Retrieval of kinetic rates in reactions with semi batch liquid phase using ill-posed inverse problem theory

A neural network procedure to solve inverse chemical kinetic problems is discussed in this work. Rate constants are calculated from the product concentration of an irreversible consecutive reaction: the hydrogenation of Citral molecule, a process with industrial interest. Simulated and experimental data are considered. Errors in the simulated data, up to 7% in the concentrations, were assumed to investigate the robustness of the inverse procedure. Also, the proposed method is compared with two common methods in nonlinear analysis; the Simplex and Levenberg-Marquardt approaches. In all situations investigated, the neural network approach was numerically stable and robust with respect to deviations in the initial conditions or experimental noises.

Sequential injection analysis system with spectrophotometric detection for determination of norfloxacin and ciprofloxacin in pharmaceutical formulations

This work proposes a sequential injection analysis (SIA) system for the spectrophotometric determination of norfloxacin (NOR) and ciprofloxacin (CIP) in pharmaceutical formulations. The methodology was based on the reaction of these drugs with p-(dimethylamino)cinnamaldehyde in micellar medium, producing orange colored products (λmax = 495 nm). Beer´s law was obeyed in the concentration range from 2.75x10-5 to 3.44x10-4 mol L-1 and 3.26x10-5 to 3.54x10-4 mol L-1 for NOR and CIP, respectively and sampling rate was 25 h-1. Commercial samples were analyzed and results obtained through the proposed method were in good agreement with those obtained using the reference procedure for a 95% confidence level.

Effect of dye structure and redox mediators on anaerobic azo and anthraquinone dye reduction

We investigated the biological decolourisation of dyes with different molecular structures. The kinetic constant values (k1) achieved with azo dye Reactive Red 120 were 7.6 and 10.1 times higher in the presence of RM (redox mediators) AQDS and riboflavin, respectively, than the assays lacking RM. The kinetic constant achieved with the azo dye Congo Red was 42 times higher than that obtained with the anthraquinone dye Reactive Blue 4. The effect of RM on dye reduction was more evident for azo dyes resistant to reductive processes, and ineffective for anthraquinone dyes because of the structural stability of the latter.

Flow-batch analyser for preparation of calibration standard mixtures in simultaneous multicomponent spectrometric analysis

The application of multivariate calibration techniques to multicomponent analysis by UV-VIS molecular absorption spectrometry is a powerful tool for simultaneous determination of several chemical species. However, when this methodology is accomplished manually, it is slow and laborious, consumes high amounts of reagents and samples, is susceptible to contaminations and presents a high operational cost. To overcome these drawbacks, a flow-batch analyser is proposed in this work. This analyser was developed for automatic preparation of standard calibration and test (or validation) mixtures. It was applied to the simultaneous determination of Cu2+, Mn2+ and Zn2+ in polyvitaminic and polymineral pharmaceutical formulations, using 4-(2-piridilazo) resorcinol as reagent and a UV-VIS spectrophotometer with a photodiode array detector. The results obtained with the proposed system are in good agreement with those obtained by flame atomic absorption spectrometry, which was employed as reference method. With the proposed analyser, the preparation of calibration and test mixtures can be accomplished about four hours, while the manual procedure requires at least two days. Moreover, it consumes smaller amounts of reagents and samples than the manual procedure. After the preparation of calibration and test mixtures, 60 samples h-1 can be carried out with the proposed flow-batch analyser.

Spot-test identification and rapid quantitative sequential analysis of dipyrone

A qualitative spot-test and tandem quantitative analysis of dipyrone in the bulk drug and in pharmaceutical preparations is proposed. The formation of a reddish-violet color indicates a positive result. In sequence a quantitative procedure can be performed in the same flask. The quantitative results obtained were statistically compared with those obtained with the method indicated by the Brazilian Pharmacopoeia, using the Student's t and the F tests. Considering the concentration in a 100 µL aliquot, the qualitative visual limit of detection is about 5×10-6 g; instrumental LOD ≅ 1.4×10-4 mol L-1 ; LOQ ≅ 4.5×10-4 mol L-1.

Physiological and biochemical characterization of the assai palm (Euterpe oleracea Mart.) during seed germination and seedling growth under aerobic and anaerobic conditions

Physiological and biochemical aspects of assai palm during seed germination and early seedling growth were investigated. Seeds collected from plants growing in flooded and upland forests were used to determine the influence of normoxic (aerobic) and anoxic (anaerobic) conditions in germination and the initial and average time of development in the roots and shoots. After 75 days, seedlings germinated under normoxia were transferred to trays and submitted to flooding. Seed reserves (lipids, proteins, soluble sugars and starch) were monitored for quiescent and germinated seeds maintained under normoxic and anoxic conditions, as well as after 5, 10 and 20 days of seedling growth. Alcohol dehydrogenase (ADH) activity was quantified in roots and leaves of seedlings without or with flooding (partial and total). Seeds were not able to germinate under anoxia. Different strategies of storage mobilization of lipids, proteins, soluble sugars and starch were observed in seeds of each environment. ADH activity was induced by anoxia, with the highest level observed in the leaves. This study showed that, under normoxic conditions, the best developmental performance of assai palm seeds, from flooded or upland forest areas, during germination was associated with primary metabolites mobilization and seedling flooding tolerance with increased ADH activity. We conclude that the assai palm is well adapted to the anoxic conditions provoked by flooding.

APROS model validation in case of fast transients in a boiling water reactor

This Master´s thesis investigates the performance of the Olkiluoto 1 and 2 APROS model in case of fast transients. The thesis includes a general description of the Olkiluoto 1 and 2 nuclear power plants and of the most important safety systems. The theoretical background of the APROS code as well as the scope and the content of the Olkiluoto 1 and 2 APROS model are also described. The event sequences of the anticipated operation transients considered in the thesis are presented in detail as they will form the basis for the analysis of the APROS calculation results. The calculated fast operational transient situations comprise loss-of-load cases and two cases related to a inadvertent closure of one main steam isolation valve. As part of the thesis work, the inaccurate initial data values found in the original 1-D reactor core model were corrected. The input data needed for the creation of a more accurate 3-D core model were defined. The analysis of the APROS calculation results showed that while the main results were in good accordance with the measured plant data, also differences were detected. These differences were found to be caused by deficiencies and uncertainties related to the calculation model. According to the results the reactor core and the feedwater systems cause most of the differences between the calculated and measured values. Based on these findings, it will be possible to develop the APROS model further to make it a reliable and accurate tool for the analysis of the operational transients and possible plant modifications.

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.

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.

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.

Swine effluent treatment using anaerobic digestion at different loading rates

The industrial swine production is characterized by generation of significant effluent amounts that require treatment. The most adopted practices by Brazilian swine farmers have been wastewater storage in lagoons and its subsequent use as a biofertilizer. Nutrient accumulation in soil and water creates the need for an effective management of these residues. The anaerobic digestion process is an important alternative and low-cost treatment for organic matter reduction. However, its efficiency is limited by the digester capacity of solid degradation, especially at low hydraulic retention times. Thus, the present study aimed to verify the behavior of an upflow anaerobic digester by increasing the organic loading rate. This was accomplished in three stages using, as a parameter, volatile solids at 0.5; 1.0 and 1.5 kgVS m-3 d-1, respectively. This digester model proved to be quite robust and effective in swine manure treatment, achieving high efficiency of volatile solid removal at all stages of the study (stage 1: 61.38%; stage 2: 55.18%; and stage 3: 43.18%). Biogas production was directly related to the increasing organic load, reaching 0.14, 0.85, and 0.86 Nm³ kgVS-1add., respectively, with no significant difference (p<0.05) of biogas methane concentration among the studied stages (73.7, 75.0, and 77.9%).

Potential of biogas production from swine manure supplemented with glycerine waste

In this study, was studied the biogas generation from swine manure, using residual glycerine supplementation. The biogas production by digestion occurred in the anaerobic batch system under mesophilic conditions (35°C), with a hydraulic retention time of 48 days. The experiment was performed with 48 samples divided into four groups, from these, one was kept as a control (without glycerin) and the other three groups were respectively supplemented with residual glycerine in the percentage of 3%, 6% and 9% of the total volume of the samples. The volume of biogas was controlled by an automated system for reading in laboratory scale and the quality of the biogas (CH4) measured from a specific sensor. The results showed that the residual glycerine has high potential for biogas production, with increases of 124.95%, 156.98% and 197.83% in the groups 3%, 6% and 9%, respectively, relative to the sample control. However, very high organic loads can compromise the process of digestion affecting the quality of the biogas generated in relation to methane.

Electro-Oxidation Treatment of Pulp and Paper Mill Circulating Waters and Wastewaters

Interest in water treatment by electrochemical methods has grown in recent years. Electrochemical oxidation has been applied particularly successfully to degrade different organic pollutants and disinfect drinking water. This study summarizes the effectiveness of the electrochemical oxidation technique in inactivating different primary biofilm forming paper mill bacteria as well as sulphide and organic material in pulp and paper mill wastewater in laboratory scale batch experiments. Three different electrodes, borondoped diamond (BDD), mixed metal oxide (MMO) and PbO2, were employed as anodes. The impact on inactivation efficiency of parameters such as current density and initial pH or chloride concentration of synthetic paper machine water was studied. The electrochemical behaviour of the electrodes was investigated by cyclic voltammetry with MMO, BDD and PbO2 electrodes in synthetic paper mill water as also with MMO and stainless steel electrodes with biocides. Some suggestions on the formation of different oxidants and oxidation mechanisms were also presented during the treatment. Aerobic paper mill bacteria species (Deinococcus geothermalis, Pseudoxanthomonas taiwanensis and Meiothermus silvanus) were inactivated effectively (>2 log) at MMO electrodes by current density of 50 mA/cm2 and the time taken three minutes. Increasing current density and initial chloride concentration of paper mill water increased the inactivation rate of Deinococcus geothermalis. The inactivation order of different bacteria species was Meiothermus silvanus > Pseudoxanthomonas taiwanensis > Deinococcus geothermalis. It was observed that inactivation was mainly due to the electrochemically generated chlorine/hypochlorite from chloride present in the water and also residual disinfection by chlorine/hypochlorite occurred. In real paper mill effluent treatment sulphide oxidation was effective with all the different initial concentrations (almost 100% reduction, current density 42.9 mA/cm2) and also anaerobic bacteria inactivation was observed (almost 90% reduction by chloride concentration of 164 mg/L and current density of 42.9 mA/cm2 in five minutes). Organic material removal was not as effective when comparing with other tested techniques, probably due to the relatively low treatment times. Cyclic voltammograms in synthetic paper mill water with stainless steel electrode showed that H2O2 could be degraded to radicals during the cathodic runs. This emphasises strong potential of combined electrochemical treatment with this biocide in bacteria inactivation in paper mill environments.

Hydrodynamics Characteristics and Gas-Liquid Mass Transfer in a Three Phase Fluidized Bed Reactor

This paper presents the experimental characterization of hydrodynamics and gas-liquid mass transfer in a three-phase fluidized bed containing polystyrene and nylon particles. The influence of gas and liquid velocities on phase holdups and volumetric gas-liquid mass transfer coefficient was investigated for flow conditions similar to those applied in biotechnological process. The phase holdups were obtained by the pressure profile technique. The volumetric gas-liquid mass transfer coefficient was obtained adjusting the experimental concentration profiles of dissolved oxygen in the liquid phase with the predictions of the axial dispersion model. According to experimental results the liquid holdup increases with the gas velocity, whereas the solid holdup decreases. The gas holdup increases significantly with the increase in gas velocity, and it shows for the three-phase fluidized bed comparable values or larger than those of bubble column. The volumetric gas-liquid mass transfer coefficient increases significantly with an increase in the air velocity for both bubble column and fluidized beds. In addition, in the operational condition of high liquid velocity, the presence of low-density particles in the bed increased the gas-liquid mass transfer, and thus the volumetric mass transfer coefficient values obtained in the fluidized bed were comparable or larger than those of bubble column.