Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Chitosan and fungicides on postharvest control of Guignardia citricarpa and on quality of 'Pêra Rio' oranges

Citrus fruits are affected by the black spot disease caused by the fungus Guignardia citricarpa. Chitosan can be used as covering for fruits and may delay the ripening process and inhibit the growth of some fungi. Thus, the control of citrus black spot using chitosan and the fungicides thiabendazole and imazalil was assessed in addition to the physicochemical quality of 'Pêra Rio' oranges. The oranges were immersed into chitosan, thiabendazole or imazalil, and in chitosan mixed with both fungicides. The fruits were then stored at 25 °C, 80% RH, for 7 days and, after this storage period, subjected to physicochemical analyses. Chitosan in association with the fungicides reduced black spot in 'Pêra Rio' oranges and delayed the change in the orange skin colour from green to yellow during the postharvest storage. Total soluble solids, titratable acidity, pH, ascorbic acid content and ratio were not influenced by the treatments. Thus, chitosan applied with the fungicides thiabendazole and imazalil showed potential to control the development of black spot lesions on 'Pêra Rio' oranges during the postharvest period.

Distribution of tree species in a geomorphological and pedological gradient of submontane semidecidual seasonal forest in the vicinity of Rio Doce state park, Minas Gerais

The objective of this study was to test the hypothesis that the distribution of tree species in a fragment of submontane seasonal semideciduous forest, a buffer zone in the Parque Estadual do Rio Doce, Minas Gerais, is influenced by geomorphological and weather and soil variables, therefore it can represent a source of information for the restoration of degraded areas where environmental conditions are similar to those of the study area. A detailed soil survey was conducted in the area by sampling three soil profiles per slope segment, totaling 12 profiles. To sample the topsoil, four composite samples were collected from the 10-20 cm layers in each topographic range totaling 16 composite samples. In the low ramp and the lower and upper concave slopes, the texture ranged from clay to sandy-clay. The soil and topographic gradient was characterized by changes in the soil physical-chemical properties. The soil in the 10-20 cm sampled layer was sandier, slightly more fertile and less acid in the low ramp than the clayer soil, nutrient-poor and highly acid soil at the top. The soil conditions in the lower and upper slope of the sampled layers, in turn, were intermediate. The P levels were limiting in all soils. The species distribution along the topographic gradient was associated with variations in chemical fertility, acidity and soil texture. The distribution of Pera leandri, Astronium fraxinifolium, Pouteria torta, Machaerium brasiliense and Myrcia rufipes was correlated with high aluminum levels and to low soil fertility and these species may be indicated for restoration of degraded areas on hillsides and hilltops in regions where environmental conditions are similar. The distribution of Pouteria venosa, Apuleia leiocarpa and Acacia polyphylla was correlated with the less acid and more fertile soil in the environment of the low ramps, indicating the potential for the restoration of similar areas.

INFLUENTIAL FACTORS IN SURFACE WATER QUALITY IN CATCHMENTS WITHIN THE PAMPA BIOME WITH DIFFERENT LAND USE1

The aim of this study was to identify, by multivariate statistical technique, the physic, chemical and biological variables that best characterize the quality of surface waters in two small rural catchments with different land uses (eucalyptus silviculture (SC) vs. pasture and extensive livestock (LC)) located in Rosário do Sul, RS - Brazil. Monitoring was conducted during the months of August 2011 to August 2012 and the following parameters were analyzed: Ca2+, Mg2+, K+, SO42-, Cl-, pH, electrical conductivity, turbidity, alkalinity, suspended and dissolved solids, biochemical oxygen demand , total coliforms, Escherichia coli and temperature, flow and rainfall. Through the use of FA/PCA, it was found that the model best fit to express water quality of in LC that was composed of five factors which account for 83.5% of the total variance, while for SC, four factors accounted for 85.12% of the variance. In LC, the five main factors were, respectively, soluble salts, diffuse pollution, solid, and both anthropogenic and organic factors. In SC, the four factors were namely: soluble salts, mineral, nutritional and diffuse pollution factors. The results of this study showed that by replacing the traditional soil usage (pasture and livestock) with planted forest, diffuse pollution was attenuated but, however, it did not result in major changes in the physical-chemical and biological characteristics of the water. Another point to note is that factorial analysis did not result in a large reduction in the number of variables, once the best model fit occurred with the addition of 15 of 18 analyzed variables (LC) and 17 of 18 analyzed variables (SC).

Studies in offset ink setting

The offset printing process is complex and involves the meeting of two essentially complex materials, printing ink and paper, upon which the final product is formed. It can therefore be expected that a multitude of chemical and physical interactions and mechanisms take place at the ink-paper interface. Interactions between ink and paper are of interest to both the papermakers and ink producers, as they wish to achieve better quality in the final product. The objective of this work is to clarify the combined influence of paper coating structure, printing ink and fountain solution on ink setting and the problems related to ink setting. A further aim is to identify the mechanisms that influence ink setting problems, and to be able to counteract them by changing properties of the coating layer or by changing the properties of the ink. The work carried out for this thesis included use of many techniques ranging from standard paper and printability tests to advanced optical techniques for detection of ink filaments during ink levelling. Modern imaging methods were applied for assessment of ink filament remain sizes and distribution of ink components inside pigment coating layers. Gravimetric filtration method and assessment of print rub using Ink-Surface-Interaction-Tester (ISIT) were utilized to study the influence of ink properties on ink setting. The chemical interactions were observed with the help of modified thin layer chromatography and contact angle measurements using both conventional and high speed imaging. The results of the papers in this thesis link the press operational parameters to filament sizes and show the influence of these parameters to filament size distribution. The relative importance between the press operation parameters was shown to vary. The size distribution of filaments is important in predicting the ink setting behaviour, which was highlighted by the dynamic gloss and ink setting studies. Prediction of ink setting behaviour was also further improved by use of separate permeability factors for different ink types in connection to filtration equations. The roles of ink components were studied in connection to ink absorption and mechanism of print rub. Total solids content and ratio of linseed oil to mineral oil were found to determine the degree of print rub on coated papers. Wax addition improved print rub resistance, but would not decrease print rub as much as lowering the total solids content in the ink. Linseed oil was shown to absorb into pigment coating pores by mechanism of adsorption to pore walls, which highlights the need for sufficient pore surface area for improved chromatographic separation of ink components. These results should help press operators, suppliers of printing presses, papermakers and suppliers to papermakers, to better understand the material and operating conditions of the press as it relates to various print quality issues. Even though paper is in competition with electronic media, high quality printed products are still in demand. The results should provide useful information for this segment of the industry.

Performance during post-harvest storage of banana cv. 'prata', 'maçã' and 'nanica' exposed to physical and chemical treatments

Banana is the most consumed fruit in the world and Brazil is the second largest producer. Despite its global position, Brazil has an average of 40% losses during the post-harvest period. So, this experiment aimed at evaluating the efficiency of post-harvest treatments to improve the storage of banana cultivars cv. 'Prata', 'Maçã' and 'Nanica'. The fruits were acquired at CEASA with green peel, and were submitted to six different treatments: T- immersion in drinking water for 3 minutes (control), H3 - hot water (50 °C for 3 minutes), H8 - hot water (50 °C for 8 minutes), HP - immersion in hypochlorite 0.2% for 3 minutes, OS - immersion in soybean oil 10% for 3 minutes, and OM - immersion in mineral oil 10% for 3 minutes. The fruits were stored at room temperature at about 21 °C for 14 days and evaluated in three periods (1, 7 and 14 days) comparing peel color, flesh/peel ratio, titratable acidity (TA), soluble solids (SS), SS/TA ratio, and pH. The fruits of cv. 'Prata' and 'Maçã' submitted to the treatments H3, H8 and HP ripened at the same time as the control for peel color, which showed increased soluble solids, flesh/peel ratio, acidity and a decrease in pH. On the other hand, the cv. 'Nanica' did not respond significantly different when compared to the applied treatments and the control. The fruits treated with OM and OS were kept green for a longer time for the cultivars 'Prata' and 'Nanica', but there were some changes on peel color due dark spots in 'Prata' banana and a softening aspect in 'Nanica', indicating some level of toxicity of these treatments. Fruits of the 'Maçã' cultivar continued green with the application of mineral oil, without toxicity symptoms. In conclusion, the treatments applied did not show any advantage for storage of these fruits.

Anaerobic biodigestion of pigs feces in the initial, growing and finishing stages fed with diets formulated with corn or sorghum

The objective of this study was to evaluate the quality and the production of biogas and biofertilizer obtained from biodigester supplied with pig feces in the initial, growing and finishing stages, fed with diets formulated based on corn or sorghum. Twenty bench biodigesters were used with hydraulic retention time of 30 days and daily loads that contained 4 to 6% of total solids (TS) and 3.6 to 5.2% of volatile solids (VS). In the effluent of the biodigesters, mean levels of TS were observed ranging between 1.6 and 2.0% and of VS between 1.2 and 1.6%. The mean reductions of TS were 57.7 to 64.7% and of VS from 61.7 to 69.0%, and there was only difference in the finishing phase, in which the major averages reductions were produced by the biodigesters supplied with feces from animals fed with diets based on corn. In biodigesters supplied with feces from animals in the initial and growing stages fed with diets based on corn, were observed higher average productions of biogas and the greatest average potentials of biogas production. The average potentials obtained were 0.033; 0.181; 0.685; 0.788 and 1.132 m³ per kg of affluent, manure, TS added, VS added and VS reduced, respectively. No differences were found on the average content of methane in the biogas between diets and stages. The average concentrations of nutrients N, P, K, Ca, Mg, Na, Fe, Mn, Zn and Cu in the biodigester affluent and effluent, ranged between diets and stages.

Rheological behavior of mixed drink of annona and milk

In this study the rheological behavior in different temperatures (0; 6; 18 e 24 ºC) and physicochemical parameters of integral annona (Annona squamosa) pulp and the annona pulp with milk in different percentages pulp/milk (75g of annona pulp/25g of milk, 50g of annona pulp/50g of milk, 25g of annona pulp/75g of milk) have been availed, in order to verify the effect of temperature and pulp concentration in the rheological behavior of these beverages. To obtain the rheological parameters a concentric cylinder rheometer has been used and the rheograms were analyzed using the Ostwald-de-Wael (power Law) and Herschel-Bulkley models. The physicochemical parameters (sugars, pH, ash, acidity and soluble solids) were determined in order to establish correlations with the rheological behavior. Finally, the best results had been obtained using the Herschel-Bulkley model; the low values for the behavior index (n <1) obtained confirm the pseudoplastic behavior of all samples.

Performance of UASB reactors in two stages under different HRT and OLR treating residual waters of swine farming

In this study it was evaluated the effects of hydraulic retention time (HRT) and Organic Loading Rate (OLR) on the performance of UASB (Upflow Anaerobic Sludge Blanket) reactors in two stages treating residual waters of swine farming. The system consisted of two UASB reactors in pilot scale, installed in series, with volumes of 908 and 188 L, for the first and second stages (R1 and R2), respectively. The HRT applied in the system of anaerobic treatment in two stages (R1 + R2) was of 19.3, 29.0 and 57.9 h. The OLR applied in the R1 ranged from 5.5 to 40.1 kg CODtotal (m³ d)-1. The average removal efficiencies of chemical oxygen demand (COD) and total suspended solids (TSS) ranged, respectively, from 66.3 to 88.2% and 62.5 to 89.3% in the R1, and from 85.5 to 95.5% and 76.4 to 96.1% in the system (R1 + R2). The volumetric production of methane in the system (R1 + R2) ranged from 0.295 to 0.721 m³CH4 (m³ reactor d)-1. It was found that the OLR applied were not limiting to obtain high efficiencies of CODtotal and TSS removal and methane production. The inclusion of the UASB reactor in the second stage contributed to increase the efficiencies of CODtotal and TSS removal, especially, when the treatment system was submitted to the lowest HRT and the highest OLR.

Anaerobic reactors with biofilter and different diameter-length ratios in cassava starch industry wastewater treatment

The use of anaerobic reactors with media support in the treatment of wastewater from the cassava starch industry has emerged as a viable option because it allows the application of high organic loads and a significant reduction of the HDT needed for the treatment. This research aimed at studying the process of biodigestion in two anaerobic reactors with bamboo support, in the treatment of effluent of cassava starch, by evaluating their performance. The two reactors used present the following diameter: length ratio, 1:6 and 1:3. The organic loads applied to the systems were 0.519, 1.156, 1.471, 3.049, 4.347, 4.708 and 5.601g.L-1.d-1. Regarding the efficiency of removal of COD, TS and TVS, no statistically significant differences were obtained between the reactors. The two systems evaluated showed a stable behavior with respect to the VA/TA (volatile acidity/total alkalinity) for all submitted loads. The reactors tended to the maintenance of biogas production as a function of consumed COD for the last three organic loads applied, indicating an ability to withstand higher organic loads.

Quality of papaya hybrid grown under different irrigation depths

Irrigation is a practice widely used in fruit production in the Brazilian Northeast region, including in the papaya crop in order to increase their productivity. For the purpose of knowing the productive potential of papaya hybrid irrigated, an experiment was carried out in order to evaluate the performance of a papaya hybrid under different irrigations depths. Four irrigation depths (50, 75, 100 and 125% of ETo) were tested and the reference evapotranspiration was calculated by the Penman-Monteith model. The hybrid papaya used was UENF/Caliman 01, which was planted in single rows, spaced 4 x 2m from each other, and irrigated by dripping. The experimental design in randomized blocks was used with six replications and three plants per plot. The following variables were evaluated: transversal diameter, longitudinal diameter, pulp thickness, external and internal appearances, soluble solids, titratable acidity, pulp pH and soluble solids/titratable acidity relation. The higher transversal and longitudinal diameters of the fruit were obtained applying an irrigation depth of about 108% of evapotranspiration. The UENF/Caliman 01 hybrid can be cultivated in the semiarid region of the State of Paraiba, Brazil, with replacement rate of 100% ETo, without compromising the quality of the fruits.

Adaptation of "Niagara Rosada" grape must to winemaking by partial cluster dehydration

This study aimed to verify the influence of partial dehydration of "Niagara Rosada" grape clusters in physicochemical quality of the pre- fermentation must. In Brazil, during the winemaking process it is common to need to adjust the grape must when the physicochemical characteristics of the raw material are insufficient to produce wines in accordance with the Brazilian legislation for classification of beverages, which establishes the minimum alcohol content of 8.6 % for the beverage to be considered wine. Therefore, given that the reduction in the water content of grape berries allows the concentration of chemical compounds present in its composition, especially the concentration of total soluble solids, we proceeded with the treatments that were formed by the combination of two temperatures (T1-37.1ºC and T2-22.9 ºC) two air speeds (S1: 1.79 m s-1 and S2: 3.21 m s-1) and a control (T0) that has not gone through the dehydration treatment. Analysis of pH, Total Titratable Acidity (TTA) were performed in mEq L-1, Total Soluble Solids (TSS) in ºBrix, water content on a dry basis and Concentration of Phenolic Compounds (CPC) in mg of gallic acid per 100g of must. The average comparison test identified statistically significant modifications for the adaptation of must for winemaking purposes, having the treatment with 22.9 ºC and air speed of 1.79 m s-1 shown the largest increase in the concentration of total soluble solids, followed by the second best result for concentration of phenolic compounds.

Evaluation of the effect of the seed extract of Moringa oleifera Lam over the efficiency of organic filters in wastewater treatment of dairy cattle breeding

This study aimed to evaluate the effect of Moringa oleifera Lam extract on the removal of total solids (TS), total suspended solids (TSS) and chemical oxygen demand (COD), in different filter media for treating wastewater of dairy cattle breeding (DCW). The moringa seed extract was obtained by grinding 50 g of seeds in one liter of distilled water and, after passing the solution through a quantitative paper filter of 25 microns, 60 mL of the extract were added to wastewater from cattle breeding before the filtration process in organic filters made of thin coal, bamboo leaves, eucalyptus leaves, gliricidia branches and sawdust. This was followed by the completely randomized experimental design, adopting a factorial of 5 x 2. Aliquots of filtered effluent were collected and the total solids (TS) concentrations, total suspended solids (TSS) and chemical oxygen demand (COD) were determined. It was found that the increase in the efficiency of removal of COD and total solids can be attributed to the coagulating power of the moringa seed extract, wherein the filter medium with bamboo leaves presented the best performance, showing potential for use as alternative filter material in the primary treatment of DCW.

COD, TSS, nutrients and coliforms removals in UASB reactors in two stages treating swine wastewater

The performance of two upflow anaerobic sludge blanket (UASB) reactors was evaluated in pilot scale (908 and 188 L), installed in series (R1 and R2), fed with swine wastewater with TSS around 5 and 13 g L-1. The UASB reactors were submitted to HDT of 36 and 18 h with VOL of 5.5 to 34.4 g COD (L d)-1 in the R1 and HDT of 7.5 e 3.7 h with VOL from 5.1 to 45.2 g COD (L d)-1 in the R2. The average removal efficiencies of COD ranged from 55 to 85% in the R1 and from 43 to 57% in the R2, resulting in values from 82 to 93% in the UASB reactors in two stage. Methane concentrations in the biogas were 69 to 74% with specific production from 0.05 to 0.27 L CH4 (g removedCOD)-1 in the R1 and of 0.10 to 0.12 L CH4 (g removedCOD)-1 in the R2. The average removal efficiencies were 61 to 75% for totalP, 39 to 69% for KN, 82 to 93% for orgN and 20 to 94% for Fe, Zn, Cu and Mn. The amN concentration were not reduced indicating the need to post-treatment for effluent disposal into water bodies. There were reductions of total coliforms from 99.8123 to 99.9989% and of thermotolerant coliforms from 99.9725 to 99.9999%. The conditions imposed to the UASB reactors in two stage provided high conversions of removedCOD into methane (up to 77%) and reductions of organic an inorganic pollution loads from swine wastewater.

Color change and quality response of ‘lane late’ orange submitted to degreening process

This study aimed at evaluating the effects of ethylene on peel color and compositional changes in ‘Lane late’ orange stored under refrigerated and ambient conditions. Physiologically mature, but green-peeled, oranges were exposed to ethylene gas under room temperature and high relative humidity for 24 hours. Storage chamber was ventilated with fresh air after 12 hours to mitigate consequences derived from fruit respiration. Both nondestructive analysis, such as peel color (hue angle, chromaticity, and brightness) and weight loss, and destructive ones (soluble solids, titratable acidity, pH, soluble solids to acidity ratio, and puncture force) were performed upon harvest, after degreening, and every three days during eighteen days in storage. Experiment was carried out using an entirely randomized design with thirty replications for nondestructive and four replications for destructive analyses, in a split plot scheme. Exposure to ethylene ensured a golden yellow peel for both fruit stored under ambient and refrigerated conditions. High relative humidity, associated with low temperature prevented fruit from losing moisture. Fruit exposure to ethylene did not affect weight loss, soluble solids, titratable acidity, pH, soluble solids, acidity ratio, or puncture force.