomass and wind energy. The study defines a methodology for designing and integrating the energy-supply system, evaluating different scenarios. The sustainability assessment, based on key performance indicators spanning economic, environmental, and social dimensions, culminates in an aggregated overall sustainability index. The results highlight scenarios integrating the GVL biorefinery system with wind power and hydrogen energy storage as promising, demonstrating high economic profitability and reduced environmental impact. Finally, sensitivity analyses validate the robustness and reliability of the methodology, generally extendable also to other technological systems
Come previsto, il mondo sta affrontando gli effetti tangibili del cambiamento climatico come conseguenza di un'economia basata sui combustibili fossili per centinaia di anni. Oltre a dover affrontare e adottare misure correttive per limitare gli effetti del riscaldamento globale, l'Europa sta affrontando una grave crisi energetica, che rivela la fragilità del sistema energetico europeo, prevalentemente dipendente dalle importazioni di combustibili fossili. La geopolitica delle risorse fossili ha innescato la necessaria rimodulazione dell'economia energetica europea, che si sta spostando "forzatamente" verso le risorse energetiche rinnovabili per diventare un'economia fossile e a zero emissioni di carbonio. Nel panorama delle rinnovabili, le risorse più sfruttate sono l'energia solare, eolica e da biomassa. Oltre alla produzione di bioenergia, la biomassa è una fonte inestimabile di biocarbonio, che può essere sfruttata e valorizzata per la produzione di molecole ad alto valore aggiunto che possono essere utilizzate in vari settori industriali, per la produzione di carburanti, prodotti chimici, materiali e sostituendo i corrispondenti prodotti di origine fossile. In questo contesto, sono stati sviluppati sistemi innovativi di bioraffinazione della biomassa di seconda generazione per trasformare e decostruire la complessa struttura della biomassa in molecole piattaforma più semplici, che possono poi essere trasformate in molecole ad alto potenziale. Tra queste, gli alchil levulinati sono stati identificati per il loro notevole potenziale come bioadditivi e biocarburanti. Esteri dell'acido levulinico, questi composti possono essere ottenuti da derivati della biomassa, come i monosaccaridi dello zucchero, secondo diverse vie di reazione; tra queste, la solvolisi acida degli zuccheri esosi può essere una via di produzione promettente ed economicamente vantaggiosa, che richiede ulteriori indagini non ancora presenti in letteratura. Il potenziale degli alchil levulinati risiede anche nella possibilità di un ulteriore trasformazione mediante idrogenazione per produrre γ-valerolattone (GVL), una molecola con un mercato promettente come bio-solvente, grazie alle sue proprietà di stabilità, ecotossicità e biodegradabilità. L'uso dell'idrogeno gassoso è la via più comune per l'idrogenazione del GVL, ma, oltre a essere un reagente chimico fondamentale, l'idrogeno è anche uno dei principali protagonisti della transizione energetica. Infatti, come vettore energetico, l'idrogeno può portare alla piena penetrazione delle fonti energetiche rinnovabili nel mercato dell'energia, costituendo un complemento-tampone per lo stoccaggio delle energie rinnovabili intermittenti, attraverso la progettazione di sistemi di stoccaggio dell'energia dell'idrogeno (HydESS). L'accumulo di energia a idrogeno a lungo termine può consentire l'autosufficienza dei sistemi di energia rinnovabile, in quanto agisce da ponte tra le funzionalità dei sistemi Power-to-Hydrogen, in grado di assorbire i surplus energetici delle energie rinnovabili e di immagazzinarli, e quelle dei sistemi Hydrogen-to-Power, che restituiscono energia rinnovabile quando le fonti di energia primaria non sono disponibili. In quest'ottica, lo sviluppo di tali sistemi può portare all'integrazione completa e stabile delle fonti di energia rinnovabile in asset industriali già esistenti, così come in nuovi mercati industriali, come le bioraffinerie di biomassa lignocellulosica, promuovendo lo sviluppo di realtà industriali "verdi" in termini di trasformazione di materiali ed energia. Il mercato industriale globale si sta evolvendo verso la decarbonizzazione e la riqualificazione di diversi asset, attraverso investimenti in efficienza energetica e l'introduzione di processi green per la valorizzazione delle fonti rinnovabili, ma l'implementazione su larga scala di queste iniziative richiede un'analisi completa e approfondita della loro sostenibilità

碩士
明志科技大學
化學工程系碩士班
104
The heterogeneous kinetic behavior for the synthesis of butyl levulinate from levulinic acid with butanol over acidic cation-exchange resin, (Amberlyst 39) was investigated by using a batch reactor. The kinetic experiments were performed at temperatures between 328.2 K and 348.2 K, and molar ratio of butanol to acid in the feed stream from 1 to 10. Additionally, the mass transfer resistances on the catalytic reaction, and the different levels of catalyst loadings were also observed. The reaction rate of acid increased with increase of reaction temperature, molar ratio of butanol to acid in the feed stream, catalyst loading, and rotational speed. Moreover, the equilibrium conversion of acid increased with increase of reaction temperature and molar ratio of butanol to acid in the feed stream. The relative adsorption strengths of the reacting species were determined by adsorption experiment. The kinetic data of the synthesis of butyl levulinate were correlated with the ideal-quasi-homogeneous (IQH), the non-ideal-quasi-homogeneous (NIQH) ,the Eley-Rideal(ER) and the Langmuir-Hinshelwood-Hougen-Watson (LHHW) models, respectively. The optimal values of the kinetic parameters were determined from the data fitting. The NRTL model was used to calculate the activity coefficients for each reacting species. The ER model, which consider the effect of adsorption was the best representation for the kinetic behavior of heterogeneous catalytic synthesis of butyl levulinate.

碩士
國立臺灣大學
化學工程學研究所
100
Butyl Levulinate (LABE) is one of the potential fuel additives due to its good characteristics such as high octane number, high oxygen content, and low water solubility, etc. In the mean time, the raw materials that can produce LABE are n-Butanol (n-butyl alcohol) and Levulinic acid (LA). Both of them can come from biochemical conversions. For example, the biobutanol can be produced by ABE (Acetone-Butanol-Ethanol) fermentation process, and LA is one of the famous intermediate from hydrolysis of lignocellulostic biomass. Therefore, LABE becomes the variable biomass material. The traditional process to manufacture levulinic ester takes two-step reactions. First, converting the Levulinic acid to angelica lactone and then followed by reaction of angelica lactone with alcohol. However, the two-step reactions may result in complicated process flowsheet and high operating cost. Direct esterification is an alternative way to produce levulinic esters, but the equilibrium limitation still have similar problem like the traditional process. This work aims to use the reactive distillation for simplifying the process of direct esterification of Levulinic acid to Butyl Levulinate. In the reactive distillation system, n-Butanol (n-butyl alcohol) and Levulinic acid are added into the column with sulfuric acid as the catalyst. Levulinic acid and n-Butanol are converted to Butyl Levulinate as bottom product in the reaction section. The rectifying section is the heterogeneous azeotropic distillation system that can separate high purity water as the top product. By using ASPEN plus as simulation platform, the economy and applicability of the proposed reactive distillation process with stoichiometric feed of Levulinic acid and n-Butanol is illustrated in this study.

Although methods both for reduction and for oxidation are well developed, there is always room for improvement. While ketones are usually reduced using metal hydrides, hydrogen gas is much less expensive on scale. Charles P. Casey of the University of Wisconsin has devised (J. Am. Chem. Soc. 2007, 129, 5816) an Fe-based catalyst that effects the transformation of 1 to 2. Note that the usually very reactive monosubstituted alkene is not reduced and does not migrate. Takeshi Oriyama of Ibaraki University has developed a catalyst, also Fe-based (Chemistry Lett. 2007, 38) for reducing aldehydes to ethers. Using this approach, an alcohol such as 3 can be converted into a variety of substituted benzyl ethers, including 5. Simple aliphatic aldehydes and alcohols also work well. Oxidation of alcohols to aldehydes or ketones is one of the most common of organic transformations. Several new processes catalytic in metal have been put forward. Tharmalingam Punniyamurthy of the Indian Institute of Technology, Guwahati has found (Adv. Synth. Cat. 2007, 349, 846) that catalytic V(IV) oxide on silica gel, stirred with t-butyl hydroperoxide in t-butyl alcohol at room temperature smoothly oxidized 6 to 7. After the reaction, the catalyst was separated by filtration. Another carbonyl can also serve as the hydride acceptor, but then the transfer can be reversible. Jonathan M. J. Williams of the University of Bath has shown (Tetrahedron Lett. 2007, 48, 3639) that with a Ru catalyst, methyl levulinate 9 could serve as the hydride acceptor, with the byproduct alcohol being drained off as the lactone 11. Hansjörg Grützmacher of the ETH Zürich developed an Ir catalyst (Angew. Chem. Int. Ed. 2007, 46, 3567) with benzoquinone as the net oxidant. that showed marked preference for the oxidation of primary over secondary alcohols. Yasuhiro Uozumi of the Institute for Molecular Science, Aichi, has devised (Angew. Chem. Int. Ed . 2007, 46, 704) a nanoencapsulated Pt catalyst that worked well with O2 or even with air. The catalyst was easily separated from the product, and maintained its activity over several cycles.