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Míriam Cristina Santos Amaralhttp://lattes.cnpq.br/1901180413775034Marcelo Machado VianaLucilaine Valéria de Souza SantosGuilherme Oliveira SiqueiraAna Cláudia Figueiras Pedreira de Cerqueirahttp://lattes.cnpq.br/1294866473833989Caique Prado Machado de Oliveira2019-10-30T17:14:38Z2019-10-30T17:14:38Z2019-07-30http://hdl.handle.net/1843/30726The first part of the present paper presents an environmentally friendly synthesis of TiO2 nanoparticles assisted by microwave from titanium tetrachloride and water with potential for oil refinery wastewater treatment. Anatase nanocrystalline particles with a mean crystallite size of 14 nm were obtained according to XRD, TEM and EELS characterization. The photocatalytic activity of the catalyst was tested first by degradation of the standard methylene blue molecule and 95% degradation was verified after 300 minutes of reaction. Kinetic tests with the dye indicated adjustment to first order kinetics. The UF permeate of a Membrane Bioreactor treating real refinery wastewater composed largely of biologically recalcitrant compounds was subjected to photodegradation in the presence of the catalyst synthesized under UV-C irradiation. The highest percentages of TOC and TN removal were 32% and 67%, respectively, under pH conditions equal to 10 and catalyst concentration of 100 mg L-1 in 90 minutes of reaction. For this condition, the Electric Energy per Order (EE0) calculated was 356.29 KWh m-3 order-1. The catalyst exhibited stability in photoactivity for 4 cycles. In the second part of the study, a hybrid system called Photocatalytic Membrane Reactor (PMR) was constructed and tested for treatment of the previously mentioned effluent. The PMR configuration was based on the use of the cleaner synthesized titanium dioxide catalyst and reverse osmosis membranes recycled by chemical oxidation with sodium hypochlorite. The system proved to be efficient in the removal of UF permeate recalcitrant compounds with values up to 60% of COD removal. It was verified that photocatalysis exerts the greatest impact on the removal of organic matter (21%) when compared to photolysis with UV light (15%) and membrane separation only (9%). The permeate fluxes of the recycled membrane remained practically constant in the tests with the presence of the catalyst in the PMR, showing that it reduces the fouling, also confirmed by the fouling resistance 7.3 times lower in the tests performed with the presence of the oxide. No evidence was detected that the catalyst damaged the membrane structure. In contrast, stabilities in fluxes and photocatalysis were verified by reuse tests. SEM analyzes of the membrane prior to permeation revealed a non-rough structure. Morphological changes were not observed on the membrane surface after permeations. However, TiO2 deposits were visualized and confirmed by EDS. Analysis of EDS in various fields of the PMR permeate did not identify the titanium element showing that the recycled membrane is able of retaining the catalyst. The compounds present in the effluent are mainly associated with microbial products such as SMPs and EPS that had their concentrations reduced based on the disappearance of the bands 3300 cm-1, 1620 cm-1 and 609 cm-1 of the infrared spectrum. The obtained data showed that the system is a promising technology for the removal of residual recalcitrant organic matter of the UF-MBR permeate before the polishing process of the petroleum refinery wastewater with a view to reuse.A primeira parte do presente trabalho apresenta uma síntese ambientalmente amigável de nanopartículas de TiO2 assistida por microondas, a partir de tetracloreto de titânio e água, com potencial para tratamento de efluentes de refinaria de petróleo. Partículas nanocristalinas de anatásio com tamanho médio de cristalito de 14 nm foram obtidas de acordo com a caracterização por DRX, MET e EELS. A atividade fotocatalítica do catalisador foi testada primeiramente pela degradação da molécula padrão de azul de metileno e 95% de degradação foram verificados após 300 minutos de reação. Testes cinéticos com o corante indicaram ajuste à cinética de primeira ordem. O permeado de UF de um Biorreator de Membrana tratando efluente real de refinaria de petróleo constituído majoritamente de compostos biologicamente recalcitrantes foi submetido a fotodegradação na presença do catalisador sintetizado sob irradiação UV-C. As maiores porcentagens de remoção de COT e NT obtidas foram de 32% e 67%, respectivamente, em condições de pH igual a 10 e concentração de catalisador de 100 mg L-1 em 90 minutos de reação. Para essa condição, a Electric Energy per Order (EE0) calculada foi 356,29 KWh m-3 ordem-1. O catalisador exibiu estabilidade na fotoatividade durante 4 ciclos. Na segunda parte do estudo, um sistema híbrido denominado Reator Fotocatalítico de Membrana (PMR) foi construído e testado para tratamento do efluente previamente mencionado. A configuração do PMR baseou-se na utilização do catalisador dióxido de titânio sintetizado por via mais limpa e membranas de osmose inversa recicladas por oxidação química com hipoclorito de sódio. O sistema se mostrou eficiente na remoção de compostos recalcitrantes do permeado de UF com valores de até aproximadamente 60% de remoção de DQO. Verificou-se que a fotocatálise exerce o maior impacto na remoção de matéria orgânica (21%) quando comparada aos valores de fotólise com luz UV (15%) e somente separação pela membrana (9%). Os fluxos de permeado da membrana reciclada permaneceram praticamente constantes nos testes com a presença do catalisador no PMR, mostrando que este reduz a incrustação, confirmada também pela resistência do fouling 7,3 vezes menor nos testes executados com a presença do óxido. Não foram detectados indícios de que o catalisador danificou a estrutura da membrana. Ao contrário, foram verificadas estabilidades nos fluxos e na fotocatálise pelos testes de reuso. As análises de MEV da membrana antes da permeação revelaram uma estrutura não rugosa. Alterações morfológicas não foram observadas na superfície da membrana após permeações. No entanto, depósitos de TiO2 foram visualizados e confirmados por EDS. A análise de EDS em vários campos do permeado do PMR não identificou o elemento titânio mostrando que a membrana reciclada é capaz de reter o catalisador. Os compostos presentes no efluente estão principalmente associados a produtos microbianos como SMPs e EPS que tiveram suas concentrações reduzidas com base no desaparecimento das bandas 3300 cm-1, 1620 cm-1 e 609 cm-1 do espectro de infravermelho. Os dados obtidos mostraram que o sistema é uma tecnologia promissora para a remoção de matéria orgânica recalcitrante residual do permeado do UF-MBR e tem potencial uso como etapa prévia aos processos de polimento do efluente de refinaria com vistas ao reuso.CNPq - Conselho Nacional de Desenvolvimento Científico e TecnológicoengUniversidade Federal de Minas GeraisPrograma de Pós-Graduação em Saneamento, Meio Ambiente e Recursos HídricosUFMGBrasilENG - DEPARTAMENTO DE ENGENHARIA SANITÁRIA E AMBIENTALEngenharia sanitáriaMeio ambienteDióxido de titânioTitanium dioxideRefinery effluentMicrowave synthesisRecycled membranePhotocatalytic membrane reactorRecalcitrant compoundsProcess intensification in the refinery effluent treatment using a photocatalytic membrane reactorIntensificação de processos no tratamento do efluente de refinaria utilizando um reator fotocatalítico de membranainfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisinfo:eu-repo/semantics/openAccessreponame:Repositório Institucional da UFMGinstname:Universidade Federal de Minas Gerais (UFMG)instacron:UFMGORIGINALPROCESS INTENSIFICATION IN THE REFINERY EFFLUENT TREATMENT USING A PHOTOCATALYTIC MEMBRANE REACTOR.pdfPROCESS INTENSIFICATION IN THE REFINERY EFFLUENT TREATMENT USING A PHOTOCATALYTIC MEMBRANE REACTOR.pdfapplication/pdf5878300https://repositorio.ufmg.br/bitstream/1843/30726/1/PROCESS%20INTENSIFICATION%20IN%20THE%20REFINERY%20EFFLUENT%20TREATMENT%20USING%20A%20PHOTOCATALYTIC%20MEMBRANE%20REACTOR.pdf8f8065f2794b0cb4aefa611d233ae01dMD51LICENSElicense.txtlicense.txttext/plain; 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