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The esterification of lactic acid with ethanol over Lewatit S 100, strong cation ion exchange resin catalyst, was studied in counter current vapor-liquid contactor type differential reactor by feeding ethanol and lactic acid solution as vapor and liquid phases, respectively. The ethanol vapor phase was diluted by dry air and the water removal was achieved by the mass transfer of water from liquid to vapor phase. Effect of ethanol to lactic acid feed molar ratio and vapor flow rate on fractional conversion and water removal efficiency were tested at 40-70&deg / C of column temperature range. It was observed that Lewatit S 100 was adequate catalyst for esterification of lactic acid with ethanol. Increase in ethanol to lactic acid feed molar ratio enhanced both lactic acid conversion and water removal by upper product stream. However, lactic acid conversion was suppressed by the increase of inlet vapor flow rate because of the decrease in ethanol concentration in gas phase which affected both esterification reaction rate and mass transfer rate. The reaction temperature is the other important parameter that affects the mass transfer of ethanol from vapor to liquid phase. Although reaction rate and equilibrium conversion values were promoted by temperature, the lower solubility of ethanol in liquid phase limited the fractional conversion while promoted the water mass transfer from liquid to vapor phase. The optimized vapor phase velocity and temperature can yield higher conversions than the equilibrium conversion at the same temperature and initial composition. Therefore, low pressure organic acids such as lactic acid can be successfully esterified by using counter current V-L contactor type reactors and by using integrated reaction and separation units.

Ethyl lactate is a promising, and environmentally benign chemical, which requires efficient separation techniques to overcome the equilibrium limitations in its production. Pervaporation based hybrid systems are successful in these type of equilibrium limited reactions, where product and/or by-product are removed from reaction medium by pervaporation unit(s) so as to drive reaction to completion. For the production of ethyl lactate four possible semi-batch hybrid systems were previously proposed. However, in order to select the suitable hybrid system within the proposed layouts phase equilibrium and reaction kinetics of the system must be well defined in addition to the performance data of the pervaporation membranes. Therefore, vapor pressure curve of ethyl lactate, VLE curves of ethanol-ethyl lactate and ethyl lactate-water were determined and performances of commercial hydrophobic membranes were investigated experimentally for the separation of ethanol-ethyl lactate mixtures. As a result of vapor pressure and VLE experiments, azeotrope was observed at 71wt% of water for ethyl lactate-water binary mixture at 80mmHg pressure. Furthermore, dependence of vapor composition on pressure was found to be slight for ethanol-ethyl lactate mixtures. Two commercial hydrophobic membranes, and an organoselective one were used in the separation of ethyl lactate-ethanol mixtures. It is found that hydrophobic membranes have sufficient fluxes and reasonable selectivities. Moreover, it is observed that as temperature increase flux increases and selectivity decreases. Finally, it is concluded that it would be possible to produce ethyl lactate by using the previously proposed integrated PV-esterification reactor systems.

iv The recovery of lactic acid from its dilute aqueous solutions is a major problem. The ester of lactic acid, namely, methyl lactate has a wide range of applications. The esterification of an aqueous solution of lactic acid with methanol is a reversible reaction. As excess of amount water is present in the reaction mixture, the conversion is greatly restricted by the chemical reaction equilibrium limitations. In this study the esterification kinetics of lactic acid with methanol both in the absence and presence of an ion exchange resin as a heterogeneous acid catalyst was investigated with isothermal batch experiments between 40 - 70 0 C and at atmospheric pressure. Self-polymerization of lactic acid was enlightened by considering the hydrolysis reaction of lactoyllactic acid at the reaction temperatures and at various initial concentrations. Both homogeneous and heterogeneous reaction rate constants were evaluated. Methyl lactate process development was also investigated. The process was based on the recovery of 10% lactic acid by reaction with methanol in a absorption column using ion-exchange resin Lewatit SPC-112 H+. The effect of various parameters including lactic acid concentration or reactant molar ratio, lactic acid feed flow rate, methanol and inert carrier rate on reactor performance were studied. The reaction of methyl lactate formation over the ion exchange resin catalyst was observed to be slower than the mass transfer rate whereas mass transfer of methanol in gas phase was the limiting step for methanol transfer to the liquid mixture. Mass transfer of water from liquid phase to the gas phase was controlled by the mass transfer resistance of liquid phase. Thus, it can be concluded that the counter-current gas-liquid reactors with acidic solid catalysts can be used as simultaneous reaction and separation equipment.

In this research, molybdophosphoric acid (PMo) was blended with polysulfone polymer (PSF) and form a film catalyst by using a common solvent dimethylformamide (DMF). Kinetic and mass transfer parameters were evaluated for catalytic films in ethanol lactic acid esterification reaction as film surface area, film thickness and catalyst loading were varied at 50&amp / #61616 / C, 1 atm and 1:1 ethyl alcohol to lactic acid mole ratio conditions. Also prepared films were characterized by DSC, TGA, FTIR, X-ray and SEM analysis. It was observed that the catalytic films showed higher activities with respect to the unloaded form of PSF and activities were increased with the increasing loading levels. The stabilities of the loaded catalysts were tested by means of deactivation experiments. A decrease was observed after 5th trial for 10wt% PMo loaded PSF film and at 4th trial for 15wt% PMo loaded PSF film. However, activities of the loaded films gave still higher conversion results than the unloaded PSF film. Also it was proved that with increasing film thickness conversion was decreased and increasing surface area conversion was increased. It was observed from the characterization studies that PMo catalysts have no chemical interaction with the PSF polymer and there was trace amount of DMF solvent was observed in the PMo-PSF catalytic film. Particulate structure of the PMo catalyst was observed and there is no catalyst agglomeration in the membrane network. However, along the thickness, catalyst particles were not homogeneously but finely dispersed in amorphous film structure.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2007. / Härtill 4 uppsatser.

Cette étude a pour objectif l'étude des processus impliqués dans la production de l'acrylate de 2-éthylhexyle, ester gras dérivé de l'acide acrylique. Cette réaction est accélérée par l'emploi d'un catalyseur solide, une résine acide sulfonée. Les interactions spécifiques des différents composés avec cette résine ont été étudiées à température ambiante. A 90°C, le couplage avec la cinétique de réaction a été analysé et modélisé en réacteur fermé. Un montage pilote spécifique conçu au laboratoire a permis la réalisation de réactions dans un réacteur en lit fixe, dont la structure tripartite permet le suivi des concentrations liquides dans le montage. Une modélisation représentant cette installation a été mise au point, associant l'affinité sélective, la cinétique de réaction et l'hydrodynamique de l'écoulement. Ce modèle a ensuite été utilisé pour l'analyse de modèles de tendances, pour déterminer des conditions de fonctionnement améliorés d'un procédé de taille industrielle / This study aims at analyzing and understanding the processes involved in the production of 2-ethylhexyl acrylate. This fatty ester is a derivative of acrylic acid. This reaction is accelerated by the use of a solid catalyst, a sulfonated resin acid. The specific interactions of compounds with this resin were studied at room temperature. At 90°C, the coupling of kinetics and selective affinity was analyzed and modeled in a closed reactor. A specific pilot installation was designed in laboratory. Esterification reactions were performed. in this fixed bed reactor. The tripartite structure allows the monitoring of liquid levels in all installation. A model representing this system was developed, involving selective affinity, kinetics and hydrodynamic. This model was then used to analyze trends models to determine improved operating conditions for an industrial size process

Orientador: Luciana Francisco Fleuri / Resumo: O processamento de suco de laranja gera grande volume residual, sendo este aproximadamente 50% do fruto. Esses resíduos contêm biomoléculas de interesse industrial tais como as lipases que são capazes de catalisar a hidrólise de glicerídeos e reações de síntese em condições micro-aquosas. A obtenção dessas enzimas diretamente de resíduos reduz os custos de produção e viabiliza diferentes aplicações. As lipases possuem características interessantes como a regioespecificidade e especificidade quanto aos tamanhos da cadeia carbônica de ácidos graxos, possibilitando a geração de produtos diferenciados. Desta forma, o presente trabalho visou, além da obtenção de lipases por meio resíduos de laranja Pera, a aplicação destas em reações capazes de promover mudanças nos substratos (lipídeos) a fim de se obter produtos diferenciados que possam apresentar atividades biológicas. Lipases foram obtidas dos resíduos de laranja Pera e caracterizadas como 1,3 específicas nas frações bagaço, casca e frit as quais apresentaram atividade lipolítica de 55,9 U/g; 58,0 U/g e 49,9 U/g, respectivamente; e da fração polpa como inespecífica com atividade de 40,4 U/g. Essas enzimas foram empregadas em reações de hidrólise e síntese com diferentes óleos vegetais e os produtos de reação analisados quanto às atividades biológicas. Foram obsevadas atividades antioxidante de até 94,87%; atividade antibacteriana sobre E. coli, L. monocytogenes, P. aureginosa, S. enteritidis e S. aureus, e influência sobre a ... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre

Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-06-05T18:19:01Z No. of bitstreams: 2 maisa_costa_santos.pdf: 2334209 bytes, checksum: 9004aeaeb9cd7b271794191d109efa36 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-06-22T12:32:04Z (GMT) No. of bitstreams: 2 maisa_costa_santos.pdf: 2334209 bytes, checksum: 9004aeaeb9cd7b271794191d109efa36 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-06-22T12:32:04Z (GMT). No. of bitstreams: 2 maisa_costa_santos.pdf: 2334209 bytes, checksum: 9004aeaeb9cd7b271794191d109efa36 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016 / Funda??o de Amparo ? Pesquisa do Estado de Minas Gerais (FAPEMIG) / O presente estudo descreve a s?ntese do catalisador heterog?neo SiO2-SO3H, obtido atrav?s da imobiliza??o dos grupos sulf?nicos em SiO2, produzida a partir de uma mistura contendo ?rea de constru??o e carbonato. A imobiliza??o do -SO3H foi confirmada, atrav?s da caracteriza??o inicial da s?lica e do catalisador por IV, MEV, DRX, TGA e isotermas de adsor??o/dessor??o BET, que demonstrou haver modifica??o da estrutura da s?lica ap?s a imobiliza??o dos grupos sulf?nicos, ocasionando diminui??o da ?rea superficial espec?fica (SBET) de 507 para 115 m2 g?1, e uma diminui??o do volume dos poros 0,78 para 0,38 cm3 g-1. Inicialmente, avaliou o desempenho catal?tico da mistura SiO2-SO3H em rea??es de esterifica??o do ?cido ac?tico e do ?cido graxo (octan?ico) com o 2,2-dimetil-1,3-dioxolano-4-metanol, conhecido como ?solketal?, que possui uma cadeia carb?nica grande, al?m de ter outro grupo funcional na sua estrutura. Os resultados obtidos demonstram a efici?ncia do SiO2-SO3H para a s?ntese do acetato 2,2- dimetil-1,3-dioxolan-4-il metil, em que utilizou-se inicialmente, como reagentes, glicerol bruto, acetona e a mistura catal?tica, ap?s 2 hora de rea??o, foi adicionado no mesmo reator, o ?cido ac?tico em um processo ?one pot?, sem a pr?via extra??o e a purifica??o do solketal (reagente intermedi?rio). Pelo o mesmo procedimento, foi obtido, em excelente rendimento, o octanoato de solketila. Nesses processos reacionais n?o houvera a necessidade do uso de solvente ou aparelhos auxiliares, como clevenger ou dean-stark, para remo??o da ?gua formada durante o processo que envolve 2 rea??es (cetaliza??o e esterifica??o), sendo dessa forma resistente ao processo de lixivia??o. Diante dos excelentes resultados, partiu para rea??es de esterifica??o com outros ?cidos graxos, com at? 18 ?tomos de carbono na cadeia, tais como o ?cido linoleico e oleico. Contudo n?o foi observado a forma??o de produtos nessas rea??es. Acredita-se que esse fato esteja relacionado com a grande afinidade que o solketal apresenta pelo SiO2-SO3H, devido a sua alta polaridade, fazendo com que fique retido dentro dos poros do catalisador. Outro ponto importante foi o tamanho da cadeia carb?nica dos ?cidos graxos utilizados, visto que quanto maior o tamanho da mol?cula, maior a hidrofobicidade, isso faz com que eles sofram repuls?o do catalisador. Acredita-se que esses dois fatores contribu?ram para que n?o ocorresse a intera??o entre os reagentes e o catalisador, levando, em alguns casos, ? forma??o de ?steres de solketila com rendimentos moderados. Essa hip?tese foi comprovada, quando utilizou-se um ?lcool de cadeia carb?nica menor, como o metanol, o qual reagiu com o ?cido linoleico e oleico na presen?a da mistura catal?tica SiO2-SO3H, para produ??o de ?steres met?licos. Os resultados obtidos comprovam a s?ntese do oleato de metila e do linoleato de metila no tempo de 15 min, com rendimento em torno de 96 a 98%. Isso demonstrou que ? de fundamental import?ncia o escoamento dos reagente para os poros do catalisador. O que sugere que para garantir o sucesso das rea??es do solketal com ?cidos de cadeia carb?nica maior o escoamento desse reagentes devem ser facilitado e isso pode ser obtido atrav?s do uso de solvente. / Disserta??o (Mestrado) ? Programa de P?s-gradua??o em Biocombust?veis, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / The synthesis of the heterogeneous SiO2-SO3H, catalyst, obtained by the immobilization of the sulfonic groups in SiO2, produced from a mixture containing building and carbonate. The immobilization of -SO3H was confirmed, through the initial characterization of the silica and the catalyst by IV, SEM, XRD, TGA and adsorption / desorption isotherms, which showed that there was modification of the silica structure after the immobilization of the sulfonic groups, resulting in a decrease of the specific surface area (SBET) from 507 to 115 m2 g-1, and decreasing in volume by 0,78 to 0,38 cm3 g-1. Initially, evaluated the catalytic performance of the SiO2 -SO3H mixture in esterification reactions of acetic acid and fatty acid (octanoic acid) with 2,2-dimethyl-1,3-dioxolane-4-methanol, known as "solketal", it has a large carbon chain, plus another functional group in its structure. The results obtained demonstrate the efficiency of SiO2 -SO3H for the synthesis of 2,2-dimethyl-1,3-dioxolan-4-yl methyl acetate, at where initially used as reagents, crude glycerol, acetone and the catalytic mixture, after 2 hour of reaction, was added in the same reactor, acetic acid in a "one pot", without prior extraction and purification of the solketal (intermediate reagent). By the same procedure, it was obtained, in excellent yield, solketila octanoate. In these reaction processes there was no need for the use of solvents or auxiliary devices, such as clevenger or dean-stark, for the removal of water formed during the process involving 2 reactions (ketalization and esterification), thus being resistant to the leaching process. Given the excellent results, started to esterification reactions with other fatty acids, with up to 18 carbon atoms in the chain, such as linoleic and oleic acid. However, the formation of products in these reactions was not observed. It is believed that this fact is related to the great affinity that the solketal presents by the SiO2-SO3H, due to its high polarity, causing it to be trapped within the catalyst pores. Another important point was the size of the carbonic chain of the fatty acids used, since the larger the size of the molecule, the greater the hydrophobicity, this causes them to undergo catalyst repulsion. It is believed that these two factors contributed to the lack of interaction between the reactants and the catalyst, leading in some cases to the formation of solketila esters with moderate yields. This hypothesis has been proven, used a lower carbon alcohol, such as methanol, which reacted with linoleic and oleic acid in the presence of the catalytic mixture SiO2 -SO3H, for the production of methyl esters. The results obtained demonstrate the synthesis of methyl oleate and methyl linoleate in the 15 min time, with yield around 96 to 98%. This has demonstrated that it is of fundamental importance the flow of the reactants into the pores of the catalyst. This suggests that to ensure the success of solketal reactions with higher carbonic acids the flow of these reagents should be facilitated and this can be obtained through the use of solvente.

Alkyl esters, identified as biodiesel, are obtained by transesterification of vegetable oils or by esterifications of fatty acids. The transesterification process, to produce biodiesel, consists of a chemical reaction of vegetable and animal oils or fats with the common alcohol (ethanol) or methanol, in the presence of a catalyst (Brönsted acid or base). By esterification, biodiesel results of the reaction of fatty acids with an alcohol, forming monoesters and water. This reaction can be catalyzed by species as Brösnted acids. Titanium and zirconium compounds, mainly the alcoxides, are known as good catalysts in transesterification and esterification reactions. However, these systems are sensible to the humidity and impurities of the reactional medium. In this context, this work presents results of the synthesis of titanium and zirconium compounds, exhibiting stability and tolerance to impurities present in the reactional medium. Complexes exhibiting the formule M (n-butoxide)x(malthol)4-x, where M=Ti or Zr, had been synthesized by the reaction of M (n-butoxide)4 with the ligand 3- hydroxi-2-methyl-4-pirone, during 48 hours, in THF. They had been washed with THF, dried and characterized. By spectroscopy in medium infra-red region, was determined that the complexation of the ligand occurs by the ά-hydroxyquinone deprotonated fragment. The most remarkable differences between the ligand spectrum and those of the complexes were the disappearance of the OH stretching mode at 3262 cm-1 and the shift of C=O stretching from 1656 cm-1 in the pyrone to ca. 1610 cm-1 in the pyronate complexes. The esterification reactions conduced in the presence of the metallic precursors (M(n-butoxide)4), (M=Ti or Zr), had confirmed the sensitivity of catalysts. In the reactions conduced in the presence of complexes M(nbutoxide) x(maltol)4-x (M=Ti or Zr) yields among 15 and 92 % (% FAMEs) were obtained, according of reactional conditions used. / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Ésteres alquílicos, denominados de biodiesel, são obtidos pela transesterificação e esterificação etílica ou metílica de óleos vegetais ou gorduras animais. O processo de transesterificação, para obtenção de biodiesel, consiste numa reação química dos óleos ou gorduras vegetais ou animais com o álcool comum (etanol) ou o metanol, na presença de um catalisador (base ou ácido de Brönsted). Já o biodiesel obtido via esterificação, resulta de uma reação onde um ácido graxo reage com um álcool formando monoésteres e água. Comumente, esta reação pode ser catalisada por espécies que atuam como ácidos de Brösnted. Compostos de titânio e de zircônio, sobretudo os alcóxidos, são conhecidos como catalisadores eficientes em reações de transesterificação e esterificação. Porém, estes sistemas são bastante sensíveis à umidade e impurezas do meio reacional. Neste contexto, este trabalho apresenta resultados visando à síntese de compostos de titânio e zircônio, que sejam mais estáveis e mais tolerantes a possíveis contaminantes, presentes no meio reacional. Complexos de fórmula geral M(n-butóxido)x(maltol)4-x, onde M=Ti ou Zr, foram obtidos pela reação de M(n-butóxido)4 com o ligante 3-hidroxi-2-metil- 4-pirona, durante 48 horas, em THF. Eles foram lavados com THF, secos e caracterizados. Por espectroscopia na região do infravermelho médio, ficou evidenciada a coordenação do ligante ao centro metálico, provavelmente pelo fragmento ά-hidroxiquinona desprotonado. A comparação, entre o espectro do ligante livre e os dos complexos, permite observar o desaparecimento da absorção de estiramento OH do ligante (3262 cm−1) e o deslocamento da banda de absorção de estiramento da C=O, de 1656 cm−1 (no ligante) para aproximadamente 1610 cm−1 (nos complexos). Testes com os precursores metálicos (M(n-butóxido)4), M=Ti e M=Zr confirmaram a sensibilidade destes ao meio reacional. Já as reações conduzidas na presença de complexos M(nbutóxido) x(maltol)4-x de Ti ou Zr, mostraram rendimentos (% ésteres metílicos) entre 15 e 92%, dependendo da condição reacional empregada.