Síntese, caracterização e atividade fotocatalítica de catalisadores nanoestruturados de TiO2 dopados com metais

Titanium dioxide nanostructured catalysts (nanotubes) doped with different metals (silver, gold, copper, palladium and zinc) were synthesized by the hydrothermal method in order to promote an increase in their photocatalytic activity under visible light. The catalysts were characterized by X-ray diffraction, diffuse reflectance spectroscopy, transmission electron microscopy and specific area and pore volume determination. The materials' photocatalytic activity was evaluated by rhodamine B decomposition in a glass batch reactor. Under UV radiation, only nanotubes doped with palladium were more active than the TiO2 P25, but the samples doped with silver, palladium and gold exhibited better results than the undoped samples under visible light.

Um reator fotoquímico barato e eficiente para experimentos de química

In this work, we present an efficient and inexpensive device for undergraduate chemistry classes aimed at teaching and learning the photolytic synthesis concepts. A photochemical reactor was tested for the synthesis of the organometallic compound enneacarbonyldiiron from iron pentacarbonyl in acetic acid, and its formation evidenced by FTIR analysis. Although similar devices have been described in other studies, none of these offered the simplicity, low cost, class-compatible reaction times and good yields afforded by the procedure reported herein.

Aplicação da radiação ultravioleta como forma de contribuição para a química verde e construção de um reator fotoquímico alternativo e de baixo custo, para pré-tratamento de amostras

Ultraviolet radiation corresponds to a fraction of electromagnetic radiation, covering wavelengths between 1 and 400 nm. Methods based on UV irradiation have become popular because it is possible to treat samples simply by applying energy, avoiding procedures that require the use of toxic substances, thus contributing to the development of Green Chemistry. This study aimed to assess the main applications of UV radiation reported in the literature and thoroughly described the construction of an alternative and low-cost photochemical reactor to be used for the pretreatment of samples in the laboratory. The use of this new photochemical reactor in the clean-up of milk samples for spectrofluorimetric measurements was also reported.

Use of heterogeneous catalysts in methylic biodiesel production induced by microwave irradiation

The effect of different heterogeneous catalysts on the microwave-assisted transesterification of sunflower oil for the production of methylic biodiesel in a monomode microwave reactor is described. The experiments were carried out at 70 ºC with a 16:1 methanolsunflower oil molar ratio and different heterogeneous basic and acidic catalysts. The results showed that the microwave-heated reactions occur up to four times faster than those carried out with conventional heating. The reactions were performed with 24 catalysts; pure calcium oxide (CaO) and potassium carbonate, either pure or supported by alumina (K2CO3/Al2O3), were the most efficient catalysts.

Desenvolvimento de reator tipo "dip catalyst" para filmes poliméricos contendo nanopartículas de metais de transição

This article describes the development of a new catalytic reactor designed to operate with nanoparticle-embedded polymer thin films. Stabilization of metal nanoparticles in films that serve as catalysts in organic reactions is relatively new; therefore, the development of reactors to facilitate their use is necessary. We describe in detail the preparation of the GDCR reactor-type "dip catalyst" and its evaluation in the Suzuki - Miyaura cross-coupling reaction of phenylboronic acid and 4-bromoanisole catalyzed by palladium nanoparticle-embedded cellulose acetate thin film (CA/PD(0)). Compared with earlier prototypes, GDCR reactor showed excellent results when operating with CA/PD(0) thin films.

CONSTRUÇÃO DE UM REATOR DE PLASMA DESCARGA CORONA PARA ELIMINAÇÃO DE COMPOSTOS ORGÂNICOS VOLÁTEIS

The impacts derived from the emission of volatile organic compounds (VOC) into the atmosphere can have harmful consequences for human health and the environment. In this regard, the present paper proposes the construction of a low-cost cold plasma reactor for the treatment of these compounds. Tests with the prototype were performed to confirm the efficiency for BTEX (benzene, toluene and xylene) samples. Degradation efficiency was confirmed by the gas chromatography method.

MICROWAVE ACTIVATION OF IMMOBILIZED LIPASE FOR TRANSESTERIFICATION OF VEGETABLE OILS

This work investigated the effect of microwave irradiation (MW) on the ethanolysis rate of soybean and sunflower oils catalyzed by supported Novozyme 435 (Candida antarctica). The effects of tert-butanol, water addition and oil:ethanol molar ratio on transesterification were evaluated under conventional heating (CH), and under optimum reaction conditions (with no added water in the system, 10% tert-butanol and 3:1 ethanol-to-oil molar ratio). The reactions were monitored up to 24 h to determine the conditions of initial reaction velocity. The investigated variables under MW (50 W) were: reaction time (5.0-180 min) and mode of reactor operation (fixed power, dynamic and cycles) in the absence and presence of tert-butanol (10% (w/w). The measured response was the reaction conversion in ethyl esters, which was linked to the enzyme catalytic activity. The results indicated that the use of microwave improved the activity at fixed power mode. A positive effect of the association of tert-butanol and MW irradiation on the catalytic activity was observed. The reaction rate improved in the order of approximately 1.5 fold compared to that under CH with soybean oil. Using soybean oil, the enzymatic transesterification under MW for conversion to FAEE (fatty acid ethyl esters) reached >99% in 3h, while with the use of CH the conversions were about 57% under similar conditions.

KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68%) and selectivity (100%) for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.

COMPARAÇÃO E CONSTRUÇÃO DE REATORES DE "MILD" E "HARD ANODISATION" PARA FABRICAÇÃO DE ALUMINA ANÓDICA POROSA

The mild anodization (MA) reactor is exemplified for its operational simplicity and its excellent control over the experimental parameters that are involved in the anodization process. This method provides porous anodic alumina films with a regular cell-arrangement structure. This offers a better cost-benefit ratio than the other equipment configurations that are used to fabricate nanoporous structures (i.e., ion beam lithography). Conversely, the hard anodization (HA) reactor produces oxides at a rate that is 25 to 35 times faster than the MA reactor. The produced oxides also have greater layer thicknesses and interpore distance, and with a uniform nanopore spatial order (> 1000). In contrast to MA reactors, the construction of an HA reactor requires special components to maintain anodisation at a high potential regime. Herein, we describe and compare both reactors from a technical viewpoint.

Direct determination of calcium in milk by atomic absorption spectrometry using flow-injection analysis

A flow-injection system with sample and reagent addition by the synchronous merging zones approach for calcium determination in milk by flame AAS is proposed. Main parameters were optimized using a factorial design with central point. The optimum conditions were 2.5% (m/v) for La concentration, 8 mL min-1 for the carrier flow-rate, 20 cm for coiled reactor and 250 ìL for sample volume. Different sample preparation procedures were evaluated such as dilution in water or acid and microwave-assisted decomposition using concentrated or diluted acids. The optimized flow system was applied to determine Ca in eleven commercial milk samples and two standard reference materials diluted in water. Similar calcium levels were encountered comparing the results obtained by the proposed method (dilution in water) with those obtained using microwave-oven digestion. Results obtained in two standard reference materials were in agreement at 95% confidence level with those certified. Recoveries of spiked samples were in the 93% - 116% range. Relative standard deviation (n = 12) was < 5.4% and the sample throughput was 150 measurements per hour, corresponding to a consumption of 250 µL of sample and 6.25 mg La per determination.

Avaliação da biodegradabilidade anaeróbia de resíduos da bovinocultura e da suinocultura

A biodegradabilidade de dejetos da bovinocultura e da suinocultura foi avaliada por meio de metodologia simplificada que permitiu a verificação da aplicabilidade de processos anaeróbios. Os ensaios foram realizados com reatores em batelada, com lodos granulados de três procedências: reator UASB tratando efluente de bovinocultura, reator UASB tratando efluente de suinocultura e reator UASB tratando efluente de abatedouro de aves. Os ensaios (1) - efluente de bovinocultura e lodo de abatedouro de aves não-adaptado; (2) - efluente de suinocultura e lodo de abatedouro de aves não- adaptado; (3) - efluente de bovinocultura e lodo de abatedouro de aves adaptado; (4) - efluente de suinocultura e lodo de abatedouro de aves adaptado; (5) - efluente de bovinocultura e lodo de bovinocultura, e (6) - efluente de suinocultura e lodo de suinocultura realizados em "Shaker", em temperatura de 35 °C, sob agitação a 150 rpm, por 5 minutos a cada 1 hora. Foi utilizada uma relação de substrato:biomassa igual a 0,5. Foram testados modelos cinéticos do tipo Monod, Ordem Zero, Primeira e Segunda Ordens e verificou-se que o modelo de Primeira Ordem foi o que melhor se ajustou para os seis ensaios realizados. A constante de velocidade de Primeira Ordem (k1) foi estimada para os ensaios 1; 2; 3; 4; 5 e 6, resultando 2,51 x 10-2; 2,49 x 10-2; 1,90 x 10-2; 3,09 x 10-2; 2,54 x 10-2, e 4,09 x 10-2 h-1, respectivamente.

Desempenho de reatores anaeróbios de fluxo ascendente com manta de lodo em dois estágios tratando águas residuárias de suinocultura

Avaliou-se o desempenho de dois reatores anaeróbios de fluxo ascendente com manta de lodo (UASB) em escala-piloto com volumes de 908 L e 188 L, instalados em série, alimentados com águas residuárias de suinocultura com concentrações médias de sólidos suspensos totais (SST) variando de 2.216 mg L-1 a 7.131 mg L-1 e submetidos a tempos de detenção hidráulica (TDH) de 62,3 e 31,1 h, no primeiro reator, e de 12,9 e 6,5 h, no segundo reator. As eficiências médias de remoção de DQOtotal variaram de 74,0% a 89,6% no Reator 1 e de 34,3% a 45,1% no Reator 2, resultando em valores médios de 86,6% a 93,1% para o sistema de tratamento em dois estágios com carga orgânica volumétrica (COV) na faixa de 3,40 a 14,44 kg DQOtotal m-3 reator d-1 no Reator 1. As concentrações de metano no biogás foram acima de 75% para o Reator 1 e de 80% para o Reator 2. Os valores médios de pH variaram na faixa de 6,9 a 8,2 para o efluente do Reator 1 e de 7,0 a 8,3 para o efluente do Reator 2. Os ácidos voláteis totais mantiveram-se estáveis com concentrações médias abaixo de 200 mg L-1. Esses resultados indicaram que as condições de carga orgânica, em termos de DQO e SSV, impostas ao sistema de tratamento anaeróbio em dois estágios, não foram limitantes para que houvesse o desenvolvimento de lodo com microbiota adaptada e com alta atividade, propiciando altas eficiências médias de remoção de matéria orgânica (86,6 a 93,1% para DQOtotal e 85,6 a 88,2% para SSV) e taxas de produção de metano de 0,156 a 0,289 m³ CH4 kg-1 de DQO removida.

Avaliação do desempenho de dois sistemas modulares no tratamento anaeróbio de esgotos em comunidades rurais

Este trabalho apresenta uma alternativa de baixo custo e fácil instalação para o tratamento de esgotos de pequenas comunidades. O experimento foi desenvolvido no Campo Experimental da Faculdade de Engenharia Agrícola (FEAGRI/UNICAMP). O volume total de esgoto gerado na FEAGRI é de cerca de 20 m³ dia-1, sendo metade desse tratado pelos sistemas modulares. O sistema da linha (A) é constituído por um reator UASB (Upflow Anaerobic Sludge Blanket), seguido de dois filtros anaeróbios e o outro sistema, linha (B), é constituído por um reator tipo RAC (Reator Anaeróbio Compartimentado), seguido de dois filtros anaeróbios (FA). Os sistemas foram operados de dezembro de 2002 a fevereiro de 2004, totalizando 30 coletas de amostras. Observou-se que, de maneira geral, o desempenho dos sistemas foram similares e com resultados satisfatórios. As eficiências médias de remoção de Sólidos Sedimentáveis, Sólidos Suspensos Totais e DQO, observadas no sistema modular da Linha (A), foram, respectivamente, 99,58%; 94,33% e 67,30%. O sistema modular da Linha (B) apresentou remoção de 99,49%; 93,34% e 70,45% para os mesmos parâmetros. Os sistemas modulares mostraram-se adequados e viáveis para promover o tratamento sanitário do esgoto produzido em pequenas comunidades.

Establishment of anammox process in sludge samples collected from swine wastewater treatment system

The high load of nitrogen present in swine wastewater is one of the biggest management challenges of the activity. The Anammox process emerges as a good alternative for biological removal of nitrogen. This study aims to acclimate sludge collected from swine effluent treatment systems to establish the Anammox process. Two sludge samples were collected at Embrapa Swine and Poultry, Concordia - SC, Brazil, one from the bottom of an inactive anaerobic pond (inoculum A) and another from an aeration tank (inoculum B). Both were acclimated until the depletion of NO3-N, being subsequently inoculated in two reactors (Reactor A - Inoculum A and Reactor B - Inoculum B). The Reactor A showed activity after 110 days of operation, while the Reactor B needed 170 days. The difference in the start-up time could be explained by the different environmental conditions to which each sludge was submitted. FISH and PCR analyses confirmed the presence of microorganisms with Anammox activity, demonstrating that the sludge of swine wastewater treatment systems is a good source of inoculum for the development of the Anammox process.