Fluid dynamic modelling and simulation of circulating fluidized bed reactors: importance of the interface turbulence transfer

The main objective of this work is to analyze the importance of the gas-solid interface transfer of the kinetic energy of the turbulent motion on the accuracy of prediction of the fluid dynamic of Circulating Fluidized Bed (CFB) reactors. CFB reactors are used in a variety of industrial applications related to combustion, incineration and catalytic cracking. In this work a two-dimensional fluid dynamic model for gas-particle flow has been used to compute the porosity, the pressure, and the velocity fields of both phases in 2-D axisymmetrical cylindrical co-ordinates. The fluid dynamic model is based on the two fluid model approach in which both phases are considered to be continuous and fully interpenetrating. CFB processes are essentially turbulent. The model of effective stress on each phase is that of a Newtonian fluid, where the effective gas viscosity was calculated from the standard k-epsilon turbulence model and the transport coefficients of the particulate phase were calculated from the kinetic theory of granular flow (KTGF). This work shows that the turbulence transfer between the phases is very important for a better representation of the fluid dynamics of CFB reactors, especially for systems with internal recirculation and high gradients of particle concentration. Two systems with different characteristics were analyzed. The results were compared with experimental data available in the literature. The results were obtained by using a computer code developed by the authors. The finite volume method with collocated grid, the hybrid interpolation scheme, the false time step strategy and SIMPLEC (Semi-Implicit Method for Pressure Linked Equations - Consistent) algorithm were used to obtain the numerical solution.

The pH-dependent phase distribution of wood pitch components in papermaking processes

Wood contains only a very small amount of lipophilic extractives, commonly known as wood pitch. The pitch is known to cause severe problems in papermaking processes. The amount of pitch in process waters can be decreased by seasoning of the raw material prior to pulping, pulp washing, removal of pitch by flotation, adsorption of pitch onto various mineral surfaces, and retention of pitch to the fibre material by cationic polymers. The aim of this study was to determine the influence of pH on some of the methods used for pitch control. Experiments were performed using laboratory-made wood pitch emulsions with varying pH, salt concentration, hemicellulose concentration and pitch composition. These emulsions were used to study the phase distribution of resin and fatty acids, the colloidal stability of pitch with and without steric stabilisation by galactoglucomannans, and the interactions between wood pitch and mineral particles. Purification of unbleached and peroxidebleached mill process water was performed by froth flotation in combination with a foaming agent. The distribution of resin and fatty acids (RFAs) between colloidal pitch droplets and the water phase was very dependent on pH. At pH 3, almost all of the RFAs were attached to the pitch droplets, while increasing the pH led to increasing concentration of dissolved RFAs in the water phase. The presence of salt shifted the release of RFAs towards higher pH, while lower ratio of neutral pitch in the emulsion resulted in release of RFAs at lower pH. It was also seen that the dissolution and adsorption of RFAs at sudden pHchanges takes place very quickly. Colloidal pitch was more stable against electrolyte-induced aggregation at higher pH, due to its higher anionic charge. The concentration of cationic polymers needed to aggregate colloidal pitch also increased with increasing pH. The surface characteristics of solid particles, such as amount of charged groups, were very important for understanding their interactions with colloidal wood pitch. Water-soluble galactoglucomannans stabilised the colloidal pitch sterically against aggregation, but could not completely prevent interactions between wood pitch and hydrophilic particles. Froth flotation of unbleached and peroxidebleached process water showed that the pitch could be removed more effectively and selectively at low pH, compared to at neutral pH. The pitch was removed more effectively, using lower concentrations of foaming agent, from peroxide-bleached water than from unbleached water. The results show that pH has a major impact on various pulping and papermaking processes. It determines the anionic charge of the colloidal pitch and the solubility of certain pitch components. Because of this, the pH influences the effectiveness of pitch retention and removal of pitch. The results indicate that pitch problems could be diminished by acknowledging the importance of pH in various papermaking processes.

Pulsed corona discharge as an advanced oxidation process for degradation of organic

Advanced oxidation processes (AOPs) have been studied and developed to suffice the effective removal of refractory and toxic compounds in polluted water. The quality and cost of wastewater treatment need improvements, and electric discharge technology has a potential to make a significant difference compared to other established AOPs based on energy efficiency. The generation of active oxidant species such as ozone and hydroxyl radicals by high voltage discharge is a relatively new technology for water treatment. Gas-phase pulsed corona discharge (PCD), where a treated aqueous solution is dispersed between corona-producing electrodes free of the dielectric barriers, was developed as an alternative approach to the problem. The short living radicals and ozone formed in the gas phase and at the gas-liquid interface react with dissolved impurities. PCD equipment has a relatively simple configuration, and with the reactor in an enclosed compartment, it is insensitive towards gas humidity and does not need the gas transport. In this thesis, PCD was used to study and evaluate the energy efficiency for degrading various organic compounds, as well as the chemistry of the oxidation products formed. The experiments investigate the aqueous oxidation of phenol, humic substances, pharmaceutical compounds (paracetamol, ibuprofen, indomethacin, salicylic acids, -estradiol), as well as lignin degradation and transformation to aldehydes. The study aims to establish the influence of initial concentration of the target pollutant, the pulsed discharge parameters, gas phase composition and the pH on the oxidation kinetics and the efficiency. Analytical methods to measure the concentrations of the target compounds and their by-products include HPLC, spectrophotometry, TOC and capillary electrophoresis. The results of the research included in this summary are presented in the attached publications and manuscripts accepted for publication. Pulsed corona discharge proved to be highly effective in oxidizing each of the target compounds, surpassing the closest competitor, conventional ozonation. The increase in oxidation efficiencies for some compounds in oxygen media and at lower pulse repetition frequencies shows a significant role of ozone. The role of the ·OH radicals was established in the surface reactions. The main oxidation products, formation of nitrates, and the lignin transformation were quantified. A compound specific approach is suggested for optimization of the PCD parameters that have the most significant impact on the oxidation energy efficiency because of the different characteristics and responses of the target compound to the oxidants, as well as different admixtures that are present in the wastewater. Further studies in the method’s safety (nitration and nitrosation of organic compounds, nitrite and nitrate formation enhancement) are needed for promoting the method.

Catalytic direct synthesis of hydrogen peroxide in a novel microstructured reactor

The direct synthesis from hydrogen and oxygen is a green alternative for production of hydrogen peroxide. However, this process suffers from two challenges. Firstly, mixtures of hydrogen and oxygen are explosive over a wide range of concentrations (4-94% H2 in O2). Secondly, the catalytic reaction of hydrogen and oxygen involves several reaction pathways, many of them resulting in water production and therfore decreasing selectivity. The present work deals with these two challenges. The safety problem was dealed by employing a novel microstructured reactor. Selectivity of the reaction was highly improved by development a set of new catalysts. The final goal was to develop an effective and safe continuous process for direct synthesis of hydrogen peroxide from H2 and O2. Activated carbon cloth and Sibunit were examined as the catalysts’ supports. Palladium and gold monometallic and palladium-gold bimetallic catalysts were thoroughly investigated by numerous kinetic experiments performed in a tailored batch reactor and several catalyst charachterization methods. A complete set of data for direct synthesis of H2O2 and its catalytic decomposition and hydrogenation was obtained. These data were used to assess factors influencing selectivity and activity of the catalysts in direct synthesis of H2O2 as well as its decomposition and hydrogenation. A novel microstructured reactor was developed based on hydrodynamics and mass transfer studies in prototype microstractural plates. The shape and the size of the structural elements in the microreactor plate were optimized in a way to get high gas-liquid interfacial area and gas-liquid mass transfer. Finally, empirical correlations for the volumetric mass transfer coefficient were derived. A bench-scale continuous process was developed by using the novel microstructral plate reactor. A series of kinetic experiments were performed to investigate the effects of the gas and the liquid feed rates and their ratio, the amount of the catalyst, the gas feed composition and pressure on the final rate of H2O2 production and selectivity.

Influence of multi-phase phenomena on semibatch crystallization processes of aqueous solutions

Crystal properties, product quality and particle size are determined by the operating conditions in the crystallization process. Thus, in order to obtain desired end-products, the crystallization process should be effectively controlled based on reliable kinetic information, which can be provided by powerful analytical tools such as Raman spectrometry and thermal analysis. The present research work studied various crystallization processes such as reactive crystallization, precipitation with anti-solvent and evaporation crystallization. The goal of the work was to understand more comprehensively the fundamentals, phenomena and utilizations of crystallization, and establish proper methods to control particle size distribution, especially for three phase gas-liquid-solid crystallization systems. As a part of the solid-liquid equilibrium studies in this work, prediction of KCl solubility in a MgCl2-KCl-H2O system was studied theoretically. Additionally, a solubility prediction model by Pitzer thermodynamic model was investigated based on solubility measurements of potassium dihydrogen phosphate with the presence of non-electronic organic substances in aqueous solutions. The prediction model helps to extend literature data and offers an easy and economical way to choose solvent for anti-solvent precipitation. Using experimental and modern analytical methods, precipitation kinetics and mass transfer in reactive crystallization of magnesium carbonate hydrates with magnesium hydroxide slurry and CO2 gas were systematically investigated. The obtained results gave deeper insight into gas-liquid-solid interactions and the mechanisms of this heterogeneous crystallization process. The research approach developed can provide theoretical guidance and act as a useful reference to promote development of gas-liquid reactive crystallization. Gas-liquid mass transfer of absorption in the presence of solid particles in a stirred tank was investigated in order to gain understanding of how different-sized particles interact with gas bubbles. Based on obtained volumetric mass transfer coefficient values, it was found that the influence of the presence of small particles on gas-liquid mass transfer cannot be ignored since there are interactions between bubbles and particles. Raman spectrometry was successfully applied for liquid and solids analysis in semi-batch anti-solvent precipitation and evaporation crystallization. Real-time information such as supersaturation, formation of precipitates and identification of crystal polymorphs could be obtained by Raman spectrometry. The solubility prediction models, monitoring methods for precipitation and empirical model for absorption developed in this study together with the methodologies used gives valuable information for aspects of industrial crystallization. Furthermore, Raman analysis was seen to be a potential controlling method for various crystallization processes.

Continuous hydride generation in the presence of L- cysteine for the determination of arsenic, bismuth, antimony and tin in steels by inductively coupled plasma atomic emission spectrometry

Arsenic, bismuth, germanium, antimony and tin were simultaneously determined by continuous hydride generation and inductively coupled plasma-atomic emission spectrometry . I Hydrides were introduced into four different types of gas-liquid separators. Two of the gas-liquid separators were available in-house. A third was developed for this project and a fourth was based on a design used by CET AC. The best signal intensity was achieved by the type II frit-based gas-liquid separator, but the modified Cetac design gave promise for the future, due to low relative standard deviation. A method was developed for the determination of arsenic, bismuth, antimony and tin in low-alloy steels. Four standard reference materials from NIST were dissolved in 10 mL aqua regia without heat. Good agreement was obtained between experimental values and certified values for arsenic, bismuth, antimony and tin. The method was developed to provide the analyst with the opportunity to determine the analytes by using simple aqueous standards to prepare calibration lines. Within the limits of the samples analyzed, the method developed is independent of matrix.

Fecal microbiota in patients receiving enteral feeding are highly variable and may be altered in those who develop diarrhea

Background: The pathogenesis of diarrhea in patients receiving enteral feeding includes colonic water secretion, antibiotic prescription, and enteropathogenic colonization, each of which involves an interaction with the gastrointestinal microbiota. Objective: The objective was to investigate temporal changes in the concentrations of fecal microbiota and short-chain fatty acids (SCFAs) in patients starting 14-d of enteral feeding and to compare these changes between patients who do and do not develop diarrhea. Design: Twenty patients starting exclusive nasogastric enteral feeding were monitored for 14 d. Fecal samples were collected at the start, middle, and end of this period and were analyzed for major bacterial groups by using culture independent fluorescence in situ hybridization and for SCFAs by using gas-liquid chromatography. Results: Although no significant changes in fecal microbiota or SCFAs were observed during enteral feeding, stark alterations occurred within individual patients. Ten patients (50%) developed diarrhea, and these patients had significantly higher concentrations of clostridia (P = 0.026) and lower concentrations (P = 0.069) and proportions (P = 0.029) of bifidobacteria. Patients with and without diarrhea had differences in the proportion of bifidobacteria (median: 0.4% and 3.7%; interquartile range: 0.8 compared with 4.3; P = 0.035) and clostridia (median: 10.4% and 3.7%; interquartile range: 14.7 compared with 7.0; P = 0.063), respectively, even at the start of enteral feeding. Patients who developed diarrhea had higher concentrations of total fecal SCFAs (P = 0.044), acetate (P = 0.029), and butyrate (P = 0.055). Conclusion: Intestinal dysbiosis occurs in patients who develop diarrhea during enteral feeding and may be involved in its pathogenesis. Am J Clin Nutr 2009; 89: 240-7.

Optimization of the physical refining of sunflower oil concerning the final contents of trans-fatty acids

The final contents of total and individual trans-fatty acids of sunflower oil, produced during the deacidification step of physical refining were obtained using a computational simulation program that considered cis-trans isomerization reaction features for oleic, linoleic, and linolenic acids attached to the glycerol part of triacylglycerols. The impact of process variables, such as temperature and liquid flow rate, and of equipment configuration parameters, such as liquid height, diameter, and number of stages, that influence the retention time of the oil in the equipment was analyzed using the response-surface methodology (RSM). The computational simulation and the RSM results were used in two different optimization methods, aiming to minimize final levels of total and individual trans-fatty acids (trans-FA), while keeping neutral oil loss and final oil acidity at low values. The main goal of this work was to indicate that computational simulation, based on a careful modeling of the reaction system, combined with optimization could be an important tool for indicating better processing conditions in industrial physical refining plants of vegetable oils, concerning trans-FA formation.

Associação entre manometria ano-retal e neuropatia pudenda em pacientes com incontinência fecal

A incontinência fecal é a incapacidade de manter o controle da eliminação do conteúdo intestinal em local e tempo socialmente adequados, resultando em escape de gases e fezes. Esta condição acarreta grande prejuízo na vida social dos acometidos. A causa conhecida mais comum é o trauma perineal, porém em uma grande proporcão a incontinência é idiopática. A avaliação da função esfincteriana anal é fundamental para o diagnóstico e para a conduta terapêutica na incontinência fecal. Para o entendimento da fisiopatologia desta condição desenvolveram-se vários exames de investigação. A manometria ano-retal é considerado imprescindível na avaliação. A correlação dos dados da manometria com a gravidade da doença e com estudos eletrofisiológicos ainda não estão bem estabelecidos. O objetivo deste estudo é correlacionar os dados da manometria ano-retal e o estudo do tempo de latência motora terminal do nervo pudendo com a incontinência fecal e comorbidades. Foram estudados prospectivamente todos os pacientes com queixa clínica de incontinência fecal atendidos no ambulatório de Serviço de Coloproctologia do Hospital Nossa Senhora da Conceição, de Porto Alegre (RS), entre março de 1997 e junho de 2000. De todos os pacientes foram coletados dados da anamnese que os classificaram segundo escore de incontinência proposto por JORGE & WEXNER (1993). Todos foram submetidos a manometria ano-retal, estudo do tempo de latência motora terminal do nervo pudendo bilateralmente e exame proctológico. Foram excluídos os pacientes que não concluíram toda a investigação, com cirurgias colo-retais baixas prévias ou neoplasia de reto e canal anal. Para análise estatística, os pacientes foram separados em grupos segundo a manometria normal ou alterada (hipotonia), presença ou não de neuropatia de nervo pudendo, por idade e por sexo. Foram estudados 39 pacientes, 85,6% do sexo feminino com idade média de 60,1 anos (±12,89). A média do escore de incontinência fecal foi de 9,30±4,93. À manometria ano-retal, vinte e três pacientes (59%) apresentaram pressões reduzidas. As pressões foram significativamente mais elevadas nos pacientes do sexo masculino. O tempo de latência motora terminal do nervo pudendo (neuropatia) foi prolongado em 14 doentes (35,9%). A idade e o tempo de latência motora terminal do nervo pudendo correlacionaram-se significativamente, r=0,422, (P=0,007). A demais correlações entre idade, pressões da manometria, tempo de latência motora terminal do nervo pudendo e escore de incontinência não foram estatisticamente significativas.

Desenvolvimento de um sistema de nitretação por plasma em fonte pulsada e sua influencia sobre a nitretação do titânio

The pulsed plasma nitriding is a solution currently used in the metallurgical industry to resolve problems earlier in the processing of parts by using plasma DC voltage. These problems consisted mainly of edge effect and opening arches caused due to non-uniformity of electric fields on uneven surfaces. By varying the pulse width can reduce these effects. However, variations in pulse width can drastically affect the population of the plasma species and hence the final microstructure of the nitrided layer. In literature, little is known about the effect of process parameters on the properties of the plasma species and, consequently, the surface properties. We have developed a system of nitriding with pulsed source with fixed period of 800  pulse width is variable. Examined the variation of these parameters on the properties of nitrided surface when keeping constant temperature, gas composition, flow, pressure and power. It was found that the values of width and pulse repetition time of considerable influence in the intensities of the species present in plasma. Moreover, we observed the existence of the edge effect for some values of pulse widths, as well as changes in surface roughness and hardness

Extraction and clean-up procedure for analysis of organochlorine pesticide residues in ethoxylated lanolin

In the present study an evaluation was made of a method for the determination of organochlorine pesticide residues in ethoxylated lanolin. Samples were homogenized with Celite, transferred to chromatographic columns, prepacked with silica gel deactivated to 10%. The pesticide elution was processed with n-hexane-dichloromethane and the concentrated eluate was analyzed using gas-liquid chromatography (GC) with electron capture detection (ECD). The composition of the elution solvent was a significant factor for the recovery of the pesticides. Mean recoveries obtained for fortified samples ranged from 87 to 94% for p,p'-DDE, dieldrin, endrin, p,p'-DDD and p,p'-DDT. Optimization of the experimental conditions resulted in a small-scale method that combines extraction and cleanup in a single step. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Metodologia rápida e eficiente para análise de pesticidas organoclorados em fubá

A rapid and efficient analytical method is presented for the quantitative analysis of 10 organochlorine pesticides in corn meal. The extraction and clean up steps are combined into one step by transferring the sample to a chromatographic column prepacked with alumina and silica gel. The pesticides are eluted with n-hexane-dichloromethane 9:1 (v/v) and the extracts analized by gas-liquid chromatography with electron capture detection, the average recoveries were between 78% and 98% and the detection limits were between 1 and 5 ng/g.

Cluster identification and characterization in the riser of a circulating fluidized bed from numerical simulation results

A methodology of identification and characterization of coherent structures mostly known as clusters is applied to hydrodynamic results of numerical simulation generated for the riser of a circulating fluidized bed. The numerical simulation is performed using the MICEFLOW code, which includes the two-fluids IIT's hydrodynamic model B. The methodology for cluster characterization that is used is based in the determination of four characteristics, related to average life time, average volumetric fraction of solid, existing time fraction and frequency of occurrence. The identification of clusters is performed by applying a criterion related to the time average value of the volumetric solid fraction. A qualitative rather than quantitative analysis is performed mainly owing to the unavailability of operational data used in the considered experiments. Concerning qualitative analysis, the simulation results are in good agreement with literature. Some quantitative comparisons between predictions and experiment were also presented to emphasize the capability of the modeling procedure regarding the analysis of macroscopic scale coherent structures. (c) 2007 Elsevier B.V. All rights reserved.

Small-scale method for the determination of selected organochlorine pesticides in soil

A small-scale method was developed for the simultaneous determination of γ-HCH, heptachlor, aldrin, dicofol, mirex, endosulfan I, endosulfan II and endosulfan sulphate in soil. The extraction and clean-up steps were combined into one step by transferring soil samples to chromatographic columns prepacked with neutral alumina. The pesticides elution was processed with n-hexane : dichloromethane (7:3) and the concentrated eluate was analysed using gas-liquid chromatography with electron capture detection. Analyses of the in vitro fortified samples with the selected pesticides were performed at three different levels. Mean recoveries for aldrin, γ-HCH and heptachlor, at levels of 2, 10 and 20 ng/g, ranged from 71 to 87%; for dicofol, at levels of 8, 40 and 80 ng/g, ranged from 97 to 103%; for endosulfan I and II, at levels of 5, 25 and 50 ng/g, ranged from 88 to 96%; for mirex, at levels of 6, 30 and 60 ng/g, ranged from 86 to 110%; and for endosulfan sulphate, at levels of 15, 75 and 150 ng/g, ranged from 93 to 104%. The method can be used for rapid determination of these pesticides in soil. © Springer-Verlag 1996.