A l’heure actuelle, la réduction de l’impact environnemental de l’industrie chimique est un enjeu majeur. Pour parvenir à ce but, le concept de Chimie Verte, né dans les années 90, cherche à promouvoir les réactions catalysées et notamment l’utilisation de catalyseurs hétérogènes. L’objectif de cette thèse a été d’utiliser des zéolithes, aluminosilicates microporeux, dopées avec un métal, pour des applications en synthèse organique, et notamment dans une synthèse multi-étapes. Ce type de catalyseur hétérogène est intéressant car il est potentiellement recyclable, facile à séparer du milieu réactionnel et stable.Afin d’atteindre notre objectif, la synthèse totale de l’acortatarine A a été effectuée en utilisant lors d’une étape, une zéolithe dopée avec du cuivre pour former un N-alcynylpyrrole et lors d’une autre étape, une zéolithe dopée avec de l’argent pour effectuer une spirocétalisation. Dans un premier temps, les méthodologies liées à ces deux réactions ont été étudiées puis dans un second temps, en se basant sur les connaissances acquises, la synthèse totale de l’acortatarine A a été effectuée avec succès. Il est à noter que lors de cette synthèse, deux étapes additionnelles ont été réalisées avec des zéolithes acides. A travers cette synthèse nous avons montré que les zéolithes dopées avec des métaux qui entrent pleinement dans le cadre de la Chimie Verte, peuvent être des outils très attractifs dans les synthèses multi-étapes. / Nowadays, reduction of the environmental impact of the chemical industry is a major challenge. To reach this goal, Green Chemistry was born in the 90s where catalysis plays an essential role especially with heterogenous catalysts. The aim of this PhD thesis was to use a support (zeolite) doped with a transition metal in organic synthesis and more specifically in a multi-step synthesis. These heterogeneous catalysts are interesting because they are potentially recyclable, easy to separate from reaction medium and stable. In order to reach our goal, we have performed the total synthesis of acortatarin A performing a step with a copper doped zeolite to form a N-alcynylpyrrole and in another step, a silver doped zeolite was used in a spiroketalization. The methodology linked to these two steps was firstly studied and then gained knowledge was successfully applied in the total synthesis of acortatarin A. Moreover, two additional steps were carried out with acidic zeolites during the synthesis. Through this total synthesis, we have demonstrated that metal-doped zeolites can be very attractiveto perform multi-step synthesis.

Le travail qui est décrit dans ce manuscrit de thèse traite de la chimie des superbases de type proazaphosphatranes, systèmes phosphorés bicycliques très utilisés en catalyse. L’objectif des investigations qui ont été menées à été d’ouvrir de nouvelles voies d’applications de ces catalyseurs. Afin de satisfaire cet objectif, plusieurs stratégies ont été envisagées. D’une part par la mise en confinement de la structure proazaphosphatrane et l’étude de l’influence de ce confinement sur la réactivité intrinsèque du proazaphosphatrane, et d’autre part par la catalyse en conditions bi-phasiques, que ce soit à l’interface entre une phase liquide et un solide ou entre deux phases liquides non-miscibles. Les recherches se sont orientées dans un premier temps sur la synthèse et la caractérisation complète d’un proazaphosphatrane supramoléculaire, obtenu par la fonctionnalisation par un proazaphosphatrane de la cavité supramoléculaire d’un récepteur macrobicyclique. Les séparations semi-préparatives des deux énantiomères d’un intermédiaire et de la molécule phosphorée finale ont également été réalisées, séparations qui ont permis de réaliser l’attribution des configurations absolues des deux structures macrobicycliques. La synthèse d’une famille de catalyseurs de type proazaphosphatrane supportés sur silice mésoporeuse a ensuite été réalisée, suivie de sa caractérisation texturale et structurale par les procédés physico-chimiques habituels, et enfin de sa mise en application dans des réactions d’intérêts de la synthèse organique. En dernier lieu, l’exploitation de la forme acide conjuguée des proazaphosphatranes, dite forme azaphosphatrane, dans des réactions de catalyse par transfert de phase a été entreprise. Il a ainsi put être démontré leur activité en tant qu’agent de transfert dans le cadre de quatre réactions significatives de la catalyse par transfert de phase en version racémique. Ce travail de thèse s’est finalement terminé par une ouverture vers la catalyse par transfert de phase en version asymétrique, par le biais de l’utilisation d’azaphosphatranes chiraux énantiopurs. / The work described in this PhD thesis deals with the chemistry of proazaphosphatrane-type superbases, which are highly reactive bicyclic phosphorous systems largely applied in catalysis. The main goal of these investigations was to devise new applications for their use in catalysis. In this way, several strategies were followed, with an emphasis on their molecular confinement and use in interfacial catalytic systems. In the first part, the manuscript describes the synthesis and characterisation of a supramolecular proazaphosphatrane obtained via the enclosing of a proazaphosphatrane moiety in a hemicryptophane-type macrobicyclic cavity. In parallel, the semi-preparative scale resolution of two macrobicyclic intermediates allowed us to assign their absolute configurations. In the second part, the synthesis and characterisation of a new class of superbases supported on mesoporous silica was achieved. The synthesis was followed by their application in base-catalysed organic reactions. The last part reports the use of their conjugate acids, or azaphosphatranes, in phase transfer catalysis. Their usefulness as achiral phase transfer agents in four relevant reactions was thus determined. The thesis ends with an introduction into asymmetric phase transfer catalysis, using enantiopure azaphosphatranes.

L'objectif de ce travail était double : obtenir des informations sur le lien structure/réactivité dans les nanoalliages et évaluer l'impact de l'addition d'or sur les propriétés catalytiques de métaux actifs en hydrogénation. Des nanoparticules bimétalliques Au-Pd et Au-Rh ont été synthétisées et supportées principalement sur des nanobâtonnets TiO2 rutile, caractérisées par différentes techniques d'analyse (DLS, UV-Vis, HR-(S)TEM, XRD, XPS et CO-FTIR), et évaluées dans deux réactions d'hydrogénation. Les catalyseurs modèles ont été principalement préparés par voie colloïdale suivie d'une immobilisation sur le support et d'un post-traitement consistant à éliminer le surfactant sans détruire la structure des nanoparticules. Les particules Au-Pd (3-5 nm) possèdent une structure alliée de type solution solide. La structure des particules Au-Rh (3-5 nm), système immiscible en volume, est plus hétérogène, avec différentes configurations en fonction du post-traitement effectué : coeur-coquille, ségrégation de phases de type « Janus » et alliage à l'échelle atomique en faible proportion. Les catalyseurs bimétalliques ont été testés en hydrogénation de la tétraline en présence de soufre et en hydrogénation sélective du cinnamaldéhyde, dans les deux cas sous haute pression d'hydrogène, et comparés à leurs homologues monométalliques. En hydrogénation du cinnamaldéhyde, un effet considérable du traitement post-synthèse sur l'activité et sélectivité est mis en évidence. Les catalyseurs fraichement synthétisés montrent une sélectivité élevée en hydrocinnamaldéhyde alors que les traitements de réduction et de calcination-réduction diminuent l'activité pour les échantillons AuRh les plus riches en Rh. En hydrogénation de la tétraline, l'alliage avec l'or a pour effet de diminuer l'activité mais d'améliorer la stabilité des systèmes à base de Pd et Rh en présence de soufre, en augmentant, par effet électronique, la barrière de chimisorption du soufre ou de sulfuration / The objectives of this work were to gain an insight into the structure-selectivity relationships in nanoalloys and to evaluate the impact of gold addition on the catalytic properties of active metals in hydrogenation reactions. For this purpose, bimetallic Au-Pd and Au-Rh nanoparticles were synthesized and supported (mostly) on rutile TiO2 nanorods before being structurally characterized by various techniques (DLS, UV-Vis, HR-(S)TEM, XRD, XPS, and CO-FTIR) and evaluated in two hydrogenation reactions. The model catalysts were mainly prepared using a colloidal method and immobilized on the support. Post-treatments were carried out in order to eliminate the surfactant used during the synthesis, with minimal impact on the nanoparticle structure. The influence of the synthesis parameters on the nanoparticle structure and catalytic properties was evaluated. The Au-Pd particles (3-5 nm) exhibit an alloyed solid solution structure. The structure of the bulk-immiscible Au-Rh particles (3-5 nm) is more heterogeneous, with several structural configurations depending on the post-treatment: core-shell, Janus-type phase segregation, and atomic-scale alloyed structure to a small extent. The catalysts were tested for tetralin hydrogenation in the presence of sulfur (0-100 ppm H2S) and for the selective hydrogenation of cinnamaldehyde, both under high hydrogen pressure. The bimetallic systems were compared to their monometallic counterparts. The post-synthesis treatments have a dramatic impact on activity and selectivity in cinnamaldehyde hydrogenation. The fresh catalysts exhibit a high selectivity toward hydrocinnamaldehyde, whereas reduction and calcination-reduction mainly decrease the activity of Rh-rich Au-Rh samples. For tetralin hydrogenation, gold decreases the activity but improves the stability of Pd and Rh-based systems in the presence of sulfur through electronic effects increasing sulfur chemisorption or sulfidation barriers

Orientador: Celso Valentim Santilli / Banca: Leila Aparecida Chiavacci Favorin / Banca: Eduardo Ferreira Molina / Resumo: Neste trabalho a metodologia sol-gel foi utilizada para a preparação de materiais híbridos orgânico-inorgânicos (HOI) à base de óxido de poli-etileno (PEO), ligado de forma covalente com o agente acoplador 3(isocianatopropil) - trietoxisilano (IsoTREOS) conjugados com um material zeolítico do tipo MFI, visando aplicações como catalisador para a reação de acetilação do glicerol e assim agregar valor a esse coproduto gerado na produção do biodiesel. O objetivo desta dissertação é demonstrar que o sinergismo entre híbridos do tipo siloxano-poliéter e as zeólitas pode ser explorado na produção de hidrogéis com atividade catalítica. As análises por Microscopia Eletrônica de Varredura (MEV) evidenciaram a homogeneidade na dispersão do material zeolítico na matriz híbrida Os difratogramas de raios-X apresentaram os picos característicos da estrutura cristalina da zeolita ZSM-5 após a conjugação com a matriz U-PEO. Os resultados de Calorimetria Diferencial de Varredura (DSC) revelaram que não ocorre uma mudança significativa na temperatura de transição vítrea (Tg), após a conjugação da matriz híbrida com a zeólita e revelaram uma diminuição do pico endotérmico associado à fusão dos domínios cristalinos do PEO1900, indicando uma possível interação matriz-zeólita. As análises por Espectroscopia no Infravermelho com Transformada de Fourier (FTIR) confirmaram a interação entre a matriz híbrida e a zeólita pelo deslocamento das bandas associadas ao oxigênio tipo éter não coordenado. Medid... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work the sol-gel methodology was used for the preparation of organic-inorganic hybrid (HOI) materials based on polyethylene oxide (PEO) - covalently bonded with the coupling agent 3 (isocyanatopropyl) triethoxysilane (IsoTREOS) conjugate with a zeolitic material of the MFI type, aiming at applications as catalyst for glycerol acetylation reaction and thus add value to this byproduct generated in biodiesel production. The objective of this dissertation is to demonstrate that the synergism between siloxane-polyether hybrids and zeolites can be explored in the production of catalytic activity hydrogels. Scanning Electron Microscopy (SEM) analyzes showed homogeneity in the dispersion of zeolite material in the hybrid matrix. XDR patterns showed the characteristic peaks of the ZSM-5 zeolite crystal structure after conjugation with the U-PEO matrix. Differential Scanning Calorimetry (DSC) results revealed that no significant change in glass transition temperature (Tg) occurs after conjugation of hybrid matrix with zeolite and revealed a decrease in endothermic peak associated with fusion of crystalline domains of PEO1900., indicating a possible matrix-zeolite interaction. Fourier Transform Infrared Spectroscopy (FTIR) analyzes confirmed the interaction between the hybrid matrix and zeolite by shifting the bands associated with uncoordinated ether oxygen. Small-angle X-ray Scattering (SAXS) measurements showed that the starting reagents in the solketal production reaction w... (Complete abstract click electronic access below) / Mestre

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[pt] A reação de acoplamento C-C de Suzuki, desde a sua descoberta, sempre atraiu o interesse de diversos pesquisadores e encontrou aplicação em diversos campos tanto na academia como na indústria. Movidos pelos problemas ambientais que tanto preocupam nossa sociedade e pelos princípios da química verde, criados para guiar os químicos na direção de uma ciência sustentável, pesquisadores tem buscado criar catalisadores eficientes para essa reação, que consigam uma alta seletividade em condições reacionais brandas. O desenvolvimento de catalisadores heterogêneos é motivado pela sua fácil remoção do meio reacional e seu possível reuso para um elevado número de reações. Uma abordagem para criação desses catalisadores é a ancoragem de íons metálicos ou de nanopartículas (Nps) metálicas em suportes que facilitem seu manuseio, remoção e reuso. Neste trabalho foram sintetizadas nanopartículas de paládio (Nps Pd) estabilizadas por carboximetilcelulose (CMC), em cuja síntese foi utilizado o ácido L-ascórbico (AA) como agente redutor. Essas Nps foram caracterizadas por UV-VIS, FT-IR-ATR, DLS, potencial zeta, MEV e EDS. A reação de redução do 4-nitrofenol foi utilizada como teste preliminar para verificar a atividade catalítica dessas Nps e, em diferentes condições, a reação ocorreu com tempos que variaram de 3 a 10 minutos. Depois, foram empregadas três diferentes metodologias para a síntese de Nps Pd que utilizaram a CMC como agente redutor e estabilizador a fim de eliminar o uso do AA. As três Nps sintetizadas foram usadas para catalisar uma reação de acoplamento entre o ácido fenilborônico e o 4-iodofenol com rendimentos de 68-76 por cento em duas horas. As Nps que obtiveram maior rendimento foram escolhidas para dar prosseguimento ao projeto. Foram caracterizadas por UV-VIS, FT-IR-ATR, DLS, potencial zeta, MEV e EDS e foram utilizadas para catalisar mais três acoplamentos de Suzuki com rendimentos de 74 por cento a 86 por cento. Um suporte lignocelulósico, mecanicamente e termicamente resistente, feito a partir da biomassa de bambu foi funcionalizado com 1-oxil-2,2,6,6-tetrametilpiperidina (TEMPO) e caracterizado por FT-IR-ATR. Foi, então, impregnado para a imobilização de Na2PdCl4 (T_PdCl2) e das Nps Pd reduzidas e estabilizadas com CMC escolhidas (T_PdCMC_R). Os catalisadores desenvolvidos foram caracterizados por FT-IR-ATR, MEV e EDS. O catalisador T_PdCl2 foi utilizado em 4 reações seguidas com perdas de rendimento a cada reação (de 92,2 por cento até 18,4 por cento). Por ICP OES foi determinado que a quantidade de paládio lixiviada foi de 0,20 ppm na primeira reação e de 0,10 ppm nas reações seguintes. O catalisador T_PdCMC_R foi usado para a reação acoplamento entre ácido fenilborônico e 4-iodofenol e, em diferentes condições, obteve rendimentos de 35 por cento e 43 por cento. / [en] Suzuki C-C coupling reaction, since its discovery, has always attracted the interest of researchers and has found application in several fields both in academia and industry. Driven by environmental problems that concern our society so much and by the principles of green chemistry, created to guide chemists towards a sustainable science, researchers have sought to create efficient catalysts for this reaction, which achieve high selectivity in mild reaction conditions. The development of heterogeneous catalysts is motivated by its easy removal from the reaction medium and its possible reuse for a high number of reactions. One approach for creating these catalysts is to anchor metallic ions or metallic nanoparticles (Nps) in supports that facilitate their handling, removal and reuse. In this work, palladium nanoparticles (Nps Pd) reduced by ascorbic acid (AA) and stabilized by carboxymethylcellulose (CMC) were synthesized. These Nps were characterized by UV-VIS, FT-IR-ATR, DLS, zeta potential, SEM and EDS. The 4-nitrophenol reduction reaction was used as a preliminary test to verify the catalytic activity of these Nps and, under different conditions, the reaction occurred with times ranging from 3 to 10 minutes. Then, three different methodologies for the synthesis of Nps Pd using CMC as reducing and stabilizing agent were proposed in order to eliminate the use of AA. The three synthesized Nps were used to catalyze the coupling reaction between phenylboronic acid and 4-iodophenol with yields of 68-76 percent in two hours. The Nps that obtained the highest yield were chosen to be used in the next steps of the project. These Nps were characterized by UV-VIS, FT-IR-ATR, DLS, zeta potential, SEM and EDS and were used to catalyze three more Suzuki couplings with yields of 74-86 percent. A mechanically and thermally resistant lignocellulosic support, made of bamboo biomass, was functionalized with 1-oxyl-2,2,6,6-tetramethylpiperidine (TEMPO) and characterized by FT-IR-ATR. It was then impregnated for the immobilization of Na2PdCl4 (T_PdCl2) and the chosen Nps Pd reduced and stabilized by CMC (T_PdCMC_R). The developed catalysts were characterized by FT-IR-ATR, MEV and EDS. The catalyst T_PdCl2 was used in 4 reactions in a row with yield losses for each reaction (from 92.2 percent to 18.4 percent). By ICP OES it was determined that the amount of palladium leached was 0.20 ppm in the first reaction and 0.10 ppm in the following reactions. The catalyst T_PdCMC_R was used for the coupling reaction between phenylboronic acid and 4-iodophenol and, under different conditions, obtained yields of 35 percent and 43 percent.

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M. Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / This study presents the use of sodium methoxide as a homogeneous catalyst and impregnated Perlite (potassium hydroxide/perlite) as heterogeneous catalyst for production of biodiesel using Baobab and Marula oil respectively. One factor at a time experimental design was used to study the effect of temperature, time, amount of catalyst and methanol to oil ratio on the transesterification of baobab oil using sodium methoxide as a catalyst. Response surface methodology was used to study the effect of temperature, time, amount of catalyst and methanol to oil ratio on the transesterification of marula oil using perlite as a catalyst. Biodiesel yield produced using sodium methoxide and baobab oil was 96% at 1 hr reaction time, 30 wt.% methanol to oil ratio, 1 gram of catalyst and 60°C reaction conditions. Biodiesel yield produced using perlite and marula oil was 91.38% at 3.55 hr reaction time, 29.86 wt.% methanol to oil ratio, 3.46 grams of catalyst and 70.41°C reaction conditions. Perlite catalyst was reusable for transesterification of marula oil while sodium methoxide was not reusable for transesterification of baobab oil. Baobab and Marula biodiesel fuel properties are comparable to American Society for Testing Materials standard (ASTM).

[ES] En la presente tesis doctoral el principal objetivo ha sido desarrollar una nueva metodología para producir monoésteres, diésteres y polioles derivados de ácidos grasos de forma continua. Una producción en continuo incrementa la producción y la productividad por tiempo de catalizador. Además, esta metodología es mucho más sostenible para el medioambiente, ya que hace decrecer el factor E (Factor E = kg totales de sustancias involucradas en el proceso/Kg de producto) y se reducen también los residuos generados, si los comparamos a un proceso discontinuo. Así mismo, el proceso en continuo se desarrollará mediante catálisis heterogénea y mediante sólidos poliméricos de nueva síntesis. Cabe destacar que actualmente no hay en la literatura ninguna referencia de producción en continuo para la esterificación de ácidos grasos lineales de cadena larga con alcoholes. En primer lugar, se realizó un "screening" de diferentes catalizadores a nivel de laboratorio para la reacción de esterificación tanto en "batch" como en un reactor de lecho fijo. De entre los catalizadores probados se vio como catalizadores como el PAFR eran altamente activos a la conversión de ácidos, pero su limitada disponibilidad a nivel comercial limitó su posterior uso. Otra tipología de catalizadores probados fueron los carbones activos funcionalizados con azufre, entre ellos el catalizador que mejor funcionó fue el Norit RBHG. Sin embargo, debido al lixiviado durante la reacción, nos impide utilizarlos a nivel de planta piloto. Por tanto, el catalizador más adecuado para ser probado en planta piloto es la resina Amberlyst-16, ya que ha presentado el mejor rendimiento y es estable a la lixiviación. Con los resultados obtenidos en el laboratorio se diseñó y se fabricó, juntamente con una empresa de ingeniería, una planta piloto para la fabricación de ésteres en un reactor de lecho fijo. En ella se realizaron estudios de viabilidad técnica y económica para la reacción de esterificación de ácido láurico. Los resultados obtenidos indicaron que es posible fabricar 2-EHL a nivel de planta piloto en conversiones cercanas al 98% utilizando un catalizador ácido como es la resina Amberlyst-16. Se llevo a cabo un estudio de viabilidad económica con el que se pudo comprobar cómo con la planta piloto no es rentable fabricar, pero si se decidiera invertir en una planta industrial en continuo para la fabricación de ésteres de ácidos grasos, el retorno de inversión sería prácticamente inmediato, ya que la eficiencia de fabricación es mucho mayor que la que se tiene en una planta de esterificación en batch. Por último, se realizaron pruebas de uso del 2-EHL fabricado en la planta piloto para determinar si era posible utilizar en 2-EHL con la conversión del 98% en formulaciones de tintas digitales cerámicas en base solvente, los resultados obtenidos fueron excelentes, ya que no había variación en las propiedades de la tinta al sustituir el 2-EHL comercial por el 2-EHL fabricado en la planta piloto, dando por concluido el estudio. / [CAT] En aquesta tesi doctoral el principal objectiu ha estat desenvolupar una nova metodologia per produir monoèsters, dièsters i poliols derivats d'àcids grassos de forma contínua. Una producció en continu incrementa la producció i la productivitat per temps de catalitzador. A més, aquesta metodologia és molt més sostenible per al medi ambient, ja que fa decréixer el factor E (Factor E = kg totals de substàncies involucrades en el procés/Kg de producte) i es redueixen també els residus generats, si els comparem a un procés en discontinu. Així mateix, el procés en continu s'ha desenvolupat mitjançant catàlisi heterogènia i mitjançant sòlids polimèrics de nova síntesi. Cal destacar que actualment no hi ha a la literatura cap referència de producció en continu per a l'esterificació d'àcids grassos lineals de cadena llarga amb alcohols. En primer lloc, es va realitzar un "screening" de diferents catalitzadors a nivell de laboratori per a la reacció d'esterificació tant a "batch" com a un reactor de llit fix. Entre els catalitzadors provats es va veure com catalitzadors com el PAFR eren altament actius a la conversió d'àcids, però la seva limitada disponibilitat a nivell comercial va limitar el seu posterior ús. Una altra tipologia de catalitzadors provats van ser els carbons actius funcionalitzats amb sofre, entre ells el catalitzador que millor va funcionar va ser el Norit RBHG. Tot i això, a causa del lixiviat durant la reacción, esta ens impedeix utilitzar-los a nivell de planta pilot. Per tant, el catalitzador més adequat per ser provat a planta pilot és la resina Amberlyst-16, ja que ha presentat el millor rendiment i és estable a la lixiviació. Amb els resultats obtinguts al laboratori es va dissenyar i fabricar, juntament amb una empresa d'enginyeria, una planta pilot per a la fabricació d'èsters en un reactor de llit fix. S'hi van fer estudis de viabilitat tècnica i econòmica per a la reacció d'esterificació d'àcid làuric. Els resultats obtinguts van indicar que és possible fabricar 2-EHL a nivell de planta pilot en conversions properes al 98% utilitzant un catalitzador àcid com és la resina Amberlyst-16. Es va dur a terme un estudi de viabilitat econòmica amb què es va poder comprovar com amb la planta pilot no és rendible fabricar, però si es decidís invertir en una planta industrial en continu per a la fabricació d'èsters d'àcids grassos, el retorn d'inversió seria pràcticament immediat ja que l'eficiència de fabricació és molt més gran que la que es té en una planta d'esterificació en batch. Finalment, es van realitzar proves d'ús del 2-EHL fabricat a la planta pilot per determinar si era possible utilitzar a 2-EHL amb la conversió del 98% en formulacions de tintes digitals ceràmiques en base solvent, els resultats obtinguts van ser excel·lents ja que no hi havia variació en les propietats de la tinta en substituir el 2-EHL comercial pel 2-EHL fabricat a la planta pilot, donant per conclòs l'estudi. / [EN] In the present doctoral thesis, the main objective has been to develop a new methodology to produce mono-esters, di-esters and polyols derived from fatty acids, continuously. Continuous production increases production and productivity per catalyst time. In addition, this methodology is much more sustainable for the environment, since it decreases the factor E (Factor E = total kg of substances involved in the process/Kg of product) and the waste generated is also reduced, if we compare to a discontinuous process. Likewise, the continuous process will be developed through heterogeneous catalysis and through newly synthesized polymeric solids. It should be noted that there is not any current continuous production reference in the literature for the esterification of long-chain linear fatty acids with alcohols. In the first place, a screening of different catalysts was carried out at the laboratory level for the esterification reaction both in batch and in a fixed-bed reactor. Among the catalysts tested, catalysts such as PAFR were found to be highly active in acid conversion, but their limited commercial availability prevented their further use. Another type of catalyst tested was sulfur-functionalized active carbon, and the catalyst that worked best was Norit RBHG. However, due to leaching during the reaction, it prevents us from using them at the pilot plant level. Therefore, the most suitable catalyst to be tested in a pilot plant was the Amberlyst-16 resin, since it presented the best performance and is stable to leaching. With the results obtained in the laboratory, a pilot plant for the manufacture of esters in a fixed-bed reactor was designed and manufactured, together with an engineering company. Technical and economic feasibility studies were carried out for the lauric acid esterification reaction. The results obtained indicated that it is possible to manufacture 2-EHL at a pilot plant level with conversions close to 98%, using an acid catalyst such as Amberlyst-16 resin. An economic feasibility study was carried out which verifies that the pilot plant it is not profitable to manufacture, but if it were decided to invest in a continuous industrial plant for the manufacture of fatty acid esters, the return on investment would be practically immediately, since the manufacturing efficiency is much higher than that of a batch esterification plant. Finally, use tests of the 2-EHL manufactured in the pilot plant were carried out to determine if it was possible to use 2-EHL with a conversion of 98% in solvent-based ceramic digital ink formulations. The results obtained were excellent since there was not any variation in the properties of the ink when substituting the commercial 2-EHL, thus ending the study so far. / Martínez Castelló, A. (2022). Esterificación de ácidos grasos en lecho fijo [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/191533