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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.
1

S?ntese de ?steres versus eterifica??o e de 1,3 e 1,5-dioxolanas versus condensa??o, catalisadas pelo catalisador amorfo e hidrof?lico, SiO2-SO3H

Ottone, Myrlene de Oliveira 09 September 2016 (has links)
?rea de concentra??o: Qu?mica org?nica. / Data de aprova??o retirada da vers?o impressa do trabalho. / Palavras-chave ausentes no Resumo/Abstract. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-08-04T17:58:56Z No. of bitstreams: 2 myrlene_oliveira_ottone.pdf: 35150534 bytes, checksum: f6a5ce4d99508eed910f62e1d6984580 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-08-14T13:58:08Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) myrlene_oliveira_ottone.pdf: 35150534 bytes, checksum: f6a5ce4d99508eed910f62e1d6984580 (MD5) / Made available in DSpace on 2017-08-14T13:58:08Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) myrlene_oliveira_ottone.pdf: 35150534 bytes, checksum: f6a5ce4d99508eed910f62e1d6984580 (MD5) Previous issue date: 2016 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / O SiO2-SO3H ? um catalisador heterog?neo, sintetizado a partir de areia de constru??o e carbonato de s?dio, o qual, vem se mostrando eficaz nas s?nteses org?nicas. No presente trabalho, esse catalisador foi usado na s?ntese de ?steres benz?licos e fen?licos, realizada em apenas uma ?nica etapa, com rendimentos entre 80 e 95%. E devido a esse alto rendimento, foi tamb?m realizado rea??es de cetaliza??es, utilizando glicerol, 2,2-dimetil-1,3-propandiol e 1,1,1-hidroximetil-propanol e diversas cetonas. As rea??es com o glicerol apresentaram rendimentos baixos, por ser uma esp?cie muito polar e interagir com os poros da s?lica, evitando a colis?o com as mol?culas de cetonas. Diante desses resultados, foi poss?vel produzir um catalisador heterog?neo que al?m de diminuir o impacto ambiental, carrega caracter?sticas ben?ficas e eficientes para s?ntese org?nica, poss?vel se tonar eficaz para futuras rotas sint?ticas. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016. / The SiO2 - SO3H is a heterogeneous catalyst synthesized from building sand and sodium carbonate. It has proven to be effective for organic syntheses. In study the catalyst was used in the synthesis of benzyl esters and phenolics and the yields between 80 and 95%. And the high yield was also performed cetaliza??es reactions using glycerol, 2,2- dimethyl- 1,3- propandiol and 1,1,1 -hydroxymethyl- propanol and various ketones. The reactions with glycerol had low yield justified very polar species and interact with the pores of silica, avoiding collision with ketone molecules. These results it was possible to produce a heterogeneous catalyst in addition to reducing environmental impact, carries beneficial and efficient features for organic synthesis. It can be effective tonar for future synthetic routes.
2

S?ntese de solketal a partir de glicerol e seu uso como precursor na s?ntese de ?steres de solketila e monoacilglicer?deos

Santos, Ma?sa da Costa 15 December 2016 (has links)
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.
3

Esterifica??o do ?cido oleico utilizando catalisadores ?cidos sulfatados e n?o sulfatados em materiais mesoporosos do tipo SBA-15

Evangelista, Jo?o Paulo da Costa 22 July 2015 (has links)
Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-05-30T22:35:16Z No. of bitstreams: 1 JoaoPauloDaCostaEvangelista_TESE.pdf: 3170006 bytes, checksum: b1459f824b08153ad43dfbda6bced227 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-06-01T20:54:29Z (GMT) No. of bitstreams: 1 JoaoPauloDaCostaEvangelista_TESE.pdf: 3170006 bytes, checksum: b1459f824b08153ad43dfbda6bced227 (MD5) / Made available in DSpace on 2016-06-01T20:54:29Z (GMT). No. of bitstreams: 1 JoaoPauloDaCostaEvangelista_TESE.pdf: 3170006 bytes, checksum: b1459f824b08153ad43dfbda6bced227 (MD5) Previous issue date: 2015-07-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Esse estudo prop?s-se a obter biodiesel a partir da esterifica??o do ?cido oleico com os catalisadores Zr-SBA-15, Nb-SBA-15, SO42-/Zr-SBA-15 e SO42-/Nb-SBA-15 obtidos pela inser??o de Zr e Nb no suporte SBA-15 e sulfata??o do suporte impregnado. O suporte SBA-15 foi sintetizado pelo m?todo hidrot?rmico. O catalisador foi incialmente sintetizado pelo m?todo de impregna??o via ?mida, adicionando 4,2 mL de uma solu??o ? 30 % do percursor do metal (Zr e Nb) em cada grama da SBA-15. Ap?s a impregna??o foi realizado o processo de sulfata??o. As condi??es reacionais da s?ntese do biodiesel utilizadas nesse estudo foram: quantidade de catalisador (5% em massa), raz?o molar de metanol:?cido oleico (20:1), tempo reacional (8 h) e temperatura de refluxo (65?C). Os catalisadores foram analisados por: difra??o de raios-X (DRX), an?lise termogravim?trica (TG/DTG), espectroscopia de infravermelho por transformada de Fourier (FTIR), adsor??o/dessor??o de nitrog?nio, microscopia eletr?nica de varredura (MEV), espectroscopia de energia dispersiva (EDS) e teste de acidez para identifica??o da estrutura, composi??o e verifica??o da presen?a de s?tios ?cidos. Os resultados de caracteriza??o indicaram que o suporte SBA-15 preservou a estrutura hexagonal ordenada, ap?s a incorpora??o de Zr e Nb. Observou-se a presen?a de nanopart?culas desses metais dispersas na superf?cie e no interior dos canais microporosos e mesoporosos dos catalisadores Zr-SBA-15 e Nb-SBA-15. Ap?s a sulfata??o, aumentou a quantidade de s?tios ?cidos e a estrutura ordenada foi mantida. Para os catalisadores Zr-SBA-15 e SO42-/Zr-SBA-15 houve a forma??o das estruturas tetragonal e monocl?nica do ZrO2, j? para os demais catalisadores Nb-SBA-15 e SO42-/Nb-SBA-15 formaram-se estruturas amorfas. A atividade catal?tica foi avaliada pela rea??o de esterifica??o do ?cido oleico via rota et?lica, utilizando todos os catalisadores sintetizados. O biodiesel obtido com SO42-/Zr-SBA-15 apresentou propriedades f?sico-qu?micas dentro das normas especificadas pela resolu??o N?7/2008 da ANP e melhor rendimento com 80,7%. Foi verificado que os catalisadores sulfatados, produziram maior rendimento com rela??o aos n?o sulfatados. O suporte SBA-15 n?o apresentou atividade catal?tica. / Fatty acids such as oleic acid, have received particular attention as raw material, due to its abundance, availability and relatively high purity, being considered as potential materials for production of biodiesel. The esterification reaction of oleic acid using heterogeneous catalysts can be a promising alternative for biodiesel production. This study proposes to find a biodiesel through esterification of oleic acid with Zr-SBA-15, Nb-SBA-15, SO42?/Zr-SBA-15 and SO4 2?/Nb-SBA-15 catalysts, obtained by insertion of Zr and Nb in support SBA-15 and sulfation of the impregnated support. SBA-15 support was synthesized by hydrothermal method. Support SBA-15 was synthesized by hydrothermal method. The catalyst was initially synthesized by the wet impregnation method, followed by sulfation process. The catalysts were analyzed: X-ray diffraction (XRD), thermal analysis (TG/DTG), Fourier transform infrared spectroscopy (FTIR), nitrogen adsorption/desorption, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and acidity test to identify the structure, composition and verification the presence acid sites. The characterization results indicated that the SBA-15 support preserved the ordered hexagonal structure after the incorporation of Zr and Nb. It was observed the presence of nanoparticles these metal dispersed on the surface and within the microporous and mesoporous channels of Zr-SBA-15 and Nb-SBA-15 catalysts. After sulfation, increased amount of acid sites and the ordered structure was maintained. For Zr-SBA-15 and SO4 2?/Zr-SBA-15 catalyst was the formation of tetragonal and monoclinic structures of ZrO2, as for the other, Nb-SBA-15 and SO42?/Nb-SBA-15 catalyst were formed amorphous structures. The catalytic activity was evaluated by the esterification reaction of oleic acid via ethyl route, using all the synthesized catalysts. Biodiesel obtained with SO42?/Zr-SBA-15 presented physicochemical properties within the standards specified by the Resolution N? 45/2014 ANP and obtained the best yield with 80.7%. It was found that sulfated catalysts, produced higher yields with respect to nonsulfated. The SBA-15 support showed no catalytic activity.
4

Integra: uma solu??o para integra??o de sistemas de HelpDesk com sistemas de Issue Tracking em ambientes heterog?neos

Ribeiro, Eduardo Lima 10 August 2016 (has links)
Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-03-15T00:01:18Z No. of bitstreams: 1 EduardoLimaRibeiro_DISSERT.pdf: 5210310 bytes, checksum: 45334f9a90781c022e4ac6b72af53fbd (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-03-16T23:20:10Z (GMT) No. of bitstreams: 1 EduardoLimaRibeiro_DISSERT.pdf: 5210310 bytes, checksum: 45334f9a90781c022e4ac6b72af53fbd (MD5) / Made available in DSpace on 2017-03-16T23:20:10Z (GMT). No. of bitstreams: 1 EduardoLimaRibeiro_DISSERT.pdf: 5210310 bytes, checksum: 45334f9a90781c022e4ac6b72af53fbd (MD5) Previous issue date: 2016-08-10 / Independente da ?rea de atua??o e devido ?s necessidades de neg?ciodado o ritmo das inova??es, organiza??es p?blicas e privadas v?m seadaptando constantemente ?s mudan?as tecnol?gicas, seja com asmelhores pr?ticas de mercado ou com a atualiza??o de suas tecnologias.Estas mudan?as frequentes muitas vezes acabam criando na empresa umambiente bastante heterog?neo, onde os sistemas envolvidos no neg?cioe que foram desenvolvidos em diversas plataformas (por exemplo,linguagem de programa??o e/ou banco de dados) operam de maneiraisolada. Em situa??es como esta, a empresa precisa adotar estrat?giaspara prover a interoperabilidade entre seus sistemas e assim garantiruma devida comunica??o, visando propiciar o interc?mbio de informa??esentre os departamentos e a integra??o das regras do neg?cio. Oobjetivo central deste trabalho foi propor e desenvolver estrat?giasque permitam a integra??o de sistemas nestes ambientes heterog?neos,independente da plataforma e linguagem de desenvolvimento dossistemas. Com o objetivo de resolver os problemas atuais decomunica??o e performance entre os diferentes sistemas de informa??ona Secretaria de Ensino a Dist?ncia (SEDIS) da Universidade Federal doRio Grande do Norte (UFRN), foi desenvolvido um middleware denominadoINTEGRA, concebido em uma arquitetura orientada a servi?os. A propostafoi criada para a SEDIS, entretanto pode ser estendida a outrasinstitui??es p?blicas de ensino superior. Uma das vantagens daarquitetura proposta ? a de proporcionar a adi??o de novos sistemassem causar fortes impactos de adapta??es e mudan?as, garantindo amanutenibilidade geral do software. O middleware comunica diferentessistemas help desk e issue tracking oferecendo uma gama de servi?osmediante um protocolo de comunica??o que padroniza a troca e oroteamento das mensagens. Atrav?s da estrat?gia proposta como mostra oestudo de caso, foi poss?vel chegar a um equil?brio entre o princ?piodo desacoplamento e o princ?pio da distribui??o de responsabilidade demaneira uniforme, garantindo assim um baixo acoplamento e uma altacoes?o, princ?pios desej?veis na engenharia de software. / Public and private organizations is coming to adapting to technological changes constantly because business needs independent of its expertise area, either with adaptation of best market practices or with the constant updating of its technologies given the pace of innovation. This constant evolution often creating a heterogeneous environment systems. This environment happens when we have a set of systems developed on multiple platforms (programming language, database) operating in isolation. Companies with this heterogeneity needs to adopt strategies to provide interoperability into their systems providing better communication between the softwares, these strategies will promote the exchange of information between the departments of companies keeping their integrated business rules. The main objective of this work is develop strategies to provide the integration of different systems with each other, ensuring interoperability between them, regardless of platform and development language thereof. In particular, the proposal was created and developed for the Department of Distance Education - SEDIS, belonging to the Federal University of Rio Grande do Norte - UFRN, but can be extended to any public institution of higher education. As result of this study it was produced a middleware that uses components of a serviceoriented architecture with the main objective to solve the current problems that exist in communication and performance between different SEDIS information systems at UFRN.
5

O problema de clustering heterog?neo fuzzy: modelos e heur?sticas

Pinheiro, Daniel Nobre 27 January 2017 (has links)
Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-04-03T19:47:15Z No. of bitstreams: 1 DanielNobrePinheiro_DISSERT.pdf: 900596 bytes, checksum: 82c38f5d0fc71d5fb71fb0c1acd283c6 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-04-06T19:26:01Z (GMT) No. of bitstreams: 1 DanielNobrePinheiro_DISSERT.pdf: 900596 bytes, checksum: 82c38f5d0fc71d5fb71fb0c1acd283c6 (MD5) / Made available in DSpace on 2017-04-06T19:26:01Z (GMT). No. of bitstreams: 1 DanielNobrePinheiro_DISSERT.pdf: 900596 bytes, checksum: 82c38f5d0fc71d5fb71fb0c1acd283c6 (MD5) Previous issue date: 2017-01-27 / Este trabalho prop?e formula??es para o Problema de Clustering Heterog?neo Fuzzy, assim como um m?todo heur?stico de Busca em Vizinhan?a Vari?vel para resolv?-lo. O Problema de Clustering Heterog?neo Fuzzy ? um problema de agrupamento de dados modelado em dois n?veis. O primeiro identifica grupos de indiv?duos cujas percep??es acerca dos objetos envolvidos sejam similares. O segundo n?vel identifica parti??es fuzzy de objetos para cada grupo de indiv?duos. O segundo n?vel ? baseado no problema das p-medianas, cujo objetivo ? particionar um conjunto de objetos em subconjuntos menores e definir um objeto para cada subconjunto como mediana, de modo que a soma das dissimilaridades entre cada objeto e sua mediana seja m?nima. O Problema de Clustering Heterog?neo Fuzzy generaliza o problema das p-medianas para ambientes fuzzy, permitindo que os n?veis de pertin?ncia de cada objeto em rela??o a cada cluster sejam fracion?rios. Essa generaliza??o permite novas interpreta??es dos resultados, como a identifica??o de rela??es simult?neas de objetos com diferentes clusters. / This work proposes formulations for the Fuzzy Heterogeneous Clustering Problem, as well as a heuristic method of Variable Neighborhood Search to solve it. The Fuzzy Heterogeneous Clustering Problem is a clustering problem that is formulated in two levels. The first identifies groups of individuals whose perceptions about the objects involved are similar. The second level identifies fuzzy partitions of objects for each group of individuals. The second level is based on the p-median problem, whose objective is to partition a set of objects into smaller subsets and to define an object as median for each subset, such that the sum of dissimilarities between each object and its median is minimal. The Fuzzy Heterogeneous Clustering Problem generalizes the p-median problem to fuzzy environments, allowing the degrees of membership between each object and each cluster to be fractionary. This generalization allows new interpretations about the results, such as the identification of simultaneous relationships of objects with different clusters.
6

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.
7

Avalia??o da efici?ncia qu?mica de catalisadores heterog?neos baseados em min?rios e rejeitos de minera??o nas rea??es de transesterifica??o de triacilglicer?is de bio-?leo

Rocha, B?rbara Gon?alves 18 December 2017 (has links)
?rea de concentra??o: Produtos e coprodutos. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2018-06-22T19:43:47Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) barbara_goncalves_rocha.pdf: 2671242 bytes, checksum: 17dfa18bc6c5622c294695227a582c58 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2018-07-18T12:29:56Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) barbara_goncalves_rocha.pdf: 2671242 bytes, checksum: 17dfa18bc6c5622c294695227a582c58 (MD5) / Made available in DSpace on 2018-07-18T12:29:56Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) barbara_goncalves_rocha.pdf: 2671242 bytes, checksum: 17dfa18bc6c5622c294695227a582c58 (MD5) Previous issue date: 2018 / A diversifica??o da matriz energ?tica, por raz?es econ?micas, ambientais e da pr?pria pol?tica energ?tica das na??es, tem suscitado foco especial nos biocombust?veis, particularmente no bioetanol e no biodiesel. Na ind?stria, o biodiesel (?steres de ?cidos graxos com um ?lcool de cadeia molecular curta) ?, mais comumente, produzido pela transesterifica??o de triacilglicer?is de ?leos vegetais ou gordura animal, com metanol ou etanol, sob cat?lise homog?nea com uma base (KOH ou NaOH). Por representarem alternativas potencialmente mais sustent?veis, dos pontos de vistas econ?micos e ambientais, o presente trabalho foi dedicado a avaliar a efici?ncia qu?mica de catalisadores heterog?neos baseados em materiais de min?rios: (i) de ni?bio, enriquecido em Nb2O5 (Geo.Nb2O5); (ii) de areia monaz?tica (Geo.Mona), uma fonte mineral de terras raras, e (iii) de rejeitos de minera??o de fosfato, ricos em magnetita (Geo.Mag.CMT e Geo.Mag.CMA). Os materiais minerais foram preparados em mistura com componentes ?cidos (H2SO4; HCl ou HF) ou b?sicos (KOH; , KBr, NaOH; CaO; KI; KF ou KCl). As rea??es de transesterifica??o foram conduzidas sob refluxo, com ?leo de soja comercial e metanol, sob a??o dos catalisadores s?lidos. A raz?o molar padr?o ?leo:metanol foi de 1:100, com 10% de catalisador em rela??o ao ?leo, a 60 ?C. Dos testes realizados com os materiais preparados com CaO sint?tico comercial, nas mesmas condi??es, a mistura calcinada a 800 ?C por 4 h rendeu ?steres met?licos sempre acima de 99%; o menor tempo de rea??o (2 h, para completar a transesterifica??o) foi conseguido com o catalisador baseado na Geo.Mona, em rela??o ao Geo.Nb2O5 (5 h), ao Geo.Mag.CMT (3 h) e o Geo.Mag.CMA tamb?m (2 h). Analisou-se o reuso consecutivo do catalisador. Ap?s cada rea??o, o catalisador s?lido era lavado com metanol e seco a 100 oC. O melhor resultado foi obtido com o rejeito magn?tico com CaO calcinados a 200 ?C por 4 h, para o que se conseguiu at? 8 rea??es consecutivas. Nas impregna??es com ?cidos e bases, os melhores resultados foram com a mistura Geo.Nb2O5 e KOH calcinada a 600 ?C, para a qual conseguiu 8 rea??es consecutivas, com rendimento qu?mico em ?steres met?licos de praticamente 100% e tempo reacional de 10 min, no primeiro uso. O efeito catal?tico sin?rgico mais significativo foi conseguido com o catalisador baseado em cada um dos tr?s materiais avaliados em mistura com CaO: nenhum efeito catal?tico significativo na rea??o de transesterifica??o de triacilglcier?is do ?leo foi observado apenas com o material mineral puro calcinado. O CaO puro como catalisador, tamb?m calcinado e usado em rea??o, levou a rendimentos qu?micos pouco acima de 80%. A mistura individual do material mineral com CaO, nas mesmas condi??es de prepara??o anteriores, levaram a rendimentos qu?micos de efetivamente 100%. Os presentes resultados revelam a excepcional potencialidade, dos pontos de vista qu?mico, econ?mico e ambiental, dos catalisadores mistos, dos materiais minerais com CaO, ora avaliados, nos processos de produ??o industrial de biodiesel. / Tese (Doutorado) ? Programa de P?s-gradua??o em Biocombust?veis, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / The diversification of the energy matrix has been drawing special attention to biofuels, especially bioethanol and biodiesel, mainly for economic and environmental reasons and national energy policies. In industry, biodiesel (esters of fatty acids with a short-chain alcohols) is most commonly produced by the transesterification of triacylglycerols in vegetable oils or animal fats with methanol or ethanol using homogeneous catalysis with a base (KOH or NaOH). The present work was devoted to the evaluation of the chemical efficiency of heterogeneous catalysts based on mineral materials: (i) niobium, enriched in Nb2O5 (Geo.Nb2O5); (ii) monazite sand (Geo.Mona), a mineral source of rare earths, and (iii) phosphate mining tailings, rich in magnetite (Geo.Mag.CMT e Geo.Mag.CMA). The mineral materials were prepared in admixture with acidic (H2SO4, HCl or HF) or basic (KOH, KBr, NaOH, CaO, KI, KF or KCl) components. The transesterification reactions were conducted under reflux with commercial soybean oil and methanol in the presence of the solid catalysts. The standard molar ratio of oil:methanol was 1:100, using 10% catalyst relatively to the quantity of oil, at 60 ?C. According to the tests performed with the materials prepared with commercial synthetic CaO under the same conditions, the yield of methyl esters with the mixture calcined at 800 ?C for 4 h was always greater than 99%. The shortest reaction time (2 h to complete the transesterification) was achieved with the Geo.Mona catalyst; the reaction times with Geo.Nb2O5 (5 h), the Geo.Mag.CMT (3 h) and the Geo.Mag.CMA also (2 h) were longer. The consecutive reuse of the catalyst was also verified. After each reaction, the solid catalyst was washed with methanol and dried at 100 ?C. The best result was obtained with the magnetic waste with CaO calcined at 200 ?C for 4 h, with which up to eight consecutive reactions were achieved. On impregnating with acids or bases, the best results are obtained with the Geo.Nb2O5 and KOH mixture calcined at 600 ?C, with which eight consecutive reactions were completed. Virtually 100% yields of methyl esters were obtained in a reaction time of 10 min in the first use. The most significant synergistic catalytic effect was achieved with each of the three minerals mixed with CaO. No significant catalytic effect on the transesterification reaction of triacylglycerols in the oil was observed with the pure calcined minerals. When the calcined CaO is used alone as catalyst, the reaction yielded just over 80%. For the mixture of the individual minerals with CaO under the same preparation conditions described above, the transesterification reaction led to virtually 100% yields. The present results reveal an outstanding potential regarding the chemical, economic and environmental aspects of the mixed catalysts (the mineral material with CaO) for chemical processes leading to the industrial production of biodiesel.
8

S?ntese de biodiesel, glicerol, solketal e ?ter de solketal

Pereira, Adeline Cristina 12 April 2018 (has links)
Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2018-11-05T21:41:01Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) adeline_cristina_pereira.pdf: 1853338 bytes, checksum: 3a89c6c8bdef22cb94ac757e146a9e2a (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2018-11-10T11:58:12Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) adeline_cristina_pereira.pdf: 1853338 bytes, checksum: 3a89c6c8bdef22cb94ac757e146a9e2a (MD5) / Made available in DSpace on 2018-11-10T11:58:12Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) adeline_cristina_pereira.pdf: 1853338 bytes, checksum: 3a89c6c8bdef22cb94ac757e146a9e2a (MD5) Previous issue date: 2018 / O catalisador denominado SiO2-SO3H foi empregado em tr?s processos reacionais distintos: transesterifica??o, cetaliza??o e eterifica??o. Utilizado em uma propor??o de 20% (m/m) contendo tolueno, o SiO2-SO3H se mostrou muito eficiente no processo de transesterifica??o de triacilglicer?deos fornecendo glicerol e ?steres met?licos de ?cidos graxos (biodiesel) com um rendimento de 98%. Empregou-se o glicerol obtido como reagente em uma mistura com acetona, em um meio reacional livre de solventes e utilizando o SiO2-SO3H, obteve-se convers?o total e 100% de seletividade para o composto contendo o anel de 5 membros [(?)- 2,2-Dimetil-4-hidroximetil-1,3-dioxolano] conhecido como solketal, um produto qu?mico vers?til, com diversas aplica??es, na ind?stria de cosm?tico e farmac?utica, al?m de aditivo para diesel com a finalidade de reduzir o ponto de congelamento, melhorar as propriedades lubrificantes e aumentar a pot?ncia anti-detonante. Posteriormente realizou-se o processo de eterifica??o do solketal, empregando o catalisador SiO2-SO3H, levando a forma??o do 4,4'-[oxibis(metileno)]-bis(2,2-dimetil-1,3-dioxolano)], ??ter de di-solketal?, precursor do diglicerol, importante emulsificante das ind?strias farmac?utica e aliment?cia com 98% de rendimento. A eterifica??o do solketal foi tamb?m promovida empregando o catalisador denominado SiO2-Nb levando a forma??o do 4,4'-[oxibis(metileno)]-bis(2,2-dimetil-1,3-dioxolano)], ??ter de di-solketal? com um rendimento de 96%. / Disserta??o (Mestrado) ? Programa de P?s-gradua??o em Biocombust?veis, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2018. / The catalyst called SiO2-SO3H was at the forefront of several distinct reaction processes: transesterification, ketalization and etherification. Used at a ratio of 20% (m / m) to toluene, SiO2 -SO3H became very efficient in the transesterification process of triacylglycerides, providing glycerol and fatty acid methyl esters (biodiesel) in 98% yield. The glycerol was used as reagent in a mixture with acetone, in a solvent-free reaction medium and in the use of SiO2 -SO3H, obtained and 100% total resolution for the compound with the 5-membered compound [(?) - 2,2-Dimethyl-4-hydroxymethyl-1,3-dioxolane], known as solalto, a versatile chemical with various applications in the cosmetic and pharmaceutical industry, as well as a diesel additive for freezing purpose, lubricants and increase anti-detonating power. Subsequently, the sputtering determination was carried out using the SiO2 -SO3H catalyst, leading to the formation of 4,4 '- [oxybis (methylene)] bis (2,2-dimethyl-1,3-dioxolane)], di-solketal, precursor of diglycerol, a major emulsifier of the pharmaceutical and food industries in 98% yield. The etherification of the solketal was also promoted using the catalyst called SiO2-Nb leading to the formation of 4,4 '- [oxybis (methylene)] bis (2,2-dimethyl-1,3-dioxolane)], di -solketal "in 96% yield.
9

Formula??es e algoritmos para o problema das p-medianas heterog?neo livre de penalidade

Santi, ?verton 14 November 2014 (has links)
Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-01-05T18:01:11Z No. of bitstreams: 1 EvertonSanti_TESE.pdf: 601652 bytes, checksum: 52767a19768856b40fcce8bb5611ef4b (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-01-11T18:20:39Z (GMT) No. of bitstreams: 1 EvertonSanti_TESE.pdf: 601652 bytes, checksum: 52767a19768856b40fcce8bb5611ef4b (MD5) / Made available in DSpace on 2016-01-11T18:20:39Z (GMT). No. of bitstreams: 1 EvertonSanti_TESE.pdf: 601652 bytes, checksum: 52767a19768856b40fcce8bb5611ef4b (MD5) Previous issue date: 2014-11-14 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Apresenta-se neste trabalho um novo modelo para o Problema das p-Medianas Heterog?neo (PPMH), proposto para recuperar a estrutura de categorias n?o-observadas presente em dados oriundos de uma tarefa de triagem, uma abordagem popular que possibilita entender a percep??o heterog?nea que um grupo de indiv?duos tem em rela??o a um conjunto de produtos ou marcas. Este novo modelo ? chamado Problema das p-Medianas Heterog?neo Livre de Penalidade (PPMHLP), uma vers?o mono-objetivo do problema original, o PPMH. O par?metro principal do modelo PPMH ? tamb?m eliminado, o fator de penalidade. Este par?metro ? respons?vel pela pondera??o dos termos de sua fun??o objetivo. O ajuste do fator de penalidade controla a maneira como o modelo recupera a estrutura de categorias n?o-observadas presente nos dados e depende de um amplo conhecimento do problema. Adicionalmente, duas formula??es complementares para o PPMHLP s?o apresentadas, ambas problemas de programa??o linear inteira mista. A partir destas formula??es adicionais, limitantes inferiores foram obtidos para o PPMHLP. Estes valores foram utilizados para validar um algoritmo de Busca em Vizinhan?a Variada (VNS), proposto para resolver o PPMHLP. Este algoritmo obteve solu??es de boa qualidade para o PPMHLP, resolvendo inst?ncias geradas de forma artificial por meio de uma Simula??o de Monte Carlo e inst?ncias reais, mesmo com recursos computacionais limitados. As estat?sticas analisadas neste trabalho sugerem que o novo algoritmo e modelo, o PPMHLP, pode recuperar de forma mais precisa que o algoritmo e modelo original, o PPMH, a estrutura de categorias n?o-observadas presente nos dados, relacionada ? percep??o heterog?nea dos indiv?duos. Por fim, uma exemplo de aplica??o do PPMHLP ? apresentado, bem como s?o consideradas novas possibilidades para este modelo, estendendo-o a ambientes fuzzy / This work presents a new model for the Heterogeneous p-median Problem (HPM), proposed to recover the hidden category structures present in the data provided by a sorting task procedure, a popular approach to understand heterogeneous individual?s perception of products and brands. This new model is named as the Penalty-free Heterogeneous p-median Problem (PFHPM), a single-objective version of the original problem, the HPM. The main parameter in the HPM is also eliminated, the penalty factor. It is responsible for the weighting of the objective function terms. The adjusting of this parameter controls the way that the model recovers the hidden category structures present in data, and depends on a broad knowledge of the problem. Additionally, two complementary formulations for the PFHPM are shown, both mixed integer linear programming problems. From these additional formulations lower-bounds were obtained for the PFHPM. These values were used to validate a specialized Variable Neighborhood Search (VNS) algorithm, proposed to solve the PFHPM. This algorithm provided good quality solutions for the PFHPM, solving artificial generated instances from a Monte Carlo Simulation and real data instances, even with limited computational resources. Statistical analyses presented in this work suggest that the new algorithm and model, the PFHPM, can recover more accurately the original category structures related to heterogeneous individual?s perceptions than the original model and algorithm, the HPM. Finally, an illustrative application of the PFHPM is presented, as well as some insights about some new possibilities for it, extending the new model to fuzzy environments
10

S?ntese, caracteriza??o e estudo das propriedades fotocatal?ticas de compostos de ni?bio em matrizes ambientais

Morais, Lidiane Alves de 16 May 2016 (has links)
Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-12-29T16:22:07Z No. of bitstreams: 1 LidianeAlvesDeMorais_TESE.pdf: 2444711 bytes, checksum: 23f2b53145f8389d4a45f7f7c2040146 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-01-02T17:55:19Z (GMT) No. of bitstreams: 1 LidianeAlvesDeMorais_TESE.pdf: 2444711 bytes, checksum: 23f2b53145f8389d4a45f7f7c2040146 (MD5) / Made available in DSpace on 2017-01-02T17:55:19Z (GMT). No. of bitstreams: 1 LidianeAlvesDeMorais_TESE.pdf: 2444711 bytes, checksum: 23f2b53145f8389d4a45f7f7c2040146 (MD5) Previous issue date: 2016-05-16 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Um dos materiais que atualmente est? em destaque s?o os compostos de ni?bio, por apresentarem caracter?sticas como acidez, propriedades oxidativas e fotocatal?ticas e por ser um dos metais mais abundantes do pa?s, sendo o Brasil o maior produtor mundial. Este trabalho avaliou a efici?ncia da fotocat?lise heterog?nea de materiais de ni?bio na oxida??o de metanol e na inativa??o do microrganismo Escherichia Coli. Foram sintetizados catalisadores a base de ni?bio Nb2O5 e foram feitas imobiliza??es (coating) utilizando ?xido de ni?bio. Diante das caracteriza??es, foi poss?vel verificar a forma??o de esp?cies de ?xido de ni?bio e niobatos de s?dio dependendo da metodologia de s?ntese adotada. Esses materiais foram avaliados na oxida??o de metanol em diferentes concentra??es de catalisadores e apresentaram uma efici?ncia na forma??o do formalde?do proveniente da oxida??o, esta efici?ncia est? diretamente relacionada com a concentra??o dos catalisadores, sendo o material de niobato de s?dio o que apresentou maior efici?ncia, devido as suas propriedades texturais, ?pticas, sendo este um material promissor no ramo da fotocat?lise. Para os sistemas de imobiliza??o (coating), verificou-se que o revestimento ideal ? obtido com tr?s imobiliza??es, estes materiais foram analisados na oxida??o de metanol e na inativa??o de microrganismo Escherichia Coli. Estes sistemas (coating) mostram uma boa atividade na oxida??o de metanol, apesar de apresentar resultados inferiores quando comparados aos materiais em suspens?o de ?xido de ni?bio, por?m a grande vantagem dos sistemas imobilizados em rela??o ao de suspens?es s?o a sua reutiliza??o. Em rela??o ? inativa??o da Escherichia Coli, foi verificado que os sistemas imobilizados n?o s?o muitos ativos e que o microrganismo ? bastante dependendo do meio em que se encontra. / One of the materials that is currently highlighted are the compounds of niobium, because they have features like acidity, oxidative and photocatalytic properties and for being one of the most abundant metals in the country, Brazil is the world's largest producer. In this scenario, the work has to evaluate the efficiency of heterogeneous photocatalysis niobium materials in the oxidation of methanol and the inactivation of Escherichia coli using immobilization systems ?coating? and suspension. Commercial niobium oxide (Nb2O5) was evaluated in suspension and immobilization in different systems (tubes and rings) for photocatalytic processes for water treatment (methanol oxidation and inactivation of Escherichia coli). From the results of the commercial Nb2O5 characterizations was observed the presence of an amorphous structure with heat thermal treatment at temperatures above 550 ?C becomes crystalline phases, however, this fact produce a significant aggregation of the particles which reduced the specific area and the photocatalytic activity. The not calcined Nb2O5 material showed a higher activity, for both oxidation of methanol as for the inactivation of bacterial tests, the latter being very sensitive to the chemical composition water. Immobilization of the photocatalyst reactor walls prevents the need for removal of Nb2O5 particles after treatment, but significantly reduction its activity. In contrast, immobilization in a fixed-bed (rings) led to a moderate reduction in activity, which is counteracted by improvement in the long-term stability of the material. Niobium catalysts were synthesized using a refluxing method with and without the use of NaOH in different conditions of synthesis and characterized by different techniques in order to verify the phase formation of niobium. From the results of X-ray diffraction for the synthesized materials were recorded forming of species niobium oxide and sodium niobates depending on the adopted synthesis methodology. The catalytic activity of these materials was evaluated in the oxidation of methanol in relation to the amount of catalyst in which the activities have different behaviors have been dependent on the structure, surface and morphological parameters. Materials with sodium niobate structure have a lineal tendency of activity in relation to the mass of catalysts, while the materials niobium oxide structure have an abrupt loss of their catalytic activity at higher catalyst concentrations, indicating that the dispersion of the light is higher in these catalysts as increases the amount of particles in suspension. Among the materials synthesized and analyzed in the oxidation of methanol, which was more efficient, was the material of sodium niobate NaNbO3 to their textural properties, optical, which is a promising material for photocatalysis.

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