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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
11

OBTENÇÃO E CARACTERIZAÇÃO DE CATALISADORES SÓLIDOS DE NIÓBIO MODIFICADOS COM METAIS ALCALINOS TERROSOS PARA REAÇÕES DE TRANSESTERIFICAÇÃO E ESTERIFICAÇÃO / OBTAINING AND CHARACTERIZATION OF SOLID CATALYSTS OF NIOBIUM MODIFIED WITH ALKALINE EARTH METALS TRANSESTERIFICATION AND ESTERIFICATION

Santos Neto, Inocêncio Sanches dos 03 April 2013 (has links)
Made available in DSpace on 2016-08-19T12:56:44Z (GMT). No. of bitstreams: 1 Dissertacao Inocencio.pdf: 2764893 bytes, checksum: 8b5e78c33e9a9309d46a3f7ff7b3a5e9 (MD5) Previous issue date: 2013-04-03 / FUNDAÇÃO DE AMPARO À PESQUISA E AO DESENVOLVIMENTO CIENTIFICO E TECNOLÓGICO DO MARANHÃO / Biodiesel is obtained mainly by homogeneous catalysis, however this process has disadvantages as saponification of the esters and difficulty of separation of the catalyst from the products formed. In this work, ceramic catalysts were prepared from the surface modification of niobia with alkaline earth metals (Ba and Ca) and transition metals (Ni and Cu) in order to improve the catalytic activity in the transesterification reaction of beef tallow and esterification of oleic acid. The catalysts were obtained by the polymeric precursor method (PPM). Therefore, such systems were characterized by X-ray diffraction (XRD) and infrared spectroscopy in the Fourier transform (FTIR), Raman spectroscopy and transmission electron microscopy (TEM) analysis of gas adsorption. The XRD results suggest that the niobium surface modification, but with secondary phases. Raman spectra of the catalysts exhibit vibrational modes near 701 cmˉ¹ corresponding to phase T-Nb₂O₅. The bands between 311 cmˉ¹ and 230 cmˉ¹, corresponding to vibrational modes of the bonds O-Nb-O, Nb-O-Nb. FTIR spectra showed vibrational modes in the region between 500 - 850 cmˉ¹ which may be associated with a NbO₆ octahedra, vibrations in modes 635 cmˉ¹, 560 cmˉ¹ and 500 cmˉ¹ are associated Nb-O bonds in Nb-O6 octahedra distorted. A cursory analysis shows that the catalysts are non-porous materials. The catalysts of niobium modified barium and copper, calcium and copper, barium and calcium, and nickel and nickel exhibited catalytic activity for transesterification of beef tallow and oleic acid esterification. The catalysts modified with 5% barium and copper, showed better conversion to oleic acid esterification and transesterification beef with 71% to 95%, respectively. Thus, these catalysts were effective for the transesterification of beef tallow and oleic acid esterification. / O biodiesel é obtido principalmente via catálise homogênea, entretanto esse processo apresenta desvantagens como saponificação dos ésteres e a dificuldade de separação do catalisador dos produtos formados. Neste trabalho, foram preparados catalisadores cerâmicos a partir da modificação da superfície da nióbia, com metais alcalinos terrosos (Ba e Ca) e metais de transição (Ni e Cu), no intuito de melhorar a atividade catalítica desses materiais na reação de transesterificação do sebo bovino e esterificação do ácido oléico. Os catalisadores foram obtidos pelo método dos precursores poliméricos (MPP). Para tanto, tais sistemas foram caracterizados por difração de raios X (DRX), espectroscopia na região do infravermelho com transformada de Fourier (FTIR), espectroscopia Raman, Microscopia eletrônica de transmissão (TEM) e Análise de adsorção de gás. Os resultados de DRX sugerem a modificação da superfície do nióbio, porém com fases secundárias. Os espectros Raman dos catalisadores exibem modos vibracionais próximos a 701 cmˉ¹ corresponde à fase T-Nb₂O₅. As faixas compreendidas entre 311 cmˉ¹ e 230 cmˉ¹, correspondem aos modos vibracionais das ligações O-Nb-O, Nb-O-Nb. Os espectros FTIR apresentaram modos vibracionais na região entre 500 - 850 cmˉ¹ que pode se associado aos octaedros de NbO6, os modos vibrações em 635 cmˉ¹, 560 cmˉ¹ e 500 cmˉ¹ são associadas as ligações Nb-O em octaedros Nb-O₆ distorcidos. A análise superficial demonstrou que os catalisadores são materiais não porosos. Os catalisadores de nióbio modificados com bário e cobre, cálcio e cobre, bário e níquel e cálcio e níquel apresentaram atividade catalítica para transesterificação de sebo bovino e esterificação do ácido oléico. Os catalisadores modificados com o bário 5% e cobre, apresentaram melhor conversão para esterificação do ácido oléico e transesterificação do sebo bovino com 71% e 95%, respectivamente. Desta forma, esses catalisadores mostraram-se eficientes para reação de transesterificação do sebo bovino e esterificação do ácido oléico.
12

Oxidação total de metano sobre catalisadores de paladio e estanho suportados em zirconia / Methane oxidation over zirconia-supported palladium and tin catalysts

Lovon Quintana, Juan Jose 12 August 2018 (has links)
Orientador: Gustavo Paim Valença / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-12T09:16:19Z (GMT). No. of bitstreams: 1 LovonQuintana_JuanJose_D.pdf: 3240261 bytes, checksum: ad92f4d1100edab50342a486f6808682 (MD5) Previous issue date: 2008 / Resumo: Pd e Sn foram suportados sobre ZrO2 por impregnação incipiente usando Pd(NO3)2.XH2O e SnC4H4O6.XH2O como precursores. Os sólidos foram secados e calcinados a 800, 1100 e 1400 K e caracterizados por ICP-AES, TEM, XRD, TPR, adsorção de H2, O2 e CO e por titulação de oxigênio adsorvido com H2. Nos sólidos contendo Pd ou Pd-Sn calcinados a 800 K as partículas de Pd foram completamente oxidadas formando fases com baixo grau de cristalinidade e os sólidos calcinados a 1400 K a fase ativa foi decomposta a Pd° e sinterizada, formando partículas de Pd com planos cristalinos expostos de baixa densidade Pd(200). A quantidade de O2 adsorvido sobre Pd-Sn ou Sn suportado sobre ZrO2 foi maior que nos sólidos contendo Pd suportado sobre ZrO2. O tamanho das partículas metálicas de Pd determinadas por adsorção de H2 foi maior que nos sólidos contendo Sn. Os testes de reação da oxidação de CH4 sobre catalisadores de Pd e Sn suportados sobre a ZrO2 foram realizados em um reator de fluxo contínuo a pressão atmosférica, na faixa de temperaturas de 450 até 750 K. A atividade catalítica dos sólidos foi dependente das condições de preparação dos catalisadores. Os sólidos Pd-Sn/ZrO2 calcinados a temperaturas = 1100 K mostraram valores de TOR de 2 a 4 vezes maiores do que para Pd/ZrO2 devido à alta capacidade de armazenamento de O2 nos sólidos contendo Pd e Sn. No entanto, com o aumento da temperatura de calcinação a contribuição do Sn diminuiu, sendo praticamente zero a 1400 K. / Abstract: Pd and Sn were supported on ZrO2 by incipient wetness using Pd(NO3)2.XH2O and SnC4H4O6.XH2O as precursors. The solids were dried and calcined at 800, 1100 and 1400K. The solids were characterized by ICP- AES, TEM, XRD, TPR, adsorption of H2, O2, and CO and by titration of adsorbed oxygen with H2. In the solids containing Pd or Pd-Sn calcined at 800 K the Pd particles were made of fully oxidized low crystalline phases and the solids calcined at 1400 K the active phase was decomposed to Pdº and sinterized, with the formation of particles with exposed low density planes such as Pd(200). The amount of adsorbed O2 on Pd-Sn or Sn supported on ZrO2 was higher than that on Pd supported on ZrO2. The size of the Pd particles determined by adsorption of H2 was larger for the Sn-containing samples. The methane catalytic combustion on palladium and tin catalysts supported on ZrO2 was carried out in a flow reactor at atmospheric pressure at the temperatures range of 450 to 750 K. The catalytic activity of the solids was strongly dependent on the preparation conditions. The solids Pd-Sn/ZrO2 calcined at temperatures = 1100K showed values of TOR twice to four times higher than the Pd/ZrO2 due to the high O2 storage capacity of the catalysts containing Pd and Sn. However, with the increase of the calcination temperature the Sn contribution decrease and was null at 1400 K. / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química
13

Výroba bionafty z použitých jedlých olejů / Biodiesel production from used edible oils

Menšíková, Petra January 2008 (has links)
This diploma thesis is engaged in considering of suitable technology for biodiesel production from used cooking oils. For the main parts of technology were made some mathematical models in a Chemcad programme. There was made a laboratory analysis of various samples of used cooking oil.
14

Catalytic Conversion of Biomass to Bio-Fuels

Wijayapala, Hevagamage Rangana Thilan 13 December 2014 (has links)
The conversion of biomass to biouel has received considerable attention as a sustainable way to produce energy. As worldwide fossil fuels become depleted these efforts grow in importance. The overall strategy is to transform the parent biomass feedstock to increase C-C bonds while reducing oxygen in the final products. A catalytic approach is often used to achieve good yields of transportation grade liquid hydrocarbons from biomass. Development of novel catalyst systems to aid in the thermochemical conversion of biomass to biouel is the focus of this thesis. Gasification of biomass produces synthesis gas (CO and H2). Synthesis gas can be converted to liquid hydrocarbons using Fischer-Tropsch (FT) synthesis. Mo/ZSM-5 FT catalysts with a potassium (K) promoter are introduced to enhance liquid hydrocarbon production and CO conversion of synthesis gas. Liquid products and CO conversion were determined using GC-MS analysis with respect to changes in K loading from 0-2%. The highest liquid product selectivity (21.7%) was found with 1.0% K loading while largest CO conversion (63%) was found with 1.2% K loading. This catalyst work was extended by introducing Ni and Co into the Mo/ZSM-5 catalysts. A copper based water gas shift catalyst (WGS) was also used in concert with the FT catalyst to improve product selectivity. This WGS catalyst promotes the in-situ production of H2 while decreasing water content. The FT+WGS catalyst were used to convert both 1:1 CO: H2 syngas and bio-syngas at 280 °C and 350 °C. The liquid hydrocarbon selectivity was significantly changed and the CO conversion was remarkably increased compared to the reactions without the dual catalyst at both temperatures. In the fourth chapter, FT+WGS catalysts were studied for upgrading bio-oil model compounds. Guaiacol and furfural were used as the model compounds and upgrading reactions were done under H2, syngas and bio-syngas at 200, 250 and 300 °C. Significant conversion of both guaiacol (85%) and furfural (100%) occurred with syngas at 300 °C. Products upgraded from syngas had a higher combined heat of combustion than the products with pure H2. This suggests the incorporation of some C from CO with model compound upgrading reactions with syngas.
15

Biodiesel production by using heterogeneous catalyst / Tillverkning av biodiesel med heterogena katalysatorer

Khurshid, Samir Najem Aldeen January 2014 (has links)
No description available.
16

Optimizing a Single Atom Catalyst for theOxygen Evolution Reaction using DensityFunctional Theory

Hjelm, Vivien January 2019 (has links)
The growing interest of renewable fuel and energy sources has steadily increased over time due to climate changes. Research is being made around the world to find solutions for the different problems; one possible solution is to produce hydrogen gas to help phase out the usage of fossil fuels. So far, the technology for the hydrogen gas production is expensive for various reasons, one of the challenges is to minimize the energy usage for the production. Hydrogen could be used in fuel cells which can be used to fuel an electric car. In a fuel cell, hydrogen and oxygen gas are mixed to produce electrical energy as the main product, but it also forms thermal energy and water. Hydrogen gas can be produced from the reversed reaction; by electrolysis of water. This reaction requires energy and one way to minimize the energy usage for this is by using acatalyst. The goal with this master thesis was to see how the reaction rate of the oxygen evolution reaction can be affected by different single atom catalyst systems. The main structure for this catalyst in this thesis is aporphyrin molecule where different transition metals were tried as the active site. Different modifications on the structure were also made by exchanging some of the structures atoms and by adding different ligands.The purpose of this is to see how these modifications change the activity of the catalyst. The catalysts were optimized and calculated in a computational chemistry program called Gaussian 16. The calculations was made by using the DFT functional PBE0 and the basis sets Def2svp and Def2tzvpp. The results show that different modifications do affect the activity of the catalyst. The biggest variations in activity are from placing ligands under the active site while exchanging hydrogens to other substituents on the outer radial position can fine tune the results. The best active sites for this system came by using iridium, rhodium and cobalt which are all elements in group 9 of the periodic table. The lowest overpotential of 0.513 V was given by an iridium based system with four hydrogens exchanged by fluorides. / Runt om i världen finns ett ökat intresse för förnyelsebara energi och bränslekällor för att tackla klimat förändringarna. Stor del av forskningen som görs idag har i syfte att hitta nya lösningar för att minska klimatpåverkan i olika områden. Ett av forskningsområderna är hitta vägar till en miljövänligare vätgasproduktion där vätgasen skulle kunna användas i bränsleceller. Dessa celler kan sättas i elbilar och på så sätt fasa ut användingen av fossila bränslen. En av utmaningarna för vätgasproduktionen är att den idag är kostsam och kräver mycket energi. Forskare försöker hitta olika katalysatorer som kan minska energiåtgången som krävs vid elektrolys av vatten där syrgas och vätgas produceras. Målet med det här examensarbetet är att se hur en single atom catalyst kan påverka reaktionskinitiken för den syrgasbildande reaktionen vid elektrolys av vatten. Huvudstrukturen för katalysatorn som beräkningarna är gjorda på är en porphyrinmolekyl där olika övergångsmetaller kommer testas som det aktiva sätet i katalysatorn. Olika ligander kommer även tillsättas systemet samt utbyte av några väteatomer till olika substituenter i porfyrinstrukturen. Katalysatorn optimerades i det kvantkemiska beräkningsprogrammet Gaussian 16 med funktionalen PBE0 med basset Def2svp och Def2tzvpp. Resultaten visade att olika modifikationer på systemet hade en påverkan på katalysatorns aktivitet. Den största påverkan hade de olika liganderna som placerades under det aktiva sätet jämfört med de olika substituenterna. De bästa metallerna för katalysatorn var iridium, rhodium och kobolt vilket alla ligger i grupp nio i det periodiska systemet. Den lägsta överpotentialen på 0.513 V gavs av iridium systemet med fyra utbyta väten till fluor.
17

Theoretical Studies on Vibronic Coupling in Condensed Phases / 凝縮相における振電相互作用に関する理論的研究

Ota, Wataru 23 January 2024 (has links)
京都大学 / 新制・課程博士 / 博士(工学) / 甲第25014号 / 工博第5191号 / 新制||工||1991(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 佐藤 徹, 教授 田中 庸裕, 教授 佐藤 啓文 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM
18

Three-dimensional structured carbon foam : synthesis and applications

Pham, Ngoc Tung January 2016 (has links)
Recently, due to the unique properties and structures such as large geometric surface area, electrical conductivity and light weight, 3D structured carbon materials have been attracting extensive attention from scientists. Moreover, the materials, which can provide well-defined pathways for reactants to easily access active sites, are extremely useful for energy conversion as well as environmental and catalysis applications. To date, many precursors have been used for fabrication of 3D structured carbon materials including pitch, carbon nanotubes, graphene, and polymer foams. This thesis, as shown in the thesis title, focus on two main aspects: the study of the characteristics of melamine based carbon foam synthesized at different conditions and their applications. In paper I, it was revealed that through a simple, one-step pyrolysis process, flexible carbon foam synthesized from melamine foam (BasotectÒ, BASF) was obtained. Additionally, through a pyrolysis-activation process, activated carbon foam which possesses hydrophilic nature and high surface area was successfully synthesized. The characteristics of carbon foam such as the hydrophobic/hydrophilic nature, electrical conductivity, mechanical properties and surface chemistry were studied. It was shown that carbon foam could be successfully used as an absorbent in environmental applications e.g. removing of spill oil from water (paper I) or as support for heterogeneous catalysts, which in turn was used not only in gas phase reactions (paper I and IV) but also in an aqueous phase reaction (paper II). Importantly, when combined with a SpinChem® rotating bed reactor (SRBR) (paper II), the monolithic carbon foam/SRBR system brought more advantages than using the foam alone. Additionally, the work in paper III showed the potential of carbon foam in an energy conversion application as anode electrode substrate in alkaline water electrolysis. In summary, the versatility of the carbon foam has been proven through abovementioned lab scale studies and due to the simple, scalable and cost effective pyrolysis and activation processes used for the production, it has potential to be used in large-scale applications.
19

Development of silver nanocatalyst for propylene selective oxidation reaction

Yu, Bin January 2018 (has links)
Propylene is the second most important starting chemical in the petrochemical industry after ethylene. Unlike ethylene, propylene readily undergoes substitution reactions including polymerisation, oxidation, halogenation, hydrohalogenation, alkylation, hydration, oligomerization and hydroformylation, which lead to a wide variety of important downstream products. One of the principal uses of propylene is to produce key chemicals from selective oxidation. In 2016, the world annual production of propylene is about 94 million tonnes, and the global proportion used to produce selective oxidation product is over 18%. They constitute a key part of the chemical industry and contribute towards substantial economic benefits. The application of Ag based heterogeneous catalysts to selective propylene oxidation is a key factor in the synthesis of nearly all downstream chemicals, however billions of pounds are lost every year due to unplanned reactor shutdown, safety control and environment unfriendly emission control as a results of inefficiency catalytic selectivity and activity. Despite, both theoretical and experimental research works have been intensively involved, the fundamental reason leading to these effects are not yet well understood. The work presented in this thesis explores a range of novel modification techniques that alter the activity of Ag nanocatalysts for selective propylene oxidation, especially in propylene epoxidation. Particular focus is placed on developing surface modified Ag catalysts through morphology control, surface architecture engineering with another sublayer metal. Using a combination of modelling, novel and traditional materials characterisation methods, it is found that these modification result in some significant electronic and/or geometric alterations to the Ag nanoparticles surface. The Ag-Ag bond distance can be dramatically enlarged by exposing a high-index Ag surface or a core-shell structure with monolayer Ag shell. When interacting with molecular oxygen, the molecular oxygen adsorption and dissociation behaviour is sensitive to the geometric changes in Ag surface. This leads to an enhanced selectivity toward propylene epoxidation than combustion resulting from preventing a C-H bond cleavage. Finally, be creating atomically dispersed Ag on zeolite, a completely different interaction between molecular oxygen and single atom Ag were discovered comparing to on a extensive silver surface. This leads to the observation of an excitingly new propylene oxidation reaction producing ethanol and CO<sub>2</sub> resulting from C=C bond cleavage. Overall, the research presented within this thesis demonstrated a number of methods for the intelligent design of novel heterogeneous Ag catalysts with remarkable activity and selectivity toward specific selective propylene oxidation. These modification methods are believed to be potentially applicable to a wide range of other catalytic reactions.
20

Novo catalisador heterog?neo magn?tico SiO2/KI/?Fe2O3 para rea??o de transesterifica??o em ?leos vegetais para produ??o de biodiesel

Macedo, Alice Lopes 21 February 2017 (has links)
Data de aprova??o retirada da vers?o impressa do trabalho. / Incluir a Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) como ag?ncia financiadora. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-12-13T16:15:41Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) alice_lopes_macedo.pdf: 5251789 bytes, checksum: e988c8abc173c91e128980414db14ef9 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2018-01-03T12:17:24Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) alice_lopes_macedo.pdf: 5251789 bytes, checksum: e988c8abc173c91e128980414db14ef9 (MD5) / Made available in DSpace on 2018-01-03T12:17:24Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) alice_lopes_macedo.pdf: 5251789 bytes, checksum: e988c8abc173c91e128980414db14ef9 (MD5) Previous issue date: 2017 / Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) / A crescente demanda global por combust?veis l?quidos para transporte, gera??o de eletricidade, atividade industrial e produ??o agropecu?ria tem imposto planejamento de a??es direcionadas ao uso de fontes ambientalmente limpas de energia. Os derivados da biomassa s?o alternativas econ?mica e tecnicamente vi?veis aos de origem f?ssil, n?o renov?vel, ora dominantes na matriz energ?tica global. O biodiesel, l?quido formado por uma mistura de ?steres de ?cidos graxos, ? adequado ? opera??o em motores de combust?o interna de ciclo Diesel, em substitui??o ou em complemento ao petrodiesel, ou em outras m?quinas t?rmicas. O prop?sito central do presente trabalho foi o desenvolvimento de um catalisador s?lido economicamente vi?vel, quimicamente eficiente e ambientalmente limpo para a produ??o de biodiesel via processos de transesterifica??o de triacilglicer?is dos ?leos de maca?ba ou de soja, com metanol. Foi preparado o catalisador heterog?neo baseado em iodeto de pot?ssio impregnado em s?lica amorfa (SiO2; derivada de areia da constru??o civil) e misturada a um componente magn?tico sint?tico (maghemita, ?Fe2O3). As estruturas qu?mica, cristalogr?fica e hiperfina essenciais e as propriedades magn?ticas dos materiais precursores e do catalisador s?lido foram investigadas. O teor de ?steres e a composi??o dos biodieseis produzidos foram determinados por cromatografia de fase gasosa acoplada a espectr?metro de massa. A composi??o qu?mica do catalisador, verificada por espectroscopias de energia dispersiva sob feixe de el?trons e por fluoresc?ncia de raios X (FRX), confirmou a ocorr?ncia de Si, Fe, K, e I. As ?reas espec?ficas BET encontradas para os componentes individuais, SiO2, ?Fe2O3 e do catalisador SiO2/KI/?Fe2O3, foram 352, 102, e 19 m2 g-1, respectivamente. A significativa redu??o da ?rea espec?fica do catalisador aponta que os componentes foram efetivamente impregnados no suporte. A morfologia das part?culas visualizadas por microscopias eletr?nicas de varredura e de transmiss?o revela a textura esponjosa do catalisador SiO2/KI/?Fe2O3, similarmente ao suporte de s?lica; o ?xido de ferro magn?tico aparece como material altamente organizado, cristalino, disperso no suporte. Os dados M?ssbauer e da magnetometria do ?xido de ferro magn?tico puro e no catalisador confirmam ser a maghemita, resultando em uma magnetiza??o de satura??o do catalisador de 4,6 emu g-1. O catalisador SiO2/KI/?Fe2O3, usado na transesterifica??o de triacilglicer?is, na propor??o em massa em rela??o ao ?leo da am?ndoa de maca?ba de 4,5% e raz?o molar ?leo:metanol de 1:35, levou ? produ??o de 94,3 massa% de ?steres, ap?s 8 h de rea??o. Foi experimentalmente observado que a maghemita tem comportamento qu?mico-catal?tico sin?rgico com os demais componentes do catalisador. O SiO2/KI/?Fe2O3 foi reutilizado em seis rea??es consecutivas com ?leo de soja, na mesma propor??o do catalisador e raz?o molar ?leo:metanol de 1:35, com rendimentos de 94,5% e tempo reacional de 110 min, para o primeiro ciclo, e de 61,2% e 150 min, para o ?ltimo ciclo. O catalisador, antes e ap?s cada ciclo de reuso, e as al?quotas das rea??es foram analisados por FRX, que mostrou que n?o h? perda significativa dos componentes do catalisador. Os resultados demonstram uma perspectiva tecnol?gica que permite redu??o substantiva do volume de efluentes poluentes e utiliza??o de diferentes mat?rias-primas oleaginosas de alto potencial para a produ??o de biodiesel. / Tese (Doutorado) ? Programa de P?s-gradua??o em Biocombust?veis, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / The global demand for liquid fuels destined to propel automobile motors and for all other types of transport has been growing significantly over the last decades in response to the needs of the population for mobility. These fuels are also necessary for the generation of electricity to support industrial and agricultural activities. However, the principal concern involved in the generation of mechanical work involves the threat that the effluents from burning fuels, particularly those from fossil origin, impart to the environment. Biomass-derived fuels are energetically, economically and environmentally interesting alternatives to the non-renewable fossil fuels, which still dominate the global energy matrix. Biodiesel, a liquid that is composed of a mixture of esters of fatty acids, is mainly suitable for use in Diesel-cycle internal combustion engines, totally replacing or partially complementing petrodiesel. The main purpose of the present work was the development of an economically viable, environmentally clean and chemically efficient solid catalyst for the production of biodiesel via the transesterification reaction of triacylglycerols from maca?ba or soybean oil with methanol. The proposed heterogeneous catalyst was based on potassium iodide-impregnated particles of amorphous silica (SiO2; derived from construction sand) mixed with a synthetic magnetic iron oxide (maghemite, ?Fe2O3). The essential chemical, crystallographic and hyperfine structures and magnetic properties of the starting materials and of the solid catalyst mixture were assessed by physical laboratory techniques. The ester content and the chemical composition of the biodiesel produced were determined by gas chromatography coupled with mass spectrometry. The chemical composition of the catalyst, as determined by electron energy dispersive and X-ray fluorescence (FRX) spectroscopies, confirmed the occurrence of Si, Fe, K, and I. Specific BET surface areas for the SiO2 and ?Fe2O3 components and for the SiO2/KI/?Fe2O3 catalyst were found to be 352; 102 and 19 m2 g-1, respectively. The significant reduction in the specific area of the catalyst indicates that the solid components were intimately mixed and that KI was indeed impregnated on the support. The morphology of the particles, as visualized from the scanning and transmission electron microscopy images, reveals the spongy texture of the SiO2/KI/?Fe2O3 catalyst, which was quite similar to that of the initial silica support. The atomic framework of the magnetic iron oxide appeared to be a highly organized, crystalline nano-material, relatively well dispersed on the silica support. The M?ssbauer and magnetometric data for the pure magnetic iron oxide and for the catalyst confirm that the component is essentially maghemite. The resulting saturation magnetization of the catalyst mixture was 4.6 emu g-1. From the chemical point of view, this maghemite was found to act synergically with the other components of the catalyst and to significantly improve its catalytic activity. The transesterification reaction of triacylglycerols using the SiO2/KI/?Fe2O3 catalyst at a mass ratio corresponding to 4.5 mass% relative to the maca?ba kernel oil and a methanol:oil molar ratio 30:1 yielded 94.3 mass% of esters after 8 h of reaction. The SiO2/KI/?Fe2O3 catalyst was reused for six consecutive transesterification reactions of triacylglicerols in soybean oil employing the same mass proportion of the catalyst and a methanol:oil molar ratio 35:1. A 94.5% yield of esters was obtained after 110 min of reaction in the first cycle, and a 61.2% yield was obtained in the last reaction cycle after 150 min. The compositions of the catalyst before and after each reaction cycle, along with detection of residual chemical elements in the liquid mixture of esters formed, were duly monitored by FRX. There was no significant leaching of the catalyst components during the reactions. These results open a perspective for (i) a substantial reduction in the volume of polluting effluents and (ii) the use bio-oils from native Brazilian flora (maca?ba) as raw materials for the industrial production of biodiesel.

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