Editorial Prof. Dr. Martín Aznar Dois importantes marcos foram atingidos no âmbito do Programa de Pós-Graduação em Engenharia Química: foram comemoradas a quingentésima defesa de doutorado e a milésima quingentésima defesa combinada (mestrado e doutorado). A Dra. Cláudia Conti Medugno defendeu a tese “Fases de membranas fluidas - L3 a partir de lipídio sintético e pentanol na região diluída - e o respectivo dialisado”, sob a orientação do Prof. Dr. Elias Basile Tambourgi, em 31 de julho (tese 500). O mestre Jener de Oliveira defendeu a dissertação “Estudo de aditivação em massa ou por recobrimento de filme de BOPP com compostos orgânicos e nanopartículas anti UV”, sob a orientação da Profa. Dra. Leila Peres, em 27 de setembro (defesa 1500). Os titulados e os seus orientadores receberam certificados de reconhecimento na 129 sessão ordinária da Congregação, em 19 de outubro de 2012. Estes números, impressionantes em se considerando a relativa juventude do Programa, só foram possíveis pelo esforço combinado de alunos, professores e funcionários ao longo destes anos. Muito em breve deveremos comemorar também a milésima dissertação de mestrado. Parabéns a toda a comunidade por esta ocasião histórica.

N E S T E N Ú M E R O 1 Editorial

1 Novo docente toma posse na FEQ

2 Artigos publicados em Julho-Setembro 2012

17 Teses e dissertações

20 Notas curtas

15 de outubro de 2012 Ano 6 Número 23

Uma publicação da Faculdade de Engenharia Química da UNICAMP Av. Albert Einstein 500, Campinas-SP, 13083-852 Editor: Prof. Dr. Martín Aznar, maznar@feq.unicamp.br, fone 3521-3962

Boletim da FEQ

Novo docente toma posse na FEQ

No dia 06 de setembro, o Prof. Dr. Guilherme José de Castilho tomou posse como Professor Doutor MS-3 junto ao Departamento de Engenharia de Processos (DEPro). O professor Guilherme possui graduação em Engenharia Química pela Universidade Estadual de Maringá (2005), mestrado em Engenharia Química pela Universidade Estadual de Campinas (2007) e doutorado em Engenharia Química pela Universidade Estadual de Campinas (2011). Trabalha na área de sistemas particulados, atuando principalmente em fluidização, leito fluidizado circulante, escoamento multifásico, riser, downer, fibra óptica e análise de caos. Entre as suas produções recentes destacam-se:

Amaral, R.L.; Castilho, G.J.; Cremasco, M.A. Experimental investigation of 3D velocity by tomographic particle

image velocimetry (Tomo-PIV) in a short riser section. Procedia Engineering, 42 (2012), 748-754. Castilho, G.J.; Cremasco, M.A. Comparison of downer and riser flows in a circulating bed by means of optical

fiber probe signals measurements. Procedia Engineering, 42 (2012), 326-333. Castilho, G.J.; Cremasco, M.A.; De Martin, L.; Aragon, J.M. Experimental fluid dynamics study in a fluidized bed

by deterministic chaos analysis. Particulate Science and Technology, 29 (2011), 179-196. Castilho, G.J.; Cremasco, M.A. Time domain analysis of optical fiber probe signals measured in a short

circulating fluidized bed riser. Particulate Science and Technology, 28 (2010), 520-528.

Boas vindas e muito sucesso!

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Artigos Publicados em Revistas Indexadas

Julho - Setembro 2012

Bases de dados: ISI Web of Knowledge, Sci Finder Scholar, Compendex, SciELO, Scopus, Scirus. Julho Use of biopolymeric membranes for adsorption of paraquat herbicide from water Cocenza, D.S.; Moraes, M.A.; Beppu, M.M.; Fraceto, L.F. Water, Air, & Soil Pollution, 223 (2012), 3093-3104. ISSN: 0049-6979. FI = 1.765. Qualis B1. doi:10.1007/s11270-012-1092-x The use of membranes prepared with alginate and chitosan to adsorb paraquat aqueous solution was evaluated as a potential alternative technique for remediation of contaminated water. Production of bilayer membranes was based on the electrostatic interaction between alginate (a polyanion) and chitosan (a polycation). Herbicide adsorption experiments were performed using three different membranes, consisting of pure alginate, pure chitosan, and a chitosan/alginate bilayer. Adsorption was characterized using the Langmuir and Freundlich isotherm models, as well as by applying pseudo-first order and pseudo-second order kinetic models. The potential use of the membranes in environmental applications was evaluated using water collected from the Sorocabinha River in São Paulo State, Brazil. The results indicated that interactions between the membranes and the herbicide were strongly related to the type of biopolymer and the physical–chemical characteristics of the herbicide. Fluid catalytic cracking environmental impact: factorial design coupled with genetic algorithms to minimize carbon monoxide pollution Cuadros , J.F.; Melo, D.C.; Maciel Filho, R.; Wolf Maciel, M.R. Chemical Engineering Transactions, 26 (2012), 243-248. ISSN: 1974-9791. Qualis B5. doi:10.3303/CET1226041 Fluid Catalytic Cracking (FCC) process is a complex process in petroleum refining industry; it cracks long chain molecules from gas oil and residues to produce high value products like diesel and gasoline. FCC process is composed by two reactors: the riser where cracking reactions take place and the regenerator where combustion reactions eliminate coke deposition from catalyst surface; the last reactors are connected by two transport lines where catalyst circulates. Regenerator flue gas emissions are composed by carbon oxides (CO and CO2), sulfur oxides (SO2 and SO3), nitrogen oxides (NO, N2O, N2), and particulates. This work focuses on the minimization of carbon monoxide (CO) in flue gases while maintaining high process conversion. A multi-objective optimization problem was established to maximize conversion and minimize emissions of CO. The problem was solved using genetic algorithms coupled with factorial design used to identify key process variables and to formulate objective optimization functions. Results showed a reduction in CO emissions in the order of 12.8 % with a conversion of 73 %, indicating genetic algorithms as an useful tool to comply environmental regulations and process demands with low computational burden and time. Improving second generation ethanol production through optimization of first generation production process from sugarcane Dias, M.O.S.; Junqueira, T.L.; Jesus, C.D.F.; Rossell, C.E.V.; Maciel Filho, R.; Bonomi, A. Energy, 43 (2012), 246-252. ISSN: 0360-5442. FI = 3.653. Qualis A2. doi:10.1016/j.energy.2012.04.034 Sugarcane bagasse and trash may be used as feedstock for second generation ethanol production. Production of second generation ethanol integrated with first generation plants processing sugarcane presents several advantages over the stand-alone second generation ethanol production process; however, bagasse is used as fuel to supply the energy demand of the first generation process, so the amount of bagasse and trash available for use as feedstock in second generation depends on the energy consumption of the integrated process. Therefore, process optimization leading to reduction in steam consumption will lead to the production of larger amounts of surplus bagasse. In this study the introduction of process improvements in the first generation autonomous distillery processing sugarcane were assessed through simulation using Aspen Plus. Second generation ethanol production was integrated to the optimized scenarios. Results show that process improvements can significantly increase the amount of lignocellulosic

Boletim da FEQ Página 3material available for use as feedstock for second generation ethanol production, thus increasing ethanol production. Development of a prototype of a colourimetric temperature indicator for monitoring food quality Maciel, V.B.V.; Yoshida, C.M.P.; Franco, T.T. Journal of Food Engineering, 111 (2012), 21-27. ISSN: 0260-8774. FI = 2.168. Qualis A1. doi:10.1016/j.jfoodeng.2012.01.037 Temperature greatly affects the food quality and safety. Temperature control is an important condition during distribution and storage. An intelligent and biodegradable temperature indicator packaging material was developed based on a natural and heat-sensitive pigment (anthocyanin – ATH). Different concentrations of ATH were incorporated into chitosan matrix films (2.00%, w/w) that were applied as a surface coating on card paper, forming the chitosan card paper system (CH-Sys). The novelty of this work is an alternative packaging material that is biodegradable, simple manufacturing and indicates temperature variations in a specific range by irreversible visual colour changes. The CH-Sys changed irreversibly the colour from light violet to light yellow in response to different temperature exposition (40°C until 70°C), independently of luminosity (0 or 1000 lx). The results indicated that the CH-Sys has a great potential for use as a temperature indicator prototype in the specific temperature range studied in this work. A model for excess volumes of salty water–acetonitrile mixtures at 298.15 K Morrone, S.R.; Francesconi, A.Z. Fluid Phase Equilibria, 313 (2012), 52-69. ISSN: 0378-3812. FI = 2.139. Qualis A1. doi:10.1016/j.fluid.2011.09.016 A model for salty water–acetonitrile mixtures at 298.15 K was proposed based on three different contributions: chemical, physical and electrostatical. The first two were accomplished by ERAS model and the third was achieved by analyzing several proposals: Debye–Hückel, Hepler and a modified ERAS model. In order to test the model values, densities for the mixtures were measured with a vibrating-tube densimeter and the excess molar volumes were determined. The salts molar concentrations varied from 0.001 to 0.004, covering the entire composition range for water–acetonitrile. For each system, the three model approaches was applied. The modified ERAS model provides the best results. Verification and validation of a thermal stratification experiment CFD simulation Rezende, H.C.; Santos, A.A.C.; Navarro, M.A.; Jordão, E. Nuclear Engineering and Design, 248 (2012), 72-81. ISSN: 0029-5493. FI = 0.083. Qualis A2. doi:10.1016/j.nucengdes.2012.03.044 Thermal stratification and striping are observed in many piping systems including those of nuclear power plants. Periodic occurrences of these thermal transients lead to fatigue and may induce undesirable failures and deformations to the piping. The Thermal Hydraulic Laboratory of the Centro de Desenvolvimento da Tecnologia Nuclear/Comissão Nacional de Energia Nuclear (CDTN/CNEN) conducts an experimental and numerical project simulating the thermal stratified flows in piping systems of pressurized water reactors (PWR) to obtain some understanding on these phenomena. Experiments were carried out in a test section simulating the steam generator injection nozzle of a PWR. A numerical simulation of one experiment was performed with the commercial finite volume Computational Fluid Dynamic code CFX 13.0. A vertical symmetry plane along the pipe was adopted to reduce the geometry in one half, reducing mesh element size and minimizing processing time. The RANS two equations RNG k– turbulence model with scalable wall function and the full buoyancy model were used in the simulation. In order to properly evaluate the numerical model it was performed a Verification and Validation (V&V) process. Numerical uncertainties due to mesh refinement and time step were evaluated. This validation process showed the great importance of a proper quantitative evaluation of numerical results. In past studies qualitative evaluations were considered enough and numerical results like the one presented here could be considered satisfactory for the prediction of thermal stratified flows. However, with the present V&V study it was possible to identify objectively the strengths and weaknesses of the model. Biodiesel production by an integrated reactive separation system: a comparative study Rios, L.F.; Martinez, E.L.; Silva, N.L.; Dantas, T.S.S.; Maciel Filho, R.; Wolf Maciel, M.R. Chemical Engineering Transactions, 26 (2012), 255-260. ISSN: 1974-9791. Qualis B5. doi:10.3303/CET1226043 The aim of this work is to present an efficient process using a reactive distillation column applied to biodiesel production. Reactive distillation is characterized by simultaneous implementation of reaction and separation within a single column. In this work, the biodiesel production from soybean oil with ethanol in presence of sodium hydroxide as catalyst was studied in a tray column. The experimental

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design applied was a full 22 factorial design with three central points. Two independent variables in two levels were selected for this study: substrate molar ratio (ethanol:soybean oil) and catalyst concentration and one variable dependent was considered, the response selected was the ethyl ester conversion. The process simulation was performed using the commercial simulator Aspen Plus 7.2. The simulation results showed a good agreement with experimental results and it can be seen that conversions above 99.84 % of ethyl esters could be achieved. Reuse of textile effluent treated with advanced oxidation process by UV/H2O2 Rosa, J.M.; Tambourgi, E.B.; Santana, J.C.C. Chemical Engineering Transactions, 26 (2012), 207-212. ISSN: 1974-9791. Qualis B5. doi:10.3303/CET1226035 The objective of this work was to study the possibility of reuse of effluent in continuous dyeing of 100% cotton. Were made five dyeing, four with reactive dyes and one with fluorescent brightener, using the same bath after treatment by advanced oxidation process (AOP) by UV/H2O2. The efficiency results were higher than 85 % in all cases allowing total reuse of the effluent. The dyeing made with treated effluent were compared against dyeing made with water, with values of deviations smaller than 1.10. Based on these results and working with 1:10 liquor ratio, the consumption of water for a monthly production of 100 tons would be about 8,000 m3. The same dyeing made with treated effluent, adding approximately 10 % loss by evaporation, would spend only 88 m3, which represents a monthly saving of water around 7,912 m3. Optimization of chitosanase production by Trichoderma koningii sp. under solid-state fermentation Silva, L.C.A.; Honorato, T.L.; Franco, T.T.; Rodrigues, S. Food and Bioprocess Technology, 5 (2012), 1564-1572. ISSN: 1935-5130. FI = 2.238. Qualis B3. doi:10.1007/s11947-010-0479-1 This study aimed at the optimization of the production of chitosanase in solid culture. Trichoderma koningii sp., an entomopathogenic fungus, was used to produce chitosanase under solid-state fermentation using a mixture of wheat bran and chitosan. The incubation period, addition of moistening water and culture medium composition were optimized. The protocol to extract the enzyme was also optimized. The optimal conditions for chitosanase production by T. koningii were obtained using a mixture of 3.0 g of wheat bran and 1.5 g of chitosan, with the addition of 2.5 mL of moistening water (pH 5.5) and of 2.5 mL of saline solution (pH 5.5) containing NaNO3 (1.0 g/L), (NH4)2HPO4 (1.0 g/L), MgSO4.7H2O (1.0 g/L), and NaCl (1.0 g/L). Optimal enzyme extraction was carried out adding 20 mL of sodium acetate buffer (200 mM, pH 5.5) at 30C under orbital agitation at 150 rpm for 6 min. The optimized production yielded 4.84 IU/gds. Agosto Correlation of the physicochemical and structural properties of pDNA/cationic liposome complexes with their in vitro transfection Balbino, T.A.; Gasperini, A.A.M.; Oliveira, C.L.P.; Azzoni, A.R.; Cavalcanti, L.P.; De la Torre, L.G. Langmuir, 28 (2012), 11535-11545. ISSN: 0743-7463. FI = 4.186. Qualis A1. doi:10.1021/la302608g In this study, we characterized the conventional physicochemical properties of the complexes formed by plasmid DNA (pDNA) and cationic liposomes (CL) composed of egg phosphatidylcholine (EPC), 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE), and 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) (50/25/25% molar ratio). We found that these properties are nearly unaffected at the studied ranges when the molar charge ratio (R±) between the positive charge from the CL and negative charge from pDNA is not close to the isoneutrality region (R± = 1). However, the results from in vitro transfection of HeLa cells showed important differences when R± is varied, indicating that the relationships between the physicochemical and biological characteristics were not completely elucidated. To obtain information regarding possible liposome structural modifications, small-angle X-ray scattering (SAXS) experiments were performed as a function of R± to obtain correlations between structural, physicochemical, and transfection properties. The SAXS results revealed that pDNA/CL complexes can be described as being composed of single bilayers, double bilayers, and multiple bilayers, depending on the R± value. Interestingly, for R± = 9, 6, and 3, the system is composed of single and double bilayers, and the fraction of the latter increases with the amount of DNA (or a decreasing R±) in the system. This information is used to explain the transfection differences observed at an R± = 9 as compared to R± = 3 and 6. Close to the isoneutrality region (R± = 1.8), there was an excess of pDNA, which induced the formation of a fraction of

Boletim da FEQ Página 5aggregates with multiple bilayers. These aggregates likely provide additional resistance against the release of pDNA during the transfection phenomenon, reflected as a decrease in the transfection level. The obtained results permitted proper correlation of the physicochemical and structural properties of pDNA/CL complexes with the in vitro transfection of HeLa cells by these complexes, contributing to a better understanding of the gene delivery process. In situ synthesis, morphology, and thermal properties of polystyrene-MgAl layered double hydroxide nanocomposites Botan, R.; Nogueira, T.R.; Wypych, F.; Lona, L.M.F. Polymer Engineering and Science, 52 (2012), 1754-1760. ISSN: 0032-3888. FI = 1.302. Qualis A1. doi:10.1002/pen.23122 Polystyrene (PS)/layered double hydroxide (LDH) nanocomposites were synthesized by in situ free radical bulk polymerization. LDH formed by magnesium and aluminum (Mg:Al-molar ratio of 2:1) was prepared by coprecipitation method and intercalated with sodium dodecyl sulfate (DDS). The nanocomposites were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and flammability test. The XRD and TEM demonstrated that synthesized nanocomposites in all compositions studied showed a high global dispersion of LDH in PS, suggesting exfoliation. The results of TGAs (when 50% mass loss was selected as a comparison point) and flammability tests for synthesized nanocomposites, presented a significant improvement in thermal stability and flammability property when compared with pure PS. This behavior and properties indicate application of the surfactant intercalated LDH reinforced PS in fields where thermal stability is an important characteristic. Effect of surface properties on particle growth kinetics for polymer coating in spouted bed Braga, M.B.; Rocha, S.C.S. Materials Science Forum, 727-728 (2012), 1616-1621. ISSN: 1662-9752. Qualis B2. doi:10.4028/www.scientific.net/MSF.727-728.1616 In this research, glass beads with size range between 1.68 and 2mm were coated with 5 polymeric suspensions. The suspensions formulations differ in relation to their employment and physical properties (solids concentration, surface tension and rheology), generating different characteristics of wettability and adhesion with the nucleus. The aim of this study was to evaluate particle coating in a spouted bed through analysis of particle growth in terms of solid surface energy, wettability, and adhesion before and after the formation of the first layer of polymeric film on the particle. The solid-suspension and film-suspension systems were characterized by contact angle and surface energy. The operating conditions were fixed for all suspensions: 1.5 kg of beads, air velocity of 0.369 m/s, air temperature of 60 °C, suspension flow rate of 4 ml and atomizing pressure of 10 psig. Analyzing particle growth kinetics, different behaviors were observed and related not only to glass-suspension wettability, but also to polymeric film-suspension surface properties. Supercritical water gasification of glucose and cellulose for hydrogen and syngas production Freitas, A.C.D.; Guirardello, R. Chemical Engineering Transactions, 27 (2012), 361-366. ISSN: 1974-9791. Qualis B5. doi:10.3303/CET1227061 Interests in large scale use of biomass for energy and in hydrogen production are motivated largely by global environmental issues. Generation of hydrogen and syngas from biomass using supercritical water gasification (SCWG) is an environmentally benign method to produce energy. In the present work the Gibbs energy minimization, at constant pressure (P) and temperature (T), and entropy maximization at constant P and enthalpy (H), were utilized to calculate the equilibrium compositions and equilibrium temperatures for SCWG of glucose and cellulose. The effect of pressure, temperature and initial composition of reactants were evaluated. The problems were formulated as non-linear programs. The formulation used ensures finding the global optimal solution with no need initial estimate. The model predictions were compared with experimental and simulated data found in literature with a good agreement between them. In both SCWG processes, hydrogen production was favored in high temperatures and low molar compositions of glucose or cellulose in the feed. The effect of pressure was found to be irrelevant. Syngas with a H2/CO molar ratio close to 2 (ideal for Fischer-Tropsch synthesis applications) are obtained with an addition of CO2 as a co-reactant. The calculated final temperatures were close to the initial temperature of the reaction in both systems thus, indicating low energy requirements for maintain these reactions, and in the reaction conditions analyzed here these systems can be considered safe. Both systems showed potential for application in hydrogen and syngas production.

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Impeller characterization and selection: balancing efficient hydrodynamics with process mixing requirements Machado, M.B.; Nunhez, J.R.; Nobes, D.; Kresta, S.M. AIChE Journal, 58 (2012), 2573-2588. ISSN: 0001-1541. FI = 2.030. Qualis A1. doi:10.1002/aic.12758 Current literature relies almost exclusively on the power number to compare and characterize impellers. Industrial mixing requirements may rely on conditions far away from the impeller. A protocol is proposed to compare impellers designed for turbulent mixing on the basis of impeller hydrodynamic performance and mixing process objectives. A hydrofoil impeller (KPC), and a mixed-flow impeller (45 down-pumping PBT), each at two diameters, were used to test the protocol. Fourteen measures were considered. Five are recommended for full characterization: power number, momentum number, and peak rate of dissipation of turbulent kinetic energy to characterize conditions at the impeller; power at just-suspended speed to compare the efficiency of solids suspension at the bottom of the tank; and point of air entrainment as a measure of turbulence penetration to the free surface. These five measures provide complete information about mixing performance and good differentiation between the impellers and geometries. Continuous synthesis and in-situ monitoring of biodiesel production in different microfluidic devices Martínez-Arias, E.L.; Martins, P.F.; Jardini-Munhoz, A.L.; Gutierrez-Rivera, L.; Maciel Filho, R. Industrial & Engineering Chemistry Research, 51 (2012), 10755-10767. ISSN: 0888-5885. FI = 2.237. Qualis A1. doi:10.1021/ie300486v Currently, there is a great interest in developing new processes for continuous biodiesel synthesis in order to overcome problems imposed by biphasic reaction and thermodynamic equilibrium, as well as to reduce production costs related to the conventional batch reaction processes. The use of microreactors can significantly improve the mixing between reactants and phases, enhancing the transfer rates, and consequently, increasing biodiesel yields. Therefore, in this work, microreactors with different internal geometries have been fabricated and used for continuous production of biodiesel from castor oil and ethanol. The influences of the microchannel geometry (Tesla-, Omega-, and T-shaped) on the performance of the biodiesel synthesis were experimentally studied. Higher biodiesel yields were reached using the Tesla- and Omega- than T-shaped microchannels due to better mixture mechanism efficiency. Using a catalyst loading of 1.0 wt.% NaOH and a reaction temperature of 50C, ethyl ester conversions of 96.7%, 95.3%, and 93.5% were achieved using Tesla-, Omega-, and T-shaped microreactors, respectively. In addition, transesterification reaction in-situ monitoring by near infrared spectroscopy using fiber-optic probe was evaluated, showing that more studies must be performed in order to allow its use in on-line monitoring of continuous processes. Mathematical model of fluidization of binary mixtures of particles Mitrofanov, A.V.; Ogurtsov, A.V.; Magnitskiy, V.A.; Mizonov, V.E.; Tannous, K. Bulletin of the Ivanovo State Power University, (2012), 45-47. ISSN: 2072-2672. http://catalog.sfu-kras.ru/cgi-bin/irbis64r_91/cgiirbis_64.exe?C21COM=S&I21DBN=MARS&P21DBN=MARS&S21FMT=&S21ALL=%28%3C.%3EK%3DMATH$%3C.%3E%29&FT_REQUEST=&FT_PREFIX=&Z21ID=&S21STN=1&S21REF=&S21CNR=20 Background: Engineering calculation of f1uidized bed must be based on mathematical models of the process that takes into account all basic features of f1uidlzation on the one hand, and are simple enough o have a reasonable computational time on the other hand. These requirements can be met by the models based on the theory of Markov chains, in which transitions probabilities must be agreed with the process physics. The objective of the study is to build such a model. Materials and methods: The proposed mathematical model is based on the theory of Markov chains. A bed is presented as a chain of cells. The transition probabilities between the cells consist of probabilities of convection transitions and probabilities of diffusion transitions. The convection transition probabilities are being formed due to local porosities of particles in the cells. The diffusion transition probabilities are allowed to any cell from a given one but decrease with the distance between cells according to the normal distribution law. Results: As result, a mathematical model of f1uidization of binary par1ícle mixture is proposed. It allows calculating bed expansion and fractions content distribution over its height. The mechanism of bed expansion during fluidization is determined by relative fraction content, as well as the features of fraction concentration distribution in it that varies with a reactor profile right up to complete segregation of the fractions.

Boletim da FEQ Página 7Conclusions: The proposed model allows to describe fluidization of polydisperse material, which is basic information for modeling of mass exchange processes. Development of new systems of nano-disperse Pt-(2%Pt-Ce0.9W0.1O2)/C electrocatalysts tolerant to carbon monoxide (CO) for PEMFC anodes Nandenha, J.; Isidoro, R.A.; Dresch, M.A.; Fernandes, V.C.; Aricó, E.M.; Santiago, E.I.; Rothenberg, G.; Oliveira, W.S.; Linardi, M. ECS Transactions, 43 (2012), 185-189. ISSN: 1938-6737. Qualis B3. doi:10.1149/1.4704956 The nanophase material (powder) of Ce0.9W0.1O2 was synthesized via coprecipitation of oxalates of cerium (IV) and tungsten cations. Pt-Ce0.9W0.1O2 (2 wt% Pt) was prepared by an alcohol-reduction process using H2PtCl6.6H2O as source of Pt, Ce0.9W0.1O2 as support and ethylene glycol as solvent and reducing agent. Pt- Ce0.9W0.1O2 was physically mixed with commercial Pt/C E-TEK (20 w% Pt) to produce the Pt-(2%Pt- Ce0.9W0.1O2)/C electrocatalyst. The prepared electrocatalysts were characterized by energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and CO stripping. The performances of Pt/C E-TEK and Pt-(2%Pt- Ce0.9W0.1O2)/C electrocatalysts were tested in single fuel cell fed with a mixture H2/CO (100 ppm of CO). The results showed that the mixture of 2%Pt- Ce0.9W0.1O2 and Pt/C E-TEK increases the CO tolerance in a single fuel cell operating at 85 ºC compared with Pt/C E-TEK. Estudo da secagem da biomassa de banana verde em spray dryer Oi, R.K.; Tambourgi, E.B.; Moraes Jr., D. Engevista, 14 (2012), 165-171. ISSN: 1415-7314. Qualis B2. http://www.uff.br/engevista/seer/index.php/engevista/article/view/345/199 The green banana biomass is a component that can be industrially applied to a wide variety offoods because do not interfere in the sensory attributes of other ingredients present and has functional properties, especially the presence of resistant starch. This use can be expanded, including for export, if this product be produced in powder form. This research presents a feasibility study of drying green banana biomass in a non-commercial (experimental) of spray dryer with rotary atomizer. The variables selected in the experimental procedure were: atomizer rotation; biomass temperature and biomass flow. It was defined as response the mass and the moisture content of the product. These variables had two levels of variation, which corresponded to the completion of eight tests. Among the variables used in the tests, the atomizer rotation was the most significant to response of mass and moisture content, the others showed low effects. In this study it was proved the feasibility of drying the green banana biomass in a spray dryer with rotary atomizer. Evaluation of TiO2, ZnO, CuO and Ga2O3 on the photocatalytic degradation of phenol using an annular-flow photocatalytic reactor Paschoalino, F.C.S.; Paschoalino, M.P.; Jordão, E.; Jardim, W.F. Open Journal of Physical Chemistry, 2 (2012), 135-140. ISSN: 2162-1977. doi:10.4236/ojpc.2012.23018 Even with rigorous environmental regulations, phenol still is a major contaminant. One possible solution is the use of heterogeneous photocatalysis due to low chemical addition, feasibility and reliability to be implanted on cost-effective industrial process. TiO2 is the most employed photocatalyst because of its favorable (photo) chemical properties and ZnO is considered one of the best alternatives for that. Other oxides were tested in lesser proportions, like CuO and Ga2O3. When the photocatalyst is dispersed as slurry, higher degradation rates are achieved due to high solid to liquid contact area when compared with supported form. The aim of this work was to develop a batch recirculating photocatalytic reactor and evaluate its efficiency when assisted by the photocatalysts TiO2 P25, ZnO, CuO and β-Ga2O3. TiO2 achieved 95% mineralization after 200 min reaction in an average degradation rate of 0.68 mg·L﹣1·min﹣1 and ZnO was less efficient (0.41 mg·L﹣1·min﹣1). Ga2O3 and CuO presented poor performance, mainly due to low surface area for the CuO syntesized and the absorption of the UV radiation by the reactor walls, decreasing Ga2O3 activity. Degradation intermediates were detected in diverse concentrations and at different operational times for each oxide tested, which indicate different degradation mechanisms. A pH/enzyme-responsive polymer film consisting of Eudragit® FS 30 D and arabinoxylane as a potential material formulation for colon-specific drug delivery system Rabito, M.F.; Reis, A.V.; Freitas, A.R.; Tambourgi, E.B.; Cavalcanti,O.A. Pharmaceutical Development and Technology, 17 (2012), 429-436. ISSN: 1083-7450. FI = 1.107. doi:10.3109/10837450.2010.546409 Polymer film based on pH-dependent Eudragit® FS 30 D acrylic polymer in association with arabinoxylane, a polysaccharide issued from gum psyllium, was produced by way of solvent casting. Physical-chemical

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characterization of the polymer film samples was performed by means of thermogravimetry (TGA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). Furthermore, water-equilibrium swelling index (Is) and weight loss of the films in KCl buffer solution of pH 1.2, in KH2PO4 buffer solution of pH 5.0, or in KH2PO4 buffer solution of pH 5.0 consisting of 4% enzyme Pectinex® 3X-L (w/v) were also carried out for the film characterization. No chemical interactions between the Eudragit® FS 30 D and the arabinoxylane polymer chains were evidenced, thus suggesting that the film-forming polymer structure was obtained from a physical mixture of both polymers. The arabinoxylane-loader films showed a more pronounced weight loss after their immersion in buffer solution containing enzyme Pectinex® 3X-L. The introduction of the arabinoxylane makes the film more susceptible to undergo an enzymatic degradation. This meant that the enzyme-dependent propriety issued from the arabinoxylane has been imprinted into the film formulation. This type of polymer film is an interesting system for applications in colon-specific drug delivery system. Optimizing SLN and NLC by 22 full factorial design: effect of homogenization technique Severino, P.; Santana, M.H.A.; Souto, E.B. Materials Science and Engineering C, 32 (2012), 1375-1379. ISSN: 0928-4931. FI = 2.178. Qualis A1. doi:10.1016/j.msec.2012.04.017 Solid lipid nanoparticles (SLN) and nanostructured lipid carrier (NLC) have been employed in pharmaceutics and biomedical formulations. The present study focuses on the optimization of the production process of SLN and NLC by High Shear Homogenization (HSH) and High Pressure Homogenization (HPH). To build up the surface response charts, a 22 full factorial design based on 2 independent variables was used to obtain an optimized formulation. The effects of the production process on the mean particle size, polydispersity index (PI) and zeta potential (ZP) were investigated. Optimized SLN were produced applying 20,000 rpm HSH and 500 bar HPH pressure and NLC process 15,000 rpm HSH and 700 bar HPH pressure, respectively. This factorial design study has proven to be a useful tool in optimizing SLN (~100 nm) and NLC (~300 nm) formulations. The present results highlight the benefit of applying statistical designs in the preparation of lipid nanoparticles. Saving energy using fuzzy control applied to a chiller: an experimental study Silva, F.V.; Schmitz, J.E.; Neves Filho, L.C.; Fileti, A.M.F.; Silveira Jr. V. Clean Technologies and Environmental Policy, 4 (2012), 535-542. ISSN: 1618-954X. FI = 1.120. doi:10.1007/s10098-011-0409-6 In this study the energy consumption of a chiller system, under different configurations and control strategies, was investigated. Two control strategies (Proportional integral—PI and fuzzy-PI) were applied to regulate the temperature of propylene glycol solution and the evaporating temperature using compressor motor supply frequency and pump rotation frequency as manipulated variables. The experiments were initiated with the system in open loop. When the steady-state condition was reached the system was submitted to a positive disturbance in its heat load and the feedback control was activated. Hence, the results were analyzed by means of integral of the time-weighted absolute error (ITAE) criterion and total energy consumption. The analysis of experimental results showed that both controllers were able to regulate the controlled variables appropriately. Also, it was verified that the use of the compressor motor supply frequency as manipulated variable can smooth out process variable oscillations. Besides, comparing the energy demands of both controllers, it was observed that the fuzzy-PI controller required 3.4% less electric energy (0.81 kWh). Considering the propylene glycol solution temperature (secondary fluid) as controlled variable and compressor motor supply frequency as manipulated variable, fuzzy-PI control achieves smaller ITAE index value, and energy consumption than the PI counterpart, consuming 0.25 kWh less energy. Thus, energy savings could be attained for control configurations that exhibit higher ITAE values. It was demonstrated that is desirable to include the energy consumption as a control performance parameter in order to increase the energetic efficiency of process. Setembro Experimental investigation of 3D velocity by tomographic particle image velocimetry (Tomo-PIV) in a short riser section Amaral, R.L.; Castilho, G.J.; Cremasco, M.A. Procedia Engineering, 42 (2012), 748-754. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.461 The measurement of instantaneous velocity field with high spatial resolution makes the Tomo-PIV (tomographic particle image velocimetry) technique attractive for the study of complex flows in

Boletim da FEQ Página 9circulating beds. The Tomo-PIV technique is employed for obtaining the velocity field of the fluid phase in three dimensions using tracer particles which follow the fluid. They are immersed in the fluid and illuminated by a source of pulsed light (laser) within a three-dimensional region. Images of the particles are recorded in the focus of several viewing directions using CCD (Charge-Coupled Device) sensors. The distribution of light intensity is discretized into a 3D array of voxels and then analyzed by interrogation of cross-correlation in three dimensions. The information field is returned in the form of instantaneous velocities of the measurement volume. This paper aims to present an experimental setup for an initial investigation of the velocity field of the particulate phase of a riser section of a circulating bed. The calibration errors were between 0.209 and 0.066 pixels and after the self-calibration errors were below 0.097 pixels. The volume investigated was 82 x 100 x 10 mm3 with a resolution of 1571 x 897 x 113 voxels. The reconstructed volumes were processed using 3D cross-correlation with a volume interrogation size of 110 voxels decreasing to a final size of 16 voxels with a 75% overlap between adjacent interrogation volumes. The velocity field produced has 224 x 393 x 28 voxels. Comparison of the properties of compacted and porous lamellar chitosan–xanthan membranes as dressings and scaffolds for the treatment of skin lesions Bellini, M.Z.; Pires, A.L.R.; Vasconcelos, M.O.; Moraes, A.M. Journal of Applied Polymer Science, 125 (2012), E421-E431. ISSN: 0021-8995. FI = 1.240. Qualis A1. doi:10.1002/app.36693 Compacted and porous lamellar membranes of xanthan (Xn) and chitosan (Ch) at mass ratios of 1:1 and 1.2:0.8 were prepared and tested to verify possible applications in the treatment of skin lesions. All membranes were prepared by complexation of the polysaccharides in solution and subsequent casting. The porous membranes were obtained by adding either Tween 80 or Pluronic F68 to the polysaccharide complexes before casting. Membranes prepared in the absence of surfactants at a mass ratio of Xn to Ch of 1:1 proved ideal for use as wound dressings, as they were thin (around 0.10 mm in thickness) and transparent and had low in vitro cytotoxicity to L929 cells, a tensile strength at break of 25 MPa, water absorption after 24 h of around 86 g/g and simulated body fluid absorption of 16% and adequate stability in the presence of the same solutions. Membranes prepared at the mass ratio of Xn to Ch of 1 : 1 in the presence of Pluronic F68 showed the most favorable characteristics for application as scaffolds for tissue engineering. These membranes consisted of a matrix with interconnected pores which were distributed homogeneously throughout the structure and had a thickness of 1.84 mm, high capacity for FBS uptake (around 18 g/g) and cell culture medium uptake (8.6 g/g), a loss of mass in the culture medium of 33% after 144 h, and low in vitro toxicity to L929 cells. In conclusion, membranes of Ch and Xn produced in the presence or absence of the surfactant Pluronic F68 have a high potential for use as scaffolds in tissue engineering or as dermal dressings, respectively, whereas in contrast, membranes prepared in the presence of Tween 80, regardless of the mass ratio of Xn to Ch, were very cytotoxic to L929 cells and therefore were not appropriate for any of the proposed applications. Characterization of the stearin obtained by thermal fractionation of anhydrous milk fat Bonomi, E.C.; Luccas, V.; Kieckbusch, T.G. Procedia Engineering, 42 (2012), 1004-1009. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.484 Thermal fractionation of anhydrous milk fat with high initial content of low molecular weight TAGs was performed based on a 22 factorial experimental design with three central and two axial points. The independent variables were the crystallization temperature and the cooling rate. A 2.0 L agitated glass reactor was used and the rotation was kept at 20 rpm. The filtration was performed under vacuum (500 mmHg), using a 14 µm average pore diameter filter paper. Curves of isothermal crystallization of the stearin fraction showed that increasing the crystallization temperature, increases the induction period and decreases the maximum solid content of stearin. An increase of the crystallization temperature resulted in an increase in solid fat content. All runs achieved an efficient fractionation using a single separation step and stearin with defined characteristics can be obtained adapting the process conditions. Comparison of downer and riser flows in a circulating bed by means of optical fiber probe signals measurements Castilho, G.J.; Cremasco, M.A. Procedia Engineering, 42 (2012), 326-333. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.420 In this work, the riser (2.42 m high) and downer (0,85 m high) sections with an ID of 82 mm in both, were analyzed to study the temporal fluid dynamics properties of a circulating bed system in terms of electrical signals of particles concentration obtained by an optical fiber probe. Experiments were conducted using

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ambient air as the fluid phase and FCC (fluid catalytic cracking) particles as the solid phase. The measurements with the optical fiber probe were conducted in the inlet and outlet zones of both riser and downer. Signals were evaluated in the phase space (chaos analysis), by reconstructing the attractors and calculating the Kolmogorov entropy and the correlation dimension. Results show that the downer presents a less chaotic flow, with lower values of Kolmogorov entropy and correlation dimension, compared to the riser. In the entrance of the downer, the flow is less complex and more predictable in the center due to the effect of the solid feeder. The flow develops in direction of the exit zone and at that position there is no much difference in complexity between the central and wall. In the case of the riser, at the entrance effect is caused by a question of configuration, due to a presence of a curve, making the solid concentration increase toward the wall. In the exit zone, the flow suffers the effect of the abrupt exit. Mechanical and biological performances of new scaffolds made of collagen hydrogels and fibroin microfibers for vascular tissue engineering De Moraes, M.A.; Paternotte, E.; Mantovani, D.; Beppu, M.M. Macromolecular Bioscience, 12 (2012), 1253-1264. ISSN: 1616-5195. doi:10.1002/mabi.201200060 A microstructured composite material made of collagen hydrogel (matrix) and silk fibroin microfibers (randomly oriented reinforcing fibers) is investigated in order to conjugate the mechanical resistance of fibroin with the suitable biological performance of collagen to design new scaffolds for vascular tissue engineering. Results show that fibroin microfibers and collagen fibrils have suitable interfacial adhesion, and the scaffold exhibits improved mechanical properties if compared with a pure collagen hydrogel. Furthermore, the overall biological performance is improved. Improvements on anhydrous ethanol production by extractive distillation using ionic liquid as solvent Figueroa, J.J.; Lunelli, B.H.; Maciel Filho, R.; Wolf Maciel, M.R. Procedia Engineering, 42 (2012), 1114-1124. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.493 Biorefineries use a variety of separation methods in order to produce high value co-products from different feed streams. The ionic liquids (IL) represent new classes of non-volatile selective solvents with large solubility, low solution viscosities, low toxicity. In this work, a computational study on extractive distillation using ionic liquids aiming to improve the properties of separation and lower energy consumption compared to conventional extraction agents, showing significant potential for this application, was developed. The ternary vapor liquid equilibrium data were taken from literature and the process was modeled and simulated using Aspen Plus TM process simulation environment. Computed results showed that 1-butyl-3-methylimidazolium methyl sulfate ([bmim][mSO4]) consumes lesser energy per kilogram of anhydrous ethanol, obtaining an ethanol purity of 0.995 (in mass) and an ethanol percentage recovery of 99.9 wt%. Water absorbing material to removal water from biodiesel and diesel Fregolente, P.B.L.; Wolf Maciel, M.R. Procedia Engineering, 42 (2012), 2170-2175. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.594 In this work, hydrogel of polyacrylamide (PAAm) was obtained by free radical polymerization of acrylamide (AAm) in the presence of N,N’-methylenebisacry1amide (MBAAm), in aqueous media. The hydrogels were cut and dried before to be used in saturated fuels. Saturated blends of biodiesel and diesel were mixed in appropriate amounts to form B0 (0% biodiesel and 100% diesel by volume), B20, B40, B60 and B100. A large study was done to synthesize an absorbing material to have appropriated characteristics to be used as water absorbing of fuel samples. The most suitable material must present high swelling ratio combined with an enough density of cross-linked structure that enables handling the material. The dried hydrogels were added to the saturated biodiesel, diesel and blends. The results showed that, for saturated diesel (B0), the water content was reduced down to 85 ppm from 220 ppm (reduction of 60% of water content). The reductions of water content for B20, B40 and B60 were 58, 57 and 64%, respectively, after 240 min of treatment with hydrogel. Oxidative reforming of methane for hydrogen and synthesis gas production: Thermodynamic equilibrium analysis Freitas, A.C.D.; Guirardello, R. Journal of Natural Gas Chemistry, 21 (2012), 571-580. ISSN: 1003-9953. FI = 1.348. Qualis B1. doi:10.1016/S1003-9953(11)60406-4 A thermodynamic analysis of methane oxidative reforming was carried out by Gibbs energy minimization (at constant pressure and temperature) and entropy maximization (at constant pressure and enthalpy)

Boletim da FEQ Página 11methods, to determine the equilibrium compositions and equilibrium temperatures, respectively. Both cases were treated as optimization problems (non-linear programming formulation). The GAMS® 23.1 software and the CONOPT2 solver were used in the resolution of the proposed problems. The hydrogen and syngas production were favored at high temperatures and low pressures, and thus the oxygen to methane molar ratio (O2/CH4) was the dominant factor to control the composition of the product formed. For O2/CH4 molar ratios higher than 0.5, the oxidative reforming of methane presented autothermal behavior in the case of either utilizing O2 or air as oxidant agent, but oxidation reaction with air possessed the advantage of avoiding peak temperatures in the system, due to change in the heat capacity of the system caused by the addition of nitrogen. The calculated results were compared with previously published experimental and simulated data with a good agreement between them. Effects of organoclay mixture on tyhe rhological properties of ABS-clay nanocomposites Galvan, D.; Carneiro, F.; Mazzucco, M.; Bartoli, J.R.; d’Ávila, M.A.; Morales, A.R.; Fernandes, E.G. Macromolecular Symposia, 319 (2012), 167-172. ISSN: 1521-3900. Qualis B3. doi:10.1002/masy.201100165 In this work, poly(acrylonotrile-butadiene-styrene) (ABS) and different organically modified montmorillonite clay nanocomposites were prepared by melt intercalation in a co-rotating twin screw extruder. The influence of the torque during processing of the mixture of the modified organoclays in the intercalation/exfoliation of the clay in the polymeric matrix was evaluated through low angle X-ray diffraction and capillary and parallel-plate rheometry. Estimation hydrodynamic parameters and mass transfer in a stirred airlift bioreactor using viscous fluids Jesus, S.S.; Martínez-Arias, E.L.; Santana, A.; Maciel Filho, R. New Biotechnology, 29 (2012), S213. ISSN: 1871-6784. FI = 2.756. Qualis B1. doi:10.1016/j.nbt.2012.08.597 Bioreactors airlift have been constructed for use in a variety of the biotechnological process such as biochemical fermentation and biological wasterwater treatment. The aims of work are the design and construction of a mechanically agitated bioreactor airlift, as well as, to perform studies with highly viscous fluids. The stirred airlift bioreactor was designed in glass with internal recirculation (a concentric draft-tube airlift vessel device); the agitation is carried out through a turbine impeller located above the gas sparger in the riser region. The gas holdup and volumetric oxygen transfer coefficient (kLa) were evaluated in order to achieve a better comprehension of the hydrodynamic and mass transfer. Air under different velocities was sparged inside the bioreactor. Glycerol 25% and CMC 1.94% were used in this work as fluid model to check the efficiency of this bioreactor. The gas holdup in the riser (ɛR) and downcomer (ɛD) for the experiments was successfully correlated with dimensionless numbers, namely, the Sherwood number (Sh) and Froude number (Fr). The correlations relating kLa to superficial gas velocity (UGR) and kinematic viscosity (υ) agree well with experimental data. In addition, the results showed that the stirred airlift bioreactor is suitable for handling viscous liquids such as those frequently used in fermentation process that require good oxygen transfer. Extension of the TBP curve of petroleum using the correlation DESTMOL Lopes, M.S.; Lopes, M.S.; Maciel Filho, R.; Wolf Maciel, M.R.; Medina, L.C. Procedia Engineering, 42 (2012), 791-798. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.465 The properties of natural petroleum and petroleum products make use of the True Boiling Point (TBP) distillation analysis and it has been proved to be very useful for petroleum characterization and design and operation of refinery units. So, the TBP distillation analysis has contributed to the petroleum science and technology, to the classification of petroleum, to the development of petroleum property correlations and it has been used worldwide. However, when applied to heavy petroleum fractions, difficulties are often encountered. Through petroleum distillation curve (TBP), it is possible to evaluate the yields of the products that will be obtained in the refineries, as well as to establish operational strategies and process optimizations, as the cracking process. The TBP curve is very important for the oil industry and is used to understand the behavior of oil before distillation. For when the oil is subjected to a distillation tower on an industrial scale is already known about the percentage of distillate obtained working at a specific temperature. In the oil refining industry as the distillations follow: Atmospheric Distillation (distillation up to 673 K - ASTM D 2892) and vacuum distillation (distillation to 838K - ASTM D 5236). This work creates the possibility of extending the temperature range of distillation of oil to 973K. The goal of this work is extend the TBP by DESTMOL, the extension of the TBP curve oil reaching approximately 973 K exceeding the curves generated so far that reach only 838 K. The DESTMOL correlation applies pretty good showing

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continuity and asymptotic profile of the TBP curve. The results help to meet the waste oil and can thus use the waste for more noble ends. As the result of DESTMOL, we can better define the strategies and operating conditions for oil processing, achieving better economic results in the use of heavy oil, due to its better characterization. Cracking of petroleum residues by reactive molecular distillation Lopes, M.S.; Lopes, M.S.; Maciel Filho, R.; Wolf Maciel, M.R.; Medina, L.C. Procedia Engineering, 42 (2012), 363-369. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.424 It is known that the Brazilian oils are more heavy -super heavy -viscous, its operation is difficult, especially its production, including all stages -elevation, runoff and primary processing -in addition to their transfer, and refining itself. Studies indicate the existence of oil fields as heavy lifting and that the simple flow of the base of the pit to the surface seems impossible at first sight, especially in off-shore fields, compromising both technically and economically a project to produce a new field. Therefore, efforts are needed to develop alternatives aimed at reducing the API gravity, viscosity and sulfur content of extra-heavy oil, adding a higher commercial value for these oils. This work aims to study, propose and develop enhanced hybrid process that transforms the extra-heavy oil, or part thereof, in lighter crude oil to generate a mixture: lower sulfur content, lower density, lower viscosity, lower content of volatile (aromatics and asphaltenes), greater resistance to the processes of purification. The process studied is the Reactive molecular distillation with the addition of tetralin that suffer from high temperature cracking of molecules, providing protons that help the breakdown of asphaltenes and residues will suffer as a consequence physicochemical changes, such as those mentioned above. This way you can improve the problems associated with the deposition of asphaltenes at high temperatures. The conversion of light with immediate reduction of API gravity and sulfur content promoted a better use of extra-heavy oil and the DMR is a product of high-value oil and very interesting for the oil industry and the environment. The experimental work proposed in this study was conducted to cracking and separation of fractions and petroleum. The evaluation and characterization of the cracking results were obtained after analysis of properties such as density, viscosity, sulfur content, molar mass and mass balance of the currents. Poly (lactic acid) production for tissue engineering applications Lopes, M.S.; Jardini, A.L.; Maciel Filho, R. Procedia Engineering, 42 (2012), 1530-1542. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.534 Tissue engineering is the most fascinating domain of medical technology and has emerged as a promising alternative approach in the treatment of malfunctioning or lost organs where patients are treated by using their own cells, grown on a polymer support so that a tissue part is regenerated from the natural cells. This support is known as scaffold and is needed to serve as an adhesive substrate for the implanted cells and a physical support to guide the formation of the new organs. In addition to facilitating cell adhesion, promoting cell growth, and allowing the retention of differentiated cell functions, the scaffold should be biocompatible, biodegradable, highly porous with a large surface/volume ratio, mechanically strong, and malleable. The scaffold degrades while a new organ or tissue is formed. A number of three-dimensional porous scaffolds fabricated from various kinds of biodegradable materials have been developed. Bioabsorbable polymers have been identified as alternative materials for biomedical applications, since these polymers are degraded by simple hydrolysis to products that can be metabolized by the human body. With their excellent biocompatibility, poly-lactones such as poly-lactic acid (PLA), poly-glycolic acid (PGA), and poly-caprolactone (PCL), as well as their copolymers are becoming the most commonly used synthetic biodegradable polymers as fixation devices materials for biomedical devices. Among the biomaterials (biopolymers) used in the medical field, the poly (lactic acid) (PLA) has received significant attention. Poly-lactic acid (PLA) is at present one of the most promising biodegradable polymers for this purpose and has convincingly demonstrated the proof of concept for using in bioabsorbable polymer as bone fixation devices, owing to its mechanical property profile, thermoplastic possibility and biological properties, such as biocompatibility and biodegradability. It is produced from lactic acid, a naturally occurring organic acid that can be produced by fermentation. The objective of this study was to investigate the synthesis of PLA in a laboratory scale in order to characterize it in accordance with the needs for biomedical use.

Boletim da FEQ Página 13 Thermodynamic performance investigation of a trigeneration cycle considering the influence of operational variables Martins, L.N.; Fábrega, F.M.; d’Angelo, J.V.H. Procedia Engineering, 42 (2012), 2061-2070. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.584 A rational use of fossil fuels together with a growing concerning about environmental issues have led to many researches aiming at an improvement of energy systems performance, trying to develop more economical and also more eco-friendly solutions. A cogeneration system (Combined Heat and Power - CHP) is an alternative technique that produces heat and power consuming less of primary energy sources, especially fossil fuels. Recently trigeneration systems, also named Combined Heat, Cooling and Power (CHCP), have gained great interest for industrial and commercial applications, due to a better energetic efficiency when compared with CHP systems. CHCP is an economical and available technology, demanding a single source of primary energy, with the advantages of saving energy, money, and making a clever user of fossil fuels with benefits to the environment. The main objective of this work is to evaluate the thermodynamic performance of a trigeneration system, using a process simulation software, considering the influence of some operational variables: compression ratio in the compressor, expansion ratio and efficiency of the power cycle turbine; boiler operation pressure; and operational pressure of the absorption cycle in both sides (high and low pressure). Natural gas is used as primary energy source. In the absorption refrigeration cycle the pair solvent-refrigerant used is H2O-NH3. For the base case studied total thermal efficiency was 78% and COP of the absorption refrigeration cycle was 0.57, while for the optimized case these values are 82% and 0.48. The most important operational variables to improve efficiency of the cycle are compressor ratio in the compressor and expansion ratio in the turbine. Evaluation of methyl chavicol concentration by different evaporation processes using central composite experimental design Martins, P.F.; Carmona, C.; Martínez-Arias, E.L.; Sbaite, P.; Maciel Filho, R.; Wolf Maciel, M.R. Separation and Purification Technology, 98 (2012), 464-471. ISSN: 1383-5866. FI = 2.921. Qualis A1. doi:10.1016/j.seppur.2012.08.009 This work describes methyl chavicol enrichment from basil essential oil by wiped film evaporation (WFE) and compares its performance with published data obtained by short path evaporation (SPE). The main difference between these processes is that the WFE presents an external condenser, while the SPE uses an internal one. The evaporation processes comparison was performed based on methyl chavicol concentration level and amount of produced material. Through central composite experimental design, the influences of evaporator temperature, condenser temperature, and feed flow rate on distilled percentage and methyl chavicol concentration at the residue stream were studied. Response surface methodology based on five level-three variable was used to describe the individual and interactive effects between factors on the process. From experimental data, models were built up to describe distilled percentage and methyl concentration at the residue stream in function of operating conditions. Results showed that, in the studied range, similar methyl chavicol concentration (near to 89%) was reached using both WFE and SPE processes, however, at different operating conditions. While higher concentrations of methyl chavicol were obtained at 28C and 0.133 kPa using WFE, similar methyl chavicol content was obtained at 70°C and 1.33 kPa using SPE. However, WFE presented higher separation efficiency because, although similar concentration levels were reached using both equipments, the amount of produced material in the residue stream was 10% higher in WFE. Effect of operating conditions for methyl chavicol separation using a hybrid evaporation system Martins, P.F.; Martínez, E.L.; Sbaite, P.; Maciel Filho, R. Wolf Maciel, M.R. Procedia Engineering, 42 (2012), 548-558. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.442 The benefits promoted by natural products on human health have motivated industry to search for alternative separation systems in order to purify active compounds present in renewable sources. Amongst natural products of current interest for food, pharmaceutical, cosmetic, and chemical industries is methyl chavicol (MC). MC is a natural ingredient found in several herbs as tarragon, sweet basil, sweet fennel, and their essential oils, and its widest application is in food industry as flavoring agent. In this work, basil essential oil was used as raw material to study MC concentration through a hybrid evaporation system. The evaporative system was constituted of a cylindrical evaporator, an internal condenser located concentrically to the evaporator, and an external condenser. It generates 3 outside streams: distilled, side, and residue, which were recovered at the bottom of external condenser, internal condenser, and

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evaporator, respectively. From experimental results, it was verified that higher MC concentration was reached at the side stream because its intermediate volatility when compared with other substances present in basil essential oil. Central composite experimental design using 2 factors and 4 replicates at central point was considered in this work to determine the effect of operating conditions on methyl chavicol separation. Response variables were methyl chavicol concentration (%MCside) at side stream, distilled (%D) and side (%S) streams amounts. The factors studied in this work were: evaporator temperature (Tevap) and feed flow rate (FFR). Analyzing the variables effects, two variables presented a statistically significant effect on distilled percentage: evaporator temperature and feed flow rate. For the side stream, the variables: evaporator temperature, feed flow rate, and the interaction between evaporator stream and feed flow rate influenced the side amount and methyl chavicol concentration. Organophilic bentonites based on Argentinean and Brazilian bentonites. Part 1. Influence of intrinsic properties of sodium bentonites on the final properties of organophilic bentonites prepared by solid-liquid and semisolid reactions Paiva, L.B.; Morales, A.R. Brazilian Journal of Chemical Engineering, 29 (2012), 525-536. ISSN: 0104-6632. FI = 0.811. Qualis A2. doi:10.1590/S0104-66322012000300010 This study describes the influence of the intrinsic properties of raw materials on the organophilization of bentonites from Argentinean raw sodium bentonites and Brazilian sodium activated bentonites. The organophilization was done with two methodologies: solid-liquid and semisolid reactions. Correlations between the properties of sodium and organophilic bentonites were established. The effectiveness of the treatments was verified by X-ray diffraction, swelling capacity in water and xylene and SEM to evaluate the morphology of the particles. The analysis was done before and after the modification process. The bentonites had organic cations intercalated, as shown by the increase of the basal spacings, and the organophilic character was confirmed because the bentonites showed xylene swelling capacity and particles with an expanded aspect in comparison to those of the sodium bentonites. Both methodologies were efficient to obtain organophilic clays. The organophilic bentonites obtained from raw sodium bentonites gave better results. Agglomeration of sodium bicarbonate in vibrofluidized bed: process analysis and evaluation of CO2 release Rocha, S.C.S.; Nunes, J.F. Drying Technology, 30 (2012), ISSN: 0737-3937. FI = 2.084. Qualis A1. doi:10.1080/07373937.2012.689403 Agglomeration of sodium bicarbonate in a vibrofluidized bed using an aqueous polymeric suspension as binding agent was studied to determine the effects of vibration parameters (amplitude and frequency) and drying air temperature on process performance and product quality. Product quality was evaluated by determination and comparison of CO2 release from agglomerated and raw sodium bicarbonate. An experimental design was developed for the process analysis. Amplitude and frequency of vibration and air temperature were analyzed as independent variables and the response for process evaluation was the particle growth, which is related to the particle protection. Analyses of CO2 release were made for the agglomerates stored under different environments of controlled relative humidity and temperatures, week by week, during 4 weeks. Also, vapor adsorption isotherms at 25C were obtained, which showed changes in the sodium bicarbonate hygroscopic characteristics after agglomeration. Response surface methodology to supercritical carbon dioxide extraction of lipids from Botryococcus Braunii for biodiesel production Santana, A.; Jesus, S.S.; Larrayoz, M.A.; Maciel Filho, R. New Biotechnology, 29 (2012), S37. ISSN: 1871-6784. FI = 2.756. Qualis B1. doi:10.1016/j.nbt.2012.08.101 Biodiesel is considered as a renewable fuel because it can be obtained from the transformation of vegetable oils, cooking greases or animal fats. Currently, oleaginous plants like rapeseed, sunflower, palm oil and soybean are the most important sources of biodiesel. However, the productivity of some of these crops is considered relatively low and they require long extension of lands. In this context, microalgae has been emerged as a source of natural oil due to its lipids, starch and hydrocarbon contents. Supercritical carbon dioxide extraction of oil from microalgae was performed in the present research. Response surface methodology was employed to investigate the effects of operating conditions and predict the optimal conditions for supercritical carbon dioxide extraction of oil from Botryococcus Braunii. The ranges of the factors investigated were 50–80C for the operating temperature (X1), 250–350 bar for the operating pressure (X2), and 8–20 min for the extraction time (X3). The statistical analysis of the experiment

Boletim da FEQ Página 15indicated that pressure, extraction time, and the interaction between temperature and pressure (X1X2) had significant effect on oil yield. The central composite design showed that polynomial regression models were in good agreement with the experimental results with the coefficients of determination of 0.919 for oil yield. From the response surface model, an optimal condition for oil content within the range of experimental study was found to be at 60C, 275 bar, and 15 min, which gave the oil yield of 28.4 mg/g dry wt. Supercritical carbon dioxide extraction of algal lipids for the biodiesel production Santana, A.; Jesus, S.S.; Larrayoz, M.A.; Maciel Filho, R. Procedia Engineering, 42 (2012), 1927-1933. ISSN: 1877-7058. Qualis B4. doi:10.1016/j.proeng.2012.07.569 Biodiesel production from algae is a promising technique. Microalgae are able to accumulate fatty acids up to 50% of their dry weight when submitted to nitrogen defaults. They are then expected to be a new potential renewable source of biodiesel. Efficiently extracting algae oil from microalgae plays an important role in the development of microalgae biofuel. Algae bio-oil is traditionally obtained using thermal liquefaction or pyrolysis, and they may be obtained after an extraction using organic solvents as hexane. Such methods have some drawbacks like inherent toxicity, poor selectivity, difficult separation of the contaminants as well as solvents from the desired product, energy consuming and pollutant. Supercritical carbon dioxide extraction is a promising green technology that can potentially displace the use of traditional organic solvents for lipid extraction. The supercritical fluid extraction has several advantages when compared to traditional extraction method (hexane, petroleum ether, chloroform/ethanol) used for obtaining lipids from algae, in which supercritical extraction provide higher selectivities, shorter extraction time and do not use toxic organic solvents. This study examines the performance of supercritical carbon dioxide extraction of lipids from Botryococcus braunii for biodiesel production. The experiments were conducted at temperatures of 50 – 80C, pressure from 200 to 250 bar. The evolution of the process was followed by gas chromatography, determining the concentration of the fatty acids at different reaction times. For supercritical carbon dioxide extraction, lipid yield was found to decrease with temperature and to increase with pressure. Relatively high recovery of polyunsaturated fatty acids and essential fatty acids in supercritical fluid extracted algal lipids were observed. The optimum operating conditions for a supercritical extraction were pressure between 220-250 bar and temperature of 50C. This research is part of a wider experimental project involving the supercritical carbon dioxide extraction of lipids from microalgae to contribute to the development of algal lipids into a variable energy source by optimizing lipid extraction techniques for efficiency, sustainability, decreased hazard, and selectivity, focusing on the use of supercritical fluids as alternative green solvents. Área superficial e porosidade da fibra alimentar do albedo de laranja Santana, M.F.S.; Katekawa, M.E.; Tannous, K.; Lima, A.K.V.O.; Gasparetto, C.A. Revista Brasileira de Produtos Agroindustriais, 14 (2012), 261-273. ISSN: 1517-8595. Qualis B3. http://www.deag.ufcg.edu.br/rbpa/rev143/Art1439.pdf As fibras alimentares são obtidas de vários vegetais e são consumidas na forma natural ou adicionadas na composição de alimentos industrializados, na forma de pó, com fins de alterar suas propriedades nutricionais e tecnológicas. Relevantes características físicas dos materiais particulados são: a área superficial e, tamanho e distribuição de poros. Estas características foram estudadas para fibra alimentar do albedo da laranja, desidratada por liofilização e secador de leito fixo, estando separadas em três intervalos granulométricos de 0,420 a 0,150 mm. As características da superfície das partículas foram investigadas usando adsorção de nitrogênio a baixa temperatura. A área superficial específica, volume e diâmetro médio de mesoporo foram determinados empregando o método BET (Brunauer, Emmett and Teller) a área superficial acumulativa, volume, diâmetro médio e distribuição de poros, usando o método BJH (Barret, Joyner and Halenda). Verificou-se que diferentes métodos de secagem e tamanhos das partículas promoveram diferenças significativas nas propriedades físicas da fibra. Study of the interfacial forces and turbulence models in a bubble column Silva, M.K.; d’Ávila, M.A.; Mori, M. Computers & Chemical Engineering, 44 (2012), 34-44. ISSN: 0098-1354. FI = 2.072. Qualis A1. doi:10.1016/j.compchemeng.2012.04.007 Three-dimensional Eulerian simulations of gas-liquid flows in a cylindrical bubble column were performed in order to evaluate the flow pattern in the heterogeneous flow regime. Simulations were conducted numerically by the finite element method using a commercial CFX code (v.12.0) and an analysis of

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interfacial forces such as drag, lift and turbulent dispersion, as well as a comparison of k- and Reynolds Stress (RSM) turbulence models were performed. Different bubble sizes and two boundary conditions for the column exit were also verified. Gas velocities and holdup profiles were compared with experimental data. Results have shown that at the sparger region and without any simplification on the boundary condition the RSM model better represents the flow. At the fully developed region k- also showed good results. Characterization and use of in natura and calcined rice husks for biosorption of heavy metals ions from aqueous effluents Vieira, M.G.A.; Almeida Neto, A.F.; Silva, M.G.C.; Nóbrega, C.C.; Melo Filho, A.A. Brazilian Journal of Chemical Engineering, 29 (2012), 619-633. ISSN: 0104-6632. FI = 0.811. Qualis A2. doi:10.1590/S0104-66322012000300019 Heavy metal removal by adsorption using rice husks as a bioadsorbent was evaluated as an alternative for wastewater treatment. Batch equilibrium experiments and kinetic sorption studies were performed using monocomponent solutions of Ni(II), Cd(II), Zn(II), Pb(II) and Cu(II) in surface samples of in natura(RH) and calcined rice husks (RHA). RHA showed higher potential for removing lead and copper. Experimental data for adsorption isotherms of lead and copper were adjusted by Langmuir, Freundlich and Dubinin-Radushkevick (D-R) models, being better represented by the Langmuir model. The calcination of RH increased its surface area, improving its adsorption properties. From a morphological analysis obtained by SEM and diffraction patterns (XRD), a longitudinal fibrous and amorphous structure was observed for RH. TGA results indicated a total mass loss of around 60% for RH and 24.5% for RHA.

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Teses e Dissertações Julho - Setembro 2012

Mestrado: 972. Ana Luíza Garcia Millás. Instalação da tecnologia de electrospinning para a produção e caracterização de nanofibras de celulose incorporadas com óleos naturais. Orientador: Prof. Dr. Cesar Costapinto Santana. Data: 04/07/2012. 973. Francini Gonçalves Manzato. Polimerização em solução mediada por nitróxidos para a produção de poliestireno monodisperso. Orientadora: Profa. Dra. Liliane Maria Ferrareso Lona. Data: 05/07/2012. 974. Diana Carolina Rueda Martin. Adsorção de o–xileno em argila fluidgel organofílica em fase gasosa. Orientador: Prof. Dr. Edson Tomaz. Data: 10/07/2012. 975. Ivanei Ferreira Pinheiro. Biocompósitos poliméricos de poli(butileno adipato-co-tereftalato – PBAT e fibra natural de munguba, nativa da Amazônia (Pseudobombax munguba). Orientadora: Profa. Dra. Ana Rita Morales. Data: 10/07/2012. 976. Maria Fernanda Miller Lopes. Simulação tridimensional de uma coluna de bolhas cilíndrica – análise em sistema bifásico por técnica de velocimetria por imagem de partícula (PIV), shadow imaging e simulação. Orientadores: Prof. Dr. Milton Mori e Prof. Dr. Marcos Akira d’Ávila (FEM/UNICAMP). Data: 16/07/2012. 977. Diana Isabel Sánchez Forero. Experimentação física do escoamento gás-líquido em uma coluna de bolhas retangular utilizando a técnica PIV e técnica de sombras. Orientador: Prof. Dr. Milton Mori. Data: 16/07/2012. 978. Alexandre Khae Wu Navarro. Cristalização preferencial de polimorfo do ácido l-glutâmico: uma abordagem por controle ótimo. Orientador: Prof. Dr. Flávio Vasconcelos da Silva. Data: 17/07/2012. 979. Rodrigo Sislian. Estudo de sistema de limpeza CIP usando identificação de sistemas. Orientadores: Prof. Dr. Flávio Vasconcelos da Silva e Prof. Dr. Rubens Gedraite (UFU). Data: 20/07/2012. 980. Mateus De Lorenzi Cancelier Mazzucco. Estudo de híbridos de montmorilonitas organicamente modificadas e ABS compatibilizados com copolímeros SEBS ou SBS. Orientador: Prof. Dr. Julio Roberto Bartoli e Prof. Dr. Humberto Gracher Riella (UFSC). Data: 26/07/2012. 981. Sebastián Moreno Cárdenas. Avaliação fluidodinâmica do HDT em regime contracorrente como uso da fluidodinâmica computacional – CFD. Orientador: Prof. Dr. José Roberto Nunhez. Data: 26/07/2012. 982. Thadeu Alfredo Farias Silva. Atenuação térmica interna nos grupos geradores de energia utilizando trocadores de calor de água gelada controlada. Orientador: Prof. Dr. Elias Basile Tambourgi. Data: 30/07/2012. 983. Jaqueline Andréa Espósito Jasiulionis. Projeto e avaliação de desempenho de torres de resfriamento de água utilizando redes neurais artificiais. Orientador: Prof. Dr. Roger Josef Zemp. Data: 30/07/2012. 984. Eulalia Vargas Tapia. Melhoramento genético da levedura oleaginosa Lipomyces starkeyi por mutagênese aleatória, visando produção de biocombustíveis de segunda geração. Orientadoras: Profa. Dra. Telma Teixeira Franco e Dra. Ana Carolina Deckmann (FEQ). Data: 31/07/2012. 985. Joana Bratz Lourenço. Estudo das características fluidodinâmicas de misturas da madeira de eucalipto e do caroço do fruto de tucumã com inerte visando aplicação em processos de termoconversão. Orientadora: Profa. Dra. Katia Tannous. Data: 31/07/2012.

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986. Natália Maira Braga Oliveira. Reação de deslocamento de gás d’água sobre catalisadores de cobre e níquel suportados em alumina e nanofibra de carbono. Orientadores: Prof. Dr. Gustavo Paim Valença e Dr. Ricardo Vieira (INPE). Data: 13/08/2012. 987. Luz Stella Gaona Galindo. Remoção de íons de chumbo e cádmio em diferentes sistemas de adsorção/troca iônica sobre argila bentonítica tipo fluidgel. Orientadores: Profa. Dra. Melissa Gurgel Adeodato Vieira e Dr. Ambrósio Florêncio de Almeida Neto (FEQ). Data: 15/08/2012. 988. Néstor David López González. Secagem convectiva de papel reciclado com incorporação de corantes naturais. Orientadoras: Profa. Dra. Melissa Gurgel Adeodato Vieira e Profa. Dra. Sandra Cristina dos Santos Rocha. Data: 15/08/2012. 989. Vicente Franco Nascimento. Caracterização de biomassas amazônicas – ouriço de castanha-do-Brasil, ouriço de sapucaia e caroço do fruto do tucumã – visando sua utilização em processos de termoconversão. Orientadora: Profa. Dra. Katia Tannous. Data: 15/08/2012. 990. José Júnior Butzge. Controle do regime fluidodinâmico estável durante o processo de umedecimento de inertes em leito de jorro utilizando análise espectral. Orientador: Prof. Dr. Osvaldir Pereira Taranto. Data: 30/08/2012. 991. Gabriel de Marins. Caracterização do licor negro de eucalipto para avaliação do potencial de incrustação em evaporadores. Orientador: Prof. Dr. José Vicente Hallak d’Angelo. Data: 14/09/2012. 992. Erick Djin Mori. Simulação de colunas de bolhas em leito de lama por técnicas de fluidodinâmica computacional. Orientadores: Prof. Dr. Milton Mori e Prof. Dr. Marcos Akira d’Ávila (FEM/UNICAMP). Data: 21/09/2012. 993. Jener de Oliveira. Estudo de aditivação em massa ou por recobrimento de filme de BOPP com compostos orgânicos e nanopartículas anti UV. Orientador: Profa. Dra. Leila Peres. Data: 27/09/2012. (Milésima quingentésima defesa do Programa) Doutorado: 498. Ivan Carlos Franco. Controle preditivo baseado em modelo neuro-fuzzy de sistemas não-lineares aplicados em sistemas de refrigeração. Orientador: Prof. Dr. Flávio Vasconcelos da Silva. Data: 03/07/2012. 499. Henderson Ivan Quintero Perez. Desenvolvimento e avaliação de metodologias para purificação de biolubrificantes via destilação molecular de filme descendente. Orientadores: Profa. Dra. Maria Regina Wolf Maciel, Prof. Dr. Rubens Maciel Filho e Dr. César Benedito Batistella (FEQ). Data: 27/07/2012. 500. Claudia Conti Medugno. Fases de membranas fluidas - L3 a partir de lipídio sintético e pentanol na região diluída - e o respectivo dialisado. Orientador: Prof. Dr. Elias Basile Tambourgi. Data: 31/07/2012. (Quingentésima tese de doutorado do Programa) 501. Giselle de Arruda Rodrigues. Produção de ácido láctico a partir de bagaço de cana de açúcar. Orientadora: Profa. Dra. Telma Teixeira Franco. Data: 31/07/2012. 502. Alex Linardi Gomes. Síntese e caracterização de misturas poliméricas condutoras para aplicação em membranas biodegradáveis e dispositivos eletroluminescentes. Orientador: Prof. Dr. João Sinézio de Carvalho Campos. Data: 02/08/2012.

Boletim da FEQ Página 19 503. Patricia Severino. Desenvolvimento e caracterização físico-química de nanopartículas lipídicas sólidas para encapsulação de proteínas. Orientadora: Profa. Dra. Maria Helena Andrade Santana. Data: 06/08/2012. 504. Luciana Rodrigues Oriqui. Guia de estabilidade para a indústria química – definição de prazo de validade e proposição de prazo de reteste. Orientadores: Prof. Dr. Milton Mori e Dr. Pedro Wongtschowski (Oxiteno). Data: 24/08/2012. 505. Germán González Silva. Metodologia para aplicar LES ao craqueamento catalítico fluido em um reator riser industrial. Orientador: Prof. Dr. Milton Mori. Data: 14/09/2012. 506. Edwin Guido Boza Condorena. Identificação de processos e controle preditivo com modelo utilizando técnicas de inteligência artificial aplicadas à produção de bioetanol. Orientador: Profa. Dra. Aline Carvalho da Costa. Data: 17/09/2012. 507. Maximilian Joachim Hodapp. Título: “Simulação trifásica por técnicas de CFD da combustão de carvão mineral em leito fluidizado circulante”. Orientadores: Prof. Dr. Milton Mori e Prof. Dr. Jhon Jairo Ramirez Behainne (UTFPR). Data: 27/09/2012.

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Notas curtas Palestras na FEQ

No dia 03 de agosto, a FEQ recebeu a visita da Profa. Dra. Nirmala Deenadayalu, do Departamento de Química da Universidade Técnica de Durban (África do Sul). Durante a visita, a professora Nirmala visitou laboratórios de pesquisa na FEQ e ministrou a palestra

“Experimental techniques for determination of thermophysical properties of ionic liquids”. A visita foi organizada pelo professor Martín Aznar, do Departamento de Desenvolvimento de Processos e Produtos (DDPP).

No dia 15 de agosto, os professores Agílio Pádua e Margarida Costa Gomes, docentes da Université Blaise Pascal e pesquisadores do CNRS (França), visitaram a FEQ com o objetivo de procurar parcerias em pesquisa científica. A visita dos professores Agílio e Margarida foi organizada pela professora Liliane Lona, Diretora da FEQ. Bioetanol de segunda geração A pesquisa desenvolvida na tese de doutorado de Sarita Cândida Rabelo, intitulada “Avaliação e otimização de pré-tratamentos e hidrólise enzimática para a produção de etanol de segunda geração”, e que ganhou o Prêmio CAPES e o Grande Prêmio CAPES de 2011, foi objeto de matéria publicada no Portal da UNICAMP. A pesquisa analisou os desafios e perspectivas da produção de etanol de segunda geração no Brasil. O estudo, orientado pelos professores Aline Carvalho da Costa e Rubens Maciel Filho, do Departamento de Desenvolvimento de Processos e Produtos (DDPP), buscou aprimorar as etapas do processo produtivo, através do emprego de novas tecnologias. “No trabalho, nós utilizamos o conceito de biorrefinaria, cuja

proposta é aproveitar os resíduos gerados pela produção do etanol celulósico para a fabricação de outros produtos, como o biogás”, explica a autora, que contou com bolsa de estudo concedida pela FAPESP. No trabalho, Sarita analisou três etapas da produção do etanol de segunda geração, aquele obtido a partir do bagaço de cana (biomassa): pré-tratamento, hidrólise enzimática e fermentação. Na primeira foram usados o peróxido de hidrogênio alcalino e o hidróxido de cálcio para o pré-tratamento do bagaço. “Ambos os reagentes apresentaram bom desempenho, possibilitando a liberação de açúcares fermentáveis a partir do bagaço de cana. Desta forma, foi possível produzir em torno de 240 a 250 litros de etanol por tonelada de biomassa, após as etapas de hidrólise e fermentação”, informa a professora Aline. Em relação à segunda fase, Sarita otimizou a carga enzimática e avaliou o impacto do aumento na concentração de sólidos. Na terceira, aperfeiçoou a fermentação dos licores resultantes da hidrólise. Estes estudos foram necessários para estabelecer as condições de processo. O passo seguinte foi produzir o biogás a partir dos resíduos obtidos durante o processo. Para tanto, a lignina, uma macromolécula oriunda do bagaço, liberada no processo de pré-tratamento, foi recuperada. A etapa de produção de biogás foi realizada pela autora da tese na França, no Institut National de la Recherche Agronomique (INRA). “Essa parceria com os pesquisadores franceses, através de um projeto conjunto INRA/FAPESP, foi importante, visto que o conceito que permeou o estudo foi o do aproveitamento de todas as frações do bagaço de cana e, de uma forma geral, de resíduos agrícolas. O objetivo é aproveitar ao máximo a matéria-prima e subprodutos, transformando-os em produtos úteis e de valor agregado. Com o etanol de segunda geração, este conceito é fundamental para o sucesso do processo. Há vários produtos que podem ser obtidos a partir dele”, explica a professora Aline. De acordo com a professora, o etanol celulósico precisa ser competitivo se comparado à energia conseguida através da queima do bagaço, processo chamado de cogeração. “A tese da Sarita demonstrou que, para uma tonelada de bagaço, é possível produzir uma quantidade de etanol que corresponde a 33% do valor energético obtido com a queima dessa biomassa.

Boletim da FEQ Página 21Isso não quer dizer, porém, que a produção do álcool seja inviável economicamente. Em termos econômicos, pode ser melhor produzir etanol, embora ele proporcione menos energia em termos absolutos. Se considerarmos o aproveitamento de todos os resíduos gerados pelo processo, é possível atingir uma recuperação de energia da ordem de 65%, como demonstraram os testes realizados. Esta recuperação pode ser ainda maior se a vinhaça, outro dos subprodutos, também for usada para produzir biogás”, detalha a professora Aline. Na opinião do professor Rubens, no campo científico os entraves a serem superados estão relacionados com algumas melhorias na metodologia de produção. O desenvolvimento de processos para a produção de etanol de segunda geração, afirma, envolvem etapas que precisam ser otimizadas de forma integrada, para que haja rentabilidade econômica, atendendo aos conceitos de sustentabilidade.

Os professores Rubens Maciel Filho e Aline Carvalho

da Costa

Para o professor Rubens, se existe um país que reúne condições favoráveis para a produção em larga escala do etanol de segunda geração, este é o Brasil. “O processo de produção do etanol de primeira geração está bem consolidado no país. Então, se nós resolvermos os desafios tecnológicos já mencionados, nós aumentaremos substancialmente a produção do biocombustível, sem a necessidade de ampliarmos a área plantada de cana-de-açúcar. Nenhum outro lugar no mundo apresenta essas vantagens, uma vez que o acoplamento dos processos de produção do etanol, de primeira e segunda gerações, traz vantagens competitivas significantes. Então, reforçando, se existe um local onde o etanol celulósico pode vir a ser comercial, esse local é o Brasil”, defende. Questionado sobre quando as primeiras plantas pilotos poderiam entrar em operação no Brasil para testar a produção do etanol de segunda

geração em escala ampliada, e assim permitir uma análise econômica mais precisa, o coorientador da tese diz que isso deve acontecer dentro de 18 a 24 meses. Ele lembra que o Laboratório Nacional de Ciência e Tecnologia do Bioetanol (CTBE), onde Sarita trabalha atualmente, e onde ele e a professora Aline atuam como pesquisadores associados, já conta com esse tipo de estrutura, que está em fase de homologação. “Quando a unidade entrar efetivamente em operação, nós teremos como avaliar as várias rotas de produção do etanol de segunda geração, o que nos permitirá discriminar aquelas mais viáveis economicamente”, adianta. Instalado em Campinas, o CTBE desenvolve cinco programas de pesquisa voltados às áreas agrícolas, industrial, avaliação tecnológica, sustentabilidade e ciência básica. São aproximadamente 85 profissionais, entre biólogos, físicos, químicos, engenheiros e técnicos, que vêm trabalhando com diferentes temas relacionados ao etanol, inclusive o de segunda geração, em colaboração com universidades e institutos de pesquisa, entre eles a UNICAMP. Em relação ao biogás que pode ser obtido a partir do aproveitamento dos resíduos, a autora da tese considera que ele pode vir a ser aproveitado pelas próprias usinas sucroalcooleiras para movimentar seus equipamentos, no lugar da energia proporcionada pela queima do bagaço. “O eventual excedente pode ser vendido para a concessionária de energia”, diz Sarita. Segundo a orientadora do trabalho, o biogás é similar ao gás natural. “É um combustível que tem uma série de aplicações, inclusive para abastecer veículos. Na França, o produto é usado para movimentar os ônibus que operam no sistema de transporte público”, informa. Tão importante quanto contribuir para o desenvolvimento de novos conhecimentos e tecnologias, pesquisas como a voltada à produção do etanol de segunda geração são fundamentais para o treinamento e formação dos alunos de pós-graduação da FEQ, como enfatizam os professores Aline e Rubens. “A formação de recursos humanos qualificados é a nossa principal missão. Nesse sentido, temos tido bastante sucesso. Nossos alunos não estão encontrando dificuldades para arranjar boas colocações no mercado de trabalho”.

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Gestão Ambiental O professor Edson Tomaz, presidente do Grupo Gestor Ambiental (GGA) da UNICAMP e docente do Departamento de Engenharia de Processos (DEPro), ministrou palestra sobre gerenciamento de resíduos durante o Fórum Permanente de Meio Ambiente, realizado no dia 07 de agosto no Centro de Convenções. Com a UNICAMP muito próxima da eliminação dos seus resíduos passivos em 2012, inclusive de inorgânicos, a expectativa do professor Edson é de que, com a busca de soluções para a criação de novas rotinas e respectivas condutas, essas informações poderão estar em breve disponíveis a todos. O GGA tem estimulado treinamentos e cursos, por acreditar num trabalho contínuo e em equipe. São 37 unidades treinadas desde 2005 e 36 planos de gerenciamento de resíduos elaborados até aqui. O professor Edson enfatizou a complexidade que tem o trabalho de gestão ambiental como um todo, sobretudo por exigir uma visão compartilhada, não tão somente iniciativas isoladas das unidades de ensino e pesquisa. Relembrou alguns números para dar a dimensão que o projeto requer. “A área total ocupada pela UNICAMP é de 3.518.602 m2, onde circulam diariamente 80 mil pessoas e 45 mil veículos”, pontuou. “Temos um longo caminho pela frente, mas promissor. Basta entendermos que cada um de nós é parte desse processo.” O GGA possui hoje uma equipe de 98 facilitadores em 48 unidades que, além da organização de rotinas, também realiza inventários dos problemas identificados em suas áreas. “A tarefa é enorme e envolve atacar resíduos biológicos, radioativos, urbanos, gestão de áreas de proteção ambiental, recursos hídricos, entre outros. Para se ter uma ideia, a UNICAMP gera cerca de 60 toneladas por mês de resíduos hospitalares. Por outro lado, a Universidade em breve contará com um entreposto, cujo objetivo será diminuir os riscos nas unidades, o qual está sendo concebido para fazer o armazenamento temporário de resíduos. E, no futuro, pensamos até em fazer algum tipo de tratamento localmente”, informou. Edital Pro-Equipamentos A FEQ for contemplada com R$ 140.000,00 no Edital CAPES Pró-Equipamentos Institucional – 2012. O projeto, desenvolvido pela doutoranda e funcionária da FEQ Kelly Roberta de Palma, chefe do Laboratório de Recursos Analíticos e Calibração (LRAC), prevê a compra de uma máquina de fusão de amostras e de uma prensa para preparo das mesmas para uso em

espectroscopia de fluorescência de raios X. Estes equipamentos deverão aumentar a capacidade e a qualidade analítica do laboratório. Prêmio Chemtech O trabalho "Estudo de arquiteturas de controle reconfigurável aplicado a sistemas de interesse de engenharia química", apresentado no XIX Congresso Brasileiro de Engenharia Química - COBEQ 2012, de autoria de Ana Maria Frattini Fileti, Flavio Vasconcelos da Silva, Luís Cláudio Lopes e Thiago Costa, recebeu o Prêmio Chemtech de Incentivo à Pesquisa em Simulação, Otimização e Controle de Processos. Parabéns à equipe pelo sucesso da pesquisa. Prêmio GE O trabalho “Produção contínua de biodiesel utilizando coluna de destilação reativa”, apresentado no XIX Congresso Brasileiro de Engenharia Química - COBEQ 2012, e de autoria de Lourival José dos Santos, Luiz Fernando de Lima Luz Júnior, Marcos Lúcio Corazza, Papa Matar Ndiaye, Luiz Pereira Ramos, Emerson Valt e Maria Regina Wolf Maciel, recebeu o Prêmio GE de Incentivo à Pesquisa em Biocombustíveis. Parabéns aos premiados. Professor Marco Cremasco publica novo livro didático A publicação do novo livro didático do professor Marco Aurélio Cremasco, do Departamento de Engenharia de Processos (DEPro), titulado “Operações Unitárias em Sistemas Particulados e Fluidomecânicos”, foi matéria do Jornal da UNICAMP n539. A obra cobre boa parte das ementas normalmente propostas para disciplinas dos cursos de engenharia química no Brasil que utilizam operações unitárias envolvendo sistemas particulados.

O professor Marco Aurélio Cremasco

Boletim da FEQ Página 23Destinado tanto a cursos de graduação como de pós-graduação, o livro pode ser utilizado ainda como material de apoio por profissionais das engenharias química, agrícola, de alimentos, de produção, mecânica, entre outros em variadas atividades. O trabalho resulta do amadurecimento adquirido pelo autor em 26 anos de docência e da sua experiência com textos de apostilas por ele elaboradas com o objetivo de subsidiar os alunos na disciplina Operações Unitárias I, do curso de Engenharia Química da UNICAMP. O texto incorpora também trocas de experiências com outros professores que lecionam a disciplina ou assemelhadas no Brasil e, além disso, menciona resultados decorrentes de trabalhos desenvolvidos por seus orientados na iniciação científica e na pós-graduação. O professor Cremasco enfatiza a sua particular preocupação e envolvimento com o ensino ao longo de sua atuação na Universidade: “Acredito que uma instituição de ensino superior é, antes de tudo, uma formadora de recursos humanos de qualidade. O livro foi elaborado com essa preocupação e nele procuro delinear um olhar para essa formação.” Para o autor, as contribuições mais significativas do texto são a linguagem conceitual mais próxima de todos os seus públicos, que envolve de certa forma uma padronização; o atendimento em geral das ementas das escolas de engenharia química do Brasil; e o resgate do que é estudado e desenvolvido na área no país. A obra se dedica a apresentar um conhecimento já sedimentado. O seu diferencial está na concepção e estrutura didática, na abordagem que adota, e nas aplicações, em grande parte ligadas à realidade nacional. Ácido lático de bagaço da cana pode ser base para a produção de um polímero verde A pesquisa desenvolvida na tese de doutorado de Giselle de Arruda Rodrigues, que versa sobre a conversão de açúcares presentes no bagaço da cana em ácido lático por ação de um micro-organismo, foi matéria publicada no Jornal da UNICAMP n 540. O ácido lático é um composto químico com alto valor agregado e com versatilidade em aplicações. A produção biotecnológica do ácido lático abre perspectiva, no futuro, para o desenvolvimento de um polímero totalmente biodegradável, o polilactato (PLA), capaz de substituir os plásticos derivados do petróleo. Por exemplo, pode ser empregado na produção de garrafas para água mineral,

copos e sacolas descartáveis, tecidos, fibras para preenchimento de estofamento, utensílios plásticos em geral e, até mesmo em próteses e enxertos ósseos. Além de utilizar uma fonte renovável , no caso o bagaço da cana-de-açúcar, o processo tem a vantagem de não competir com a produção de alimentos, que explora amplamente o ácido lático.

Giselle de Arruda Rodrigues

O estudo foi conduzido sob orientação da professora Telma Franco, do Departamento de Engenharia de Processos (DEPro), em parceria com o doutor Joachim Venus, do Departamento de Bioengenharia do Instituto Leibniz, em Potsdam (Alemanha). Na indústria, a produção do ácido lático é comumente obtida por microrganismos que atuam na fermentação dos açúcares presentes no leite e seus derivados. As propriedades acidulantes, capazes de deixar certos alimentos com gostos azedos, tornaram o ácido lático indispensável na indústria alimentícia, principalmente para os queijos, iogurtes, refrigerantes, sucos artificiais e cervejas. Os seres vivos também produzem ácido lático, que é liberado durante a realização de atividades físicas. “O PLA é um poliéster bastante versátil. Possui muitas vantagens do ponto de vista de processos industriais. Ele possui atributos como transparência, brilho, resistência mecânica, termorresistência e biodegradabilidade”, enumera Giselle. Para a produção de PLA, o ácido lático é frequentemente obtido a partir de açúcares de seis carbonos encontrados no melaço da cana-de-açúcar no Brasil e no amido do milho nos Estados Unidos. É a primeira vez, no entanto, que se obtém o ácido lático a partir de açúcares de cinco carbonos presentes no bagaço da cana.

Página 24 Boletim da FEQ

“O desafio é não usar o melaço da cana ou o amido do milho nesta produção. Fica difícil pensar em produzir, por exemplo, sacolas plásticas de supermercados a partir de uma matéria-prima que pode servir na alimentação humana. O ácido lático obtido do bagaço – uma fonte renovável – não irá competir com o fornecimento de alimentos e pode, ao mesmo tempo, ser utilizado para a produção de materiais biodegradáveis”, reforça Giselle. Ela ficou um ano e meio na Alemanha; lá, foi selecionada a bactéria utilizada no estudo – a cepa Bacillus coagulans 162, dentre a rica variedade do banco de microrganismos alemão. “A maioria dos microrganismos que produzem ácido lático utilizando açúcares de cinco carbonos também gera outros compostos secundários, como o ácido acético, o que não queríamos por vários motivos. Além de desperdiçar a matéria-prima para produzir algo que não tínhamos interesse, o ácido acético é tóxico para o crescimento da bactéria.” Para que o microrganismo pudesse atuar, o bagaço da cana-de-açúcar passou por um processo de hidrólise, a fim de liberar os açúcares. “São estes açúcares que utilizamos na fermentação, em uma via homofermentativa, ou seja, que fornece um único produto, o ácido lático, a partir de açúcares de cinco carbonos”, esclarece Giselle. Os microrganismos em geral usam a rota metabólica heterofermentativa que produz mais de um composto, o ácido lático e o ácido acético por exemplo. “Neste caso teríamos uma etapa a mais no processamento que seria a purificação, isto é, a separação do ácido lático dos outros compostos. Mas essa bactéria que obtivemos consegue metabolicamente utilizar todos os átomos de carbono presentes no açúcar para a produção apenas de ácido lático. Isso é um ganho muito grande do ponto de vista produtivo”, revela. A pesquisa demonstrou que a bactéria testada produziu ácido lático com 99% de pureza. O microrganismo também apresentou ótima eficiência, próxima a 90%, chegando a acumular mais de 100 gramas/litro de ácido lático em fermentação semicontínua. “A bactéria se destacou em produtividade e eficiência nos testes sequenciais que incluíam procedimentos de fermentação em biorreator”, confirma a pesquisadora. Os estudos foram financiados por meio de acordo bilateral entre a Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) e o Serviço Alemão de Intercâmbio Acadêmico (DAAD). O Conselho Nacional de Desenvolvimento Tecnológico e Científico (CNPq) também financiou a pesquisa.