Development of a Continuous Emulsion Copolymerization Process in a Tubular Reactor

This contribution describes the development of a continuous emulsion copolymerization processs for vinyl acetate and n-butyl acrylate in a tubular reactor. Special features of this reactor include the use of oscillatory (pulsed) flow and internals (sieve plates) to prevent polymer fouling and promote good radial mixing, along with a controlled amount of axial mixing. The copolymer system studied (vinyl acetate and butyl acrylate) is strongly prone to composition drift due to very different reactivity ratios. An axially dispersed plug flow model, based on classical free radical copolymerization kinetics, was developed for this process and used successfully to optimize the lateral feeding profile to reduce compositional drift. An energy balance was included in the model equations to predict the effect of temperature variations on the process. The model predictions were validated with experimental data for monomer conversion, copolymer composition, average particle size, and temperature measured along the reactor length.

Modeling Vinyl Acetate and n-Butyl Acrylate Emulsion Copolymerization Process

This work presents a mathematical model for the vinyl acetate and n-butyl acrylate emulsion copolymerization process in batch reactors. The model is able to explain the effects of simultaneous changes in emulsifier concentration, initiator concentration, monomer-to-water ratio, and monomer feed composition on monomer conversion, copolymer composition and, to lesser extent, average particle size evolution histories. The main features of the system, such as the increase in the rate of polymerization as temperature, emulsifier, and initiator concentrations increase are correctly represented by the model. The model accounts for the basic features of the process and may be useful for practical applications, despite its simplicity and a reduced number of adjustable parameters.

MODELING ELECTRODIALYSIS AND A PHOTOCHEMICAL PROCESS FOR THEIR INTEGRATION IN SALINE WASTEWATER TREATMENT

Oxidation processes can be used to treat industrial wastewater containing non-biodegradable organic compounds. However, the presence of dissolved salts may inhibit or retard the treatment process. In this study, wastewater desalination by electrodialysis (ED) associated with an advanced oxidation process (photo-Fenton) was applied to an aqueous NaCl solution containing phenol. The influence of process variables on the demineralization factor was investigated for ED in pilot scale and a correlation was obtained between the phenol, salt and water fluxes with the driving force. The oxidation process was investigated in a laboratory batch reactor and a model based on artificial neural networks was developed by fitting the experimental data describing the reaction rate as a function of the input variables. With the experimental parameters of both processes, a dynamic model was developed for ED and a continuous model, using a plug flow reactor approach, for the oxidation process. Finally, the hybrid model simulation could validate different scenarios of the integrated system and can be used for process optimization.

A mechanistic kinetic model for phenol degradation by the Fenton process

The objective of this paper is to develop and validate a mechanistic model for the degradation of phenol by the Fenton process. Experiments were performed in semi-batch operation, in which phenol, catechol and hydroquinone concentrations were measured. Using the methodology described in Pontes and Pinto [R.F.F. Pontes, J.M. Pinto, Analysis of integrated kinetic and flow models for anaerobic digesters, Chemical Engineering journal 122 (1-2) (2006) 65-80], a stoichiometric model was first developed, with 53 reactions and 26 compounds, followed by the corresponding kinetic model. Sensitivity analysis was performed to determine the most influential kinetic parameters of the model that were estimated with the obtained experimental results. The adjusted model was used to analyze the impact of the initial concentration and flow rate of reactants on the efficiency of the Fenton process to degrade phenol. Moreover, the model was applied to evaluate the treatment cost of wastewater contaminated with phenol in order to meet environmental standards. (C) 2009 Elsevier B.V. All rights reserved.

Control charts for individual observations of a bivariate Poisson process

In this paper, three single-control charts are proposed to monitor individual observations of a bivariate Poisson process. The specified false-alarm risk, their control limits, and ARLs were determined to compare their performances for different types and sizes of shifts. In most of the cases, the single charts presented better performance rather than two separate control charts ( one for each quality characteristic). A numerical example illustrates the proposed control charts.

Diagnostic errors and repetitive sequential classifications in on-line process control by attributes

The procedure of on-line process control by attributes, known as Taguchi`s on-line process control, consists of inspecting the mth item (a single item) at every m produced items and deciding, at each inspection, whether the fraction of conforming items was reduced or not. If the inspected item is nonconforming, the production is stopped for adjustment. As the inspection system can be subject to diagnosis errors, one develops a probabilistic model that classifies repeatedly the examined item until a conforming or b non-conforming classification is observed. The first event that occurs (a conforming classifications or b non-conforming classifications) determines the final classification of the examined item. Proprieties of an ergodic Markov chain were used to get the expression of average cost of the system of control, which can be optimized by three parameters: the sampling interval of the inspections (m); the number of repeated conforming classifications (a); and the number of repeated non-conforming classifications (b). The optimum design is compared with two alternative approaches: the first one consists of a simple preventive policy. The production system is adjusted at every n produced items (no inspection is performed). The second classifies the examined item repeatedly r (fixed) times and considers it conforming if most classification results are conforming. Results indicate that the current proposal performs better than the procedure that fixes the number of repeated classifications and classifies the examined item as conforming if most classifications were conforming. On the other hand, the preventive policy can be averagely the most economical alternative rather than those ones that require inspection depending on the degree of errors and costs. A numerical example illustrates the proposed procedure. (C) 2009 Elsevier B. V. All rights reserved.

Effects of the preventive and corrective adjustments in economical designs for online process control for attributes with misclassification errors

The procedure for online process control by attributes consists of inspecting a single item at every m produced items. It is decided on the basis of the inspection result whether the process is in-control (the conforming fraction is stable) or out-of-control (the conforming fraction is decreased, for example). Most articles about online process control have cited the stoppage of the production process for an adjustment when the inspected item is non-conforming (then the production is restarted in-control, here denominated as corrective adjustment). Moreover, the articles related to this subject do not present semi-economical designs (which may yield high quantities of non-conforming items), as they do not include a policy of preventive adjustments (in such case no item is inspected), which can be more economical, mainly if the inspected item can be misclassified. In this article, the possibility of preventive or corrective adjustments in the process is decided at every m produced item. If a preventive adjustment is decided upon, then no item is inspected. On the contrary, the m-th item is inspected; if it conforms, the production goes on, otherwise, an adjustment takes place and the process restarts in-control. This approach is economically feasible for some practical situations and the parameters of the proposed procedure are determined minimizing an average cost function subject to some statistical restrictions (for example, to assure a minimal levelfixed in advanceof conforming items in the production process). Numerical examples illustrate the proposal.

Single step process for particles surface modification or thin film composite production

Adsorbent materials and composites are quite useful for sensor development. Therefore, the aim of this work is the surface modification of particulates and/or composite formation. The material was produced by plasma polymerization of HMDS (hexamethyldisilazane) in a single step. SEM analysis shows good surface coverage of particulates with a plasma polymerized film formed by several clusters that might increase adsorption. Particles (starch. 5 5 mu m) recovered with HMDS films show good properties for retention of medium-size Organic molecules, such as dye. Thin films formed by a mixture of particles and plasma polymerized thin film HMDS species were obtained in a single step and can be used for retention of organic compounds, in liquid or gaseous phase. (C) 2009 Elsevier B.V. All rights reserved.

Valve friction and nonlinear process model closed-loop identification

Among several process variability sources, valve friction and inadequate controller tuning are supposed to be two of the most prevalent. Friction quantification methods can be applied to the development of model-based compensators or to diagnose valves that need repair, whereas accurate process models can be used in controller retuning. This paper extends existing methods that jointly estimate the friction and process parameters, so that a nonlinear structure is adopted to represent the process model. The developed estimation algorithm is tested with three different data sources: a simulated first order plus dead time process, a hybrid setup (composed of a real valve and a simulated pH neutralization process) and from three industrial datasets corresponding to real control loops. The results demonstrate that the friction is accurately quantified, as well as ""good"" process models are estimated in several situations. Furthermore, when a nonlinear process model is considered, the proposed extension presents significant advantages: (i) greater accuracy for friction quantification and (ii) reasonable estimates of the nonlinear steady-state characteristics of the process. (C) 2010 Elsevier Ltd. All rights reserved.

TL and OSL properties of KAlSi(3)O(8):Mn, obtained by sol-gel process

Thermoluminescence (TL) and Optically Stimulated Luminescence (OSL) properties of KAlSi(3)O(8):Mn glasses obtained through the sol gel technique were investigated. Samples were obtained with five different molar concentrations of 0.25, 0.5, 1, 2 and 5 mol% of manganese. Transmission Electronic Microscopy (TEM) indicated the occurrence of nanoparticles composed by glass matrix elements with Mn. Best results for TL response were obtained with 0.5 mol% Mn doped sample, which exhibits a TL peak at 180 degrees C. The TL spectrum of this sample presents a broad emission band from 450 to 700 nm with a peak at 575 nm approximately. The emission band fits very well with the characteristic lines of the Mn(2+) emission features. According to this fact, the band at 410 nm can be ascribed to (6)A(1)(S) -> (4)A(1)(G), (4)E(G) transition, while the 545 nm band can be attributed to the superposition of the transitions (6)A(1)(S) -> (4)T(2)(G) and (6)A(1)(S) -> (4)T(1)(G). The dependence of the TL response with the energy of X-rays (27-41 keV) showed a small decrease of the TL intensity in the high energy region. Excitation with blue LEDs showed OSL in the UV region with a fast decay component. (C) 2011 Elsevier Ltd. All rights reserved.

Surface modification of bovine bone ash prepared by milling and acid washing process

Bovine bone ash is the main raw material for fabrication of bone china, a special kind of porcelain that has visual and mechanical advantages when compared to usual porcelains. The properties of bone china are highly dependent on the characteristics of the bone ash. However, despite a relatively common product, the science behind formulations and accepted fabrication procedures for bone china is not completely understood and deserves attention for future processing optimizations. In this paper, the influence of the preparation steps (firing, milling, and washing of the bones) on the physicochemical properties of bone ash particles was investigated. Bone powders heat-treated at temperatures varying from 700 to 1000 degrees C were washed and milled. The obtained materials were analyzed in terms of particle size distribution, chemical composition, density, specific surface area, FTIR spectroscopy, dynamic electrophoretic mobility, crystalline phases and scanning electron microscopy. The results indicated that bone ash does not significantly change in terms of chemistry and physical features at calcination temperatures above 700 degrees C. After washing in special conditions, one could only observe hydroxyapatite in the diffraction pattern. By FTIR it was observed that carbonate seems to be mainly concentrated on the surface of the powders. Since this compound can influence in the dispersion stability, and consequently in the quality of the final bone china product, and considering optimal washing parameters based on the dynamic electrophoretic mobility results, we describe a procedure for surface cleaning. (c) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

OPTIMIZATION OF THE TREATMENT PROCESS FOR RESIDUAL WATER FROM A BEER INDUSTRY

The optimization of the treatment process for residual waters from a brewery operating under the modality of an anaerobic reactor and activated sludge combination was studied in two phases. In the first stage, lasting for six months, the characteristics and parameters of the plant operation were analyzed, wherein a diversion rate of more than 50% to aerobic treatment, the use of two aeration tanks and a high sludge production prevailed. The second stage comprised four months during which the system worked under the proposed operational model, with the aim of improving the treatment: reduction of the diversion rate to 30% and use of only one aeration tank At each stage, TSS, VSS and COD were measured at the entrance and exit of the anaerobic reactor mid the aeration tanks. The results were compared with the corresponding design specifications and the needed conditions were applied to reduce the diversion rate towards the aerobic process through monitoring the volume and concentration of the affluent, while applying the strategic changes in reactor parameters needed to increase its efficiency. A diversion reduction from 53 to 34% was achieved, reducing the sludge discharge generated in the aerobic system from 3670mg TSS/l. with two aeration tanks down to 2947mf TSS/l using one tank keeping the same relation VSS:TSS (0.55) and an efficiency of total removal of 98% in terms of COD.

Association between decay fungi and subterranean termites in the wood biodeterioration process of Tipuana tipu (Benth.) O. Kuntze trees of Sao Paulo city, SP

In the present paper the process of wood biodeterioration of tipuana trees planted in 7 regions of the city of Sao Paulo, SP was evaluated. On the sidewalks, 1109 trees were analyzed taking into consideration the occurrence and association of the xylophagous organisms (decay fungi and subterranean termites), the wood deterioration and the BHD (breast height diameter). The percentage of wood internal deterioration (%) was obtained by non destructive analysis, using a penetrometer. The results had shown that 75% of the tipuana trees presented BHD superior to 50 cm, characterizing them as adult. Decay fungi in the roots and/or trunk had been observed in 338 trees (30.5%). Subterranean termites of Heterotermes sp. and Coptotermes gestroi species had occurred in 307 trees (27.7%), the latter in high infestation level. The association between the fungi and termites was observed, as well as its relation with the BHD, where a greater value of BHD meant higher wood biodeterioration intensity. For tipuana trees, the BHD was considered an indicative attribute of the internal deterioration intensity, caused by these xylophagous organisms.

Podzolization as a deferralitization process: dynamics and chemistry of ground and surface waters in an Acrisol-Podzol sequence of the upper Amazon Basin

Hydrochemical processes involved in the development of hydromorphic Podzols are a major concern for the upper Amazon Basin because of the extent of the areas affected by such processes and the large amounts of organic carbon and associated metals exported to the rivers. The dynamics and chemical composition of ground and surface waters were studied along an Acrisol-Podzol sequence lying in an open depression of a plateau. Water levels were monitored along the sequence over a period of 2 years by means of piezometers. Water was sampled in zero-tension lysimeters for groundwater and for surface water in the drainage network of the depression. The pH and concentrations of organic carbon and major elements (Si, Fe and Al) were determined. The contrasted changes reported for concentrations of Si, organic carbon and metals (Fe, Al) mainly reflect the dynamics of the groundwater and the weathering conditions that prevail in the soils. Iron is released by the reductive dissolution of Fe oxides, mostly in the Bg horizons of the upslope Acrisols. It moves laterally under the control of hydraulic gradients and migrates through the iron-depleted Podzols where it is exported to the river network. Aluminium is released from the dissolution of Al-bearing minerals (gibbsite and kaolinite) at the margin of the podzolic area but is immobilized as organo-Al complexes in spodic horizons. In downslope positions, the quick recharge of the groundwater and large release of organic compounds lead to acidification and a loss of metals (mainly Al), previously stored in the Podzols.

Development and Characterization of L-Alanyl-L-Glutamine Containing Pellets employing Extrusion-Spheronization Method and Drying Process in Fluidized Bad Equipment.

Development and Characterization of L-Alanyl-L-Glutamine Containing Pellets employing Extrusion-Spheronization Method and Drying Process in Fluidized Bad Equipment"". In this work, five formulations of L-alanyl-L-glutamine (glutamine dipeptide) containing pellets with different drug concentration were developed and evaluated: F1 (9.07%); F2 (17.70%); F3 (27.98%); F4 (37.74%) e F5 (47.53%). Pellets were prepared by extrusion-spheronization method and, further, dried in fluidized bad equipment. The following assays were carried out with the batches obtained: granulometry, friability, true density and morphologic analysis. Between the five formulations evaluated, pellets obtained from F3 present best yield (75.80%), most uniform particle size distribution (89.67% of pellets with size in the range of 0.80 to 1.18), most high true density (2.1634 g/ml) and best aspect (1.0795 +/- 0.0410). Due to these features, pellets obtained from F3 were considered adequate to further polymeric coating process in order to produce a multiparticulate system to prolong L-alanyl-L-glutamine release.