Nanotubos óxidos aplicados a resinas compostas fotoativadas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Chemical composition and in vitro digestibility of fresh sugarcane hydrolysed with calcium oxide (CaO)

The objective was to evaluate the chemical composition and in vitro digestibility of sugarcane hydrolysed with increasing doses of calcium oxide and varying air exposure times. A completely randomised, split plot design was used; the doses were allocated to the plots, and the air exposure times were allocated to the subplots, with four repetitions. The data underwent analysis of variance and were laid out according to the effect of the treatment on the components of polynomial regressions, and evaluated at the 5% probability. The increase in the dosage negatively affected the quantities of neutral-detergent fibre (NDF), acid-detergent fibre (ADF), lignin (LIG), total carbohydrates (TC), cellulose (CEL), crude protein (CP), and ether extract (EE); and positively affected the quantities of non-fibrous carbohydrates (NFC) and mineral matter (MM). The addition of calcium oxide improved the in vitro digestible dry matter (IVDMD) coefficients and was able to keep up to 72 hours. The in vitro digestibility of the neutral-detergent fibre (IVDNDF) and of the acid-detergent fibre (IVDADF) coefficients decreased when calcium oxide was added. Calcium oxide has the ability to hydrolyse the fibrous fraction and conserve chopped sugarcane. Doses of 0.5 and 1.0% lime exhibited similar results to those achieved at higher doses; therefore, higher doses are not required in the hydrolyses of sugarcane. Over time, the sugarcane deteriorates, but this deterioration is reduced by the addition of calcium oxide.

Efeito prebiótico de xilo-oligossacarídeos produzidos a partir da hemicelulose de bagaço de cana-de-açúcar utilizando extração alcalina e hidrólise de xilanases fúngicas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Obtenção e caracterização de nanocelulose a partir de fibras de Chorisia speciosa St. Hil

Natural fibers have been highlighted as a renewable material that can replace materials from oil and its derivatives. In this context, Brazil becomes the perfect setting because of the diversity of fibers found in its territory, such as sugarcane, sisal, rice, cotton, coconut, pineapple, among others. The paineiras (Chorisia speciosa St. Hil) are typically Brazilian trees, which produce paina as fruit. These fruits are still little studied as a source of lignocellulose by research groups. This project aimed obtaining and characterization of cellulose nanofibers from the fibers from the paina fibers. Obtaining nanocellulose is practically made through simplified chemical processes. First, was performed out pre-treatments to removal of waxes, lignin and hemicellulose. The first stage of pre-treatment was carried out by alkaline aqueous solution of sodium hydroxide (NaOH) at 5wt%, where the fibers were under constant agitation for 1h at 70°C. Through alkali treatment it was possible to remove most of the lignin, hemicellulose, waxes and extractives. After the alkaline treatment was done bleaching with an aqueous solution of sodium hydroxide (NaOH) to 4wt% and hydrogen peroxide (H2O2) to 24wt% 1:1 during 2h with constant stirring to 50 °C. Through bleaching was possibe to remove residual lignin, and got cellulose with 72% of crystallinity. Nanocellulose of paina fibers was extracted using different conditions of acid hydrolysis with sulfuric acid (H2SO4) to 50wt%. After acid hydrolysis, the suspensions were centrifuged during 30 min and dialyzed in water to remove excess acid until neutral pH (6-7). Then the suspensions were passed by ultrasonification in an ultrasound 20 kHz during 1h in an ice bath. Untreated, alkalinized and bleached fibers as well as cellulose nanoparticles were characterized by the techniques of thermogravimetry ... (Complete abastract click electronic access below)

Obtenção e caracterização de nanocelulose a partir de fibras de Chorisia speciosa St. Hil

Natural fibers have been highlighted as a renewable material that can replace materials from oil and its derivatives. In this context, Brazil becomes the perfect setting because of the diversity of fibers found in its territory, such as sugarcane, sisal, rice, cotton, coconut, pineapple, among others. The paineiras (Chorisia speciosa St. Hil) are typically Brazilian trees, which produce paina as fruit. These fruits are still little studied as a source of lignocellulose by research groups. This project aimed obtaining and characterization of cellulose nanofibers from the fibers from the paina fibers. Obtaining nanocellulose is practically made through simplified chemical processes. First, was performed out pre-treatments to removal of waxes, lignin and hemicellulose. The first stage of pre-treatment was carried out by alkaline aqueous solution of sodium hydroxide (NaOH) at 5wt%, where the fibers were under constant agitation for 1h at 70°C. Through alkali treatment it was possible to remove most of the lignin, hemicellulose, waxes and extractives. After the alkaline treatment was done bleaching with an aqueous solution of sodium hydroxide (NaOH) to 4wt% and hydrogen peroxide (H2O2) to 24wt% 1:1 during 2h with constant stirring to 50 °C. Through bleaching was possibe to remove residual lignin, and got cellulose with 72% of crystallinity. Nanocellulose of paina fibers was extracted using different conditions of acid hydrolysis with sulfuric acid (H2SO4) to 50wt%. After acid hydrolysis, the suspensions were centrifuged during 30 min and dialyzed in water to remove excess acid until neutral pH (6-7). Then the suspensions were passed by ultrasonification in an ultrasound 20 kHz during 1h in an ice bath. Untreated, alkalinized and bleached fibers as well as cellulose nanoparticles were characterized by the techniques of thermogravimetry ... (Complete abastract click electronic access below)

Tratamento do efluente alcalino do branqueamento da polpa de celulose pelo processo de separação por membranas

O presente trabalho estuda o reaproveitamento do efluente alcalino do branqueamento da polpa, da indústria de celulose, através de processos de separação com membranas. Para tanto, foram realizados testes com o efluente industrial para diferentes membranas e, simultaneamente, foi pesquisada a aplicação do processo de flotação como pré-tratamento para retirada de fibras do efluente. A avaliação dos resultados foi realizada por meio de determinações analíticas e monitoramento de alguns parâmetros. Os experimentos foram executados em equipamentos de bancada e piloto. A etapa de separação com membranas envolveu os processos de ultrafiltração, nanofiltração, osmose reversa e combinações destas operações. De forma a escolher um processo com retenção e fluxo permeado adequados variou-se durante os testes a pressão através das membranas e a temperatura. As análises realizadas para a caracterização do efluente foram: pH, condutividade elétrica, turbidez, sólidos totais (ST), demanda química de oxigênio (DQO), compostos organo-halogenados (AOX), ferro, magnésio, cálcio, sódio, potássio e manganês. A DQO foi o principal critério utilizado para avaliar a qualidade do permeado. Os ensaios de flotação foram realizados com e sem adição de compostos químicos auxiliares. A eficiência do processo foi avaliada através das análises de ST, condutividade elétrica, pH, recuperação de fibras, teor de alumínio, turbidez e visualmente Os resultados indicaram que todos os processos testados trouxeram uma melhoria nas características do efluente, incluindo reduções de até 90% no valor de DQO em alguns casos. O processo que apresentou a melhor performance foi a combinação UF5+ORP. A investigação preliminar sobre a flotação das fibras mostrou que, apesar de ter atingido uma remoção de fibras de 95% ainda havia a presença de partículas grosseiras, as quais poderiam causar danos aos processos com membranas. Mais estudos devem ser realizados no sentido de otimizar o processo de flotação.

Estudo de titanatos nanoestruturados obtidos por tratamento hidrotérmico de óxido de titânio em meio alcalino

TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800ºC), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7·nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200ºC, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400ºC. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150ºC, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase

Avaliação da influência de surfactantes químico e biológico na hidrólise enzimática de casca de coco verde após pré-tratamento ácido/alcalino e com peróxido de hidrogênio alcalino

In Brazil many types of bioproducts and agroindustrial waste are generated currently, such as cacashew apple bagasse and coconut husk, for example. The final disposal of these wastes causes serious environmental issues. In this sense, waste lignocellulosic content, as the shell of the coconut is a renewable and abundant raw material in which its use has an increased interest mainly for the 2nd generation ethanol production. The hydrolysis of cellulose to reducing sugars such as glucose and xylose is catalysed by a group of enzymes called cellulases. However, the main bottleneck in the enzymatic hydrolysis of cellulose is the significant deactivation of the enzyme that shows irreversible adsorption mechanism leading to reduction of the cellulose adsorption onto cellulose. Studies have shown that the use of surfactants can modify the surface property of the cellulose therefore minimizing the irreversible binding. The main objective of the present study was to evaluate the influence of chemical and biological surfactants during the hydrolysis of coconut husk which was subjected to two pre-treatment in order to improve the accessibility of the enzymes to the cellulose, removing this way, part of the lignin and hemicellulose present in the structure of the material. The pre-treatments applied to coconut bagasse were: Acid/Alkaline using 0.6M H2SO4 followed by 1M NaOH, and the one with Alkaline Hydrogen Peroxide at a concentration of 7.35% (v/v) and pH 11.5. Both the material no treatment and pretreated were characterized using analysis of diffraction X-ray (XRD), Scanning Electron Microscopy (SEM) and methods established by NREL. The influence of both surfactants, chemical and biological, was used at concentrations below the critical micelle concentration (CMC), and the concentrations equal to the CMC. The application of pre-treatment with coconut residue was efficient for the conversion to glucose, as well as for the production of total reducing sugars, it was possible to observe that the pretreatment fragmented the structure as well as disordered the fibers. Regarding XRD analysis, a significant increase in crystallinity index was observed for pretreated bagasse acid/alkali (51.1%) compared to the no treatment (31.7%), while that for that treated with PHA, the crystallinity index was slightly lower, around 29%. In terms of total reducing sugars it was not possible to observe a significant difference between the hydrolysis carried out without the use of surfactant compared to the addition of Triton and rhamnolipid. However, by observing the conversions achieved during the hydrolysis, it was noted that the best conversion was using the rhamnolipíd for the husk pretreated with acid/alkali, reaching a value of 33%, whereas using Triton the higher conversion was 23.8%. The coconut husk is a residue which can present a high potential to the 2nd generation ethanol production, being the rhamonolipid a very efficient biosurfactant for use as an adjuvant in the enzymatic process in order to act on the material structure reducing its recalcitrance and therefore improving the conditions of access for enzymes to the substrate increasing thus the conversion of cellulose to glucose.

Avaliação da influência de surfactantes químico e biológico na hidrólise enzimática de casca de coco verde após pré-tratamento ácido/alcalino e com peróxido de hidrogênio alcalino

In Brazil many types of bioproducts and agroindustrial waste are generated currently, such as cacashew apple bagasse and coconut husk, for example. The final disposal of these wastes causes serious environmental issues. In this sense, waste lignocellulosic content, as the shell of the coconut is a renewable and abundant raw material in which its use has an increased interest mainly for the 2nd generation ethanol production. The hydrolysis of cellulose to reducing sugars such as glucose and xylose is catalysed by a group of enzymes called cellulases. However, the main bottleneck in the enzymatic hydrolysis of cellulose is the significant deactivation of the enzyme that shows irreversible adsorption mechanism leading to reduction of the cellulose adsorption onto cellulose. Studies have shown that the use of surfactants can modify the surface property of the cellulose therefore minimizing the irreversible binding. The main objective of the present study was to evaluate the influence of chemical and biological surfactants during the hydrolysis of coconut husk which was subjected to two pre-treatment in order to improve the accessibility of the enzymes to the cellulose, removing this way, part of the lignin and hemicellulose present in the structure of the material. The pre-treatments applied to coconut bagasse were: Acid/Alkaline using 0.6M H2SO4 followed by 1M NaOH, and the one with Alkaline Hydrogen Peroxide at a concentration of 7.35% (v/v) and pH 11.5. Both the material no treatment and pretreated were characterized using analysis of diffraction X-ray (XRD), Scanning Electron Microscopy (SEM) and methods established by NREL. The influence of both surfactants, chemical and biological, was used at concentrations below the critical micelle concentration (CMC), and the concentrations equal to the CMC. The application of pre-treatment with coconut residue was efficient for the conversion to glucose, as well as for the production of total reducing sugars, it was possible to observe that the pretreatment fragmented the structure as well as disordered the fibers. Regarding XRD analysis, a significant increase in crystallinity index was observed for pretreated bagasse acid/alkali (51.1%) compared to the no treatment (31.7%), while that for that treated with PHA, the crystallinity index was slightly lower, around 29%. In terms of total reducing sugars it was not possible to observe a significant difference between the hydrolysis carried out without the use of surfactant compared to the addition of Triton and rhamnolipid. However, by observing the conversions achieved during the hydrolysis, it was noted that the best conversion was using the rhamnolipíd for the husk pretreated with acid/alkali, reaching a value of 33%, whereas using Triton the higher conversion was 23.8%. The coconut husk is a residue which can present a high potential to the 2nd generation ethanol production, being the rhamonolipid a very efficient biosurfactant for use as an adjuvant in the enzymatic process in order to act on the material structure reducing its recalcitrance and therefore improving the conditions of access for enzymes to the substrate increasing thus the conversion of cellulose to glucose.

Avaliação e Otimização do Consumo de Água no Processo e do Sistema de Tratamento de Efluentes

O elevado consumo de água associado à escassez deste recurso contribuiu para que alternativas de reutilização/reciclagem de água fossem estudadas que permitam diminuir o seu consumo e minimizar a dependência das indústrias. Monitorizar e avaliar os consumos de água, a nível industrial, é imprescindível para assegurar uma gestão sustentável dos recursos hídricos, sendo este o objetivo da presente dissertação. As alternativas encontradas na unidade industrial em estudo foram a substituição do equipamento sanitário e o aproveitamento do efluente tratado para operações de lavagem e/ou arrefecimento por contacto direto. A maioria do equipamento sanitário não é eficiente, tendo-se proposto a substituição desse sistema por um de menor consumo que permitirá uma poupança de 30 % no consumo de água, que corresponderá a 12 149,37 €/ano, sendo o retorno do investimento estimado em 3 meses. O efluente industrial na entrada da ETAR e nas diferentes etapas - tratamento primário de coagulação/floculação; tratamento secundário ou biológico em SBR; tratamento terciário de coagulação/floculação - foi caracterizado através da medição da temperatura, pH, oxigénio dissolvido e pela determinação da cor, turvação, sólidos suspensos totais (SST), azoto total, carência química de oxigénio (CQO), Carência Bioquímica de Oxigénio ao fim de 5 dias (CBO5) e razão CBO5/CQO. Esta caracterização permitiu avaliar o efluente industrial bruto que se caracteriza por um pH alcalino (8,3 ± 1,7); condutividade baixa (451 ± 200,2 μS/cm); elevada turvação (11 255 ± 8812,8 FTU); cor aparente (63 670 ± 42293,4 PtCo) e cor verdadeira (33 621 ± 19547,9 PtCo) elevadas; teores elevados de CQO (24 753 ± 11806,7 mg/L O2) SST (5 164 ± 3845,5 mg/L) e azoto total (718 mg/L) e um índice de biodegradabilidade baixo (razão CBO5/CQO de 1,4). Este estudo permitiu verificar que a eficiência global do tratamento do efluente foi 82 % na remoção da turvação, 83 % na remoção da cor aparente, 96 % na remoção da cor verdadeira, 85 % na remoção da CQO e 30 % na remoção dos SST. Quanto às eficiências de remoção associadas ao tratamento primário no que diz respeito à turvação, cor aparente, CQO e SST, apresentam valores inferiores aos referidos na literatura para o mesmo tipo de tratamento em efluentes similares. As eficiências de remoção obtidas no tratamento secundário são inferiores às do tratamento primário: turvação, cor aparente, CQO e SST, pelo que procurou-se otimizar a primeira etapa do processo de tratamento Neste estudo de otimização estudou-se a influência de cinco coagulantes – Sulfato de Alumínio, PAX XL – 10, PAX 18, cloreto de ferro e a conjugação de PAX 18 com sulfato de ferro - e seis floculantes – Superfloc A 150, Superfloc A 130, PA 1020, Ambifloc 560, Ambifloc C58 e Rifloc 54 - no tratamento físico-químico do efluente. O PAX 18 e o Ambifloc 560 UUJ foram os que apresentaram as mais elevadas eficiências de remoção (99,85 % na cor, 99,87 % na turvação, 90,12 % na CQO e 99,87 % nos SST). O custo associado a este tratamento é de 1,03 €/m3. Pela comparação com os critérios de qualidade no guia técnico ERSAR, apenas o parâmetro da CQO excede o valor, contudo o valor obtido permite diminuir os custos associados a um tratamento posterior para remoção da CQO remanescente no efluente residual tratado.

Emprego da técnica de eletrodiálise no tratamento de soluções aquosas contendo cádmio e cianeto

O presente trabalho teve como objetivo avaliar a possibilidade de empregar a técnica de eletrodiálise para remoção e recuperação de cádmio e cianeto a partir de soluções aquosas simulando diluições da composição de um banho alcalino de cádmio à base de cianeto. Para isso, foram utilizadas células de eletrodiálise de bancada de diferentes configurações e dois tipos de membranas íon-seletivas, uma catiônica (NafionÒ 450) e uma aniônica (SelemionÒ AMV). Foram realizados ensaios em células de dois e três compartimentos para avaliar o comportamento do potencial total da célula e o potencial das membranas em função da corrente aplicada com soluções de diferentes concentrações. Através destes ensaios foi possível definir as concentrações das soluções e as densidades de corrente a serem utilizadas na célula de cinco compartimentos. Os ensaios na célula de cinco compartimentos foram realizados para avaliar a remoção e recuperação de cádmio e cianeto em diferentes tempos de ensaio, diferentes densidades de corrente, diferentes concentrações das soluções e na presença de outros íons metálicos como cobre, cromo e ferro. Os resultados demonstram que a extração percentual e a eficiência de corrente de cádmio e cianeto dependem da densidade de corrente aplicada, da concentração das soluções e do tempo de ensaio A remoção total das espécies iônicas é limitada pela precipitação de cádmio sobre a membrana catiônica do compartimento central da célula a partir de uma determinada remoção dos íons. No entanto, através de sucessivas trocas da solução de cádmio e cianeto, antes do momento em que ocorre a precipitação, os resultados demonstram a possibilidade de se obter uma solução concentrada em cádmio e cianeto em outro compartimento da célula, o que demonstra a possibilidade de recuperar cádmio e cianeto no banho de deposição de cádmio. Com a presença de cobre, cromo e ferro esta recuperação é prejudicada, pois estes íons são transportados na mesma direção do cádmio e do cianeto, o que pode representar uma contaminação para o banho de deposição.

Aplicação da água residuária das salinas no tratamento de efluente têxtil

The treatment of colored and alkaline effluent has been a challenge to the textile industry. An alternative to remove the colors of those effluents is applying magnesium chloride as a coagulant agent. The magnesium ion, in high pH, hydrolyzes itself, forming the magnesium hydroxide which has a large adsorptive area and positive electrostatic charges able to act as an efficient coagulant. The bittern wastewater from the salt industries has been studied as a potential font of this magnesium ion. Nowadays, this bittern wastewater is evicted into the sea, without any treatment or other use. This thesis has evaluated the potential of applying the wastewater from the salt industries in the treatment of dyeing effluent containing indigo dye and alkaline pH. All the experiments were made in jar tests simulating the chemical coagulation, flocculation and decantation steps ranging the pH and the concentration of magnesium ion. Were obtained removals between 96% and 76% for turbidity, apparent color, and true color, respectively, using 200mg/L Mg2+. The reduction of costs with acid, when were used the salt industries wastewater, comparing with Al2(SO4)3, was 62%. For the degradation of organic matter remaining in the clarified, around 900 mg/L, was applyed the advanced process of oxidation: photo-Fenton. The preliminary results showed 57% reduction in DOC. According to the results obtained, the salt industries wastewater can be applied, as coagulant, in the physical-chemical treatment of the denim dyeing wastewater, so it is not necessary a previous adjust of pH, efficiently and economically

Tratamento de manipueira de fecularia utilizando processos oxidativos com peróxido de hidrogênio, ôzônio e radiação ultravioleta

Pós-graduação em Agronomia (Energia na Agricultura) - FCA

Pré-tratamento oxidativo de bagaço de cana com persulfato de sódio para sacarificação enzimática e produção de etanol celulósico

Pós-graduação em Química - IBILCE

Desenvolvimento de catalisadores sem platina: estudos comparativos da oxidação de metanol em 'PD''RU'/'C' e 'PT''RU'/'C' em meio alcalino

Pós-graduação em Química - IQ