Editorial Prof. Dr. Martín Aznar O presente número do Boletim da FEQ traz algumas modificações sutis na diagramação das páginas, com o objetivo de uniformizar as diferentes seções. Além disso, as informações acerca dos artigos publicados passam a incluir o ISSN da revista, bem como o Digital Object Identifier (DOI), para facilitar o acesso aos documentos e ajudar no preenchimento de algumas ferramentas como o currículo Lattes e o SIPEX. Entre as notícias a destacar, a colaboração com a Universidade Estadual do Amazonas, através dos projetos de mestrado e doutorado interinstitucionais (MINTER/DINTER) foi aprovada pela CAPES. As primeiras turmas devem começar no primeiro semestre de 2009. A empresa júnior PROPEQ inaugura a sua colaboração com o Boletim da FEQ com uma notícia alvissareira, a criação de uma parceria com uma das mais fortes indústrias do setor químico, a Dow Chemical do Brasil. Destaque também para atuação do nosso aluno de graduação Luís Fernando Paolucci, funcionário da Replan/Petrobrás, que ganhou por três anos consecutivos o Prêmio Apoena/Petrobrás na categoria rentabilidade e lucratividade. Parabéns!

N E S T E N ÚM E RO

1 Editorial

1 Palestras na FEQ

2 Artigos publicados em Abril-Junho 2008

10 Teses e dissertações

12 Notas curtas

Luís Fernando Paolucci,

aluno da FEQ e funcionário

Petrobrás ganha Prêmio

Apoena pelo terceiro ano

consecutivo.

15 de julho de 2008 Ano 2 Número 6

Uma publ icação da Facu ldade de Engenharia Química da UNICAMP Av. Albert Einstein 500, Campinas-SP, 13081-970 Editor: P rof. Dr. Mart ín Aznar, bolet imfeq@feq.unicamp.br, fone 3521-3962

Boletim da

FEQ

Palestras na FEQ � Dr. Joachim Venus, Leibniz-Institut für Agrartechnik Potsdam-Bornim

(Alemanha). “Renewables for bioconversions”. 07/04/2008. � Dr. César Zuin, GE Healthcare Life Sciences. ”Estratégias de Purificação

de Proteínas, da Bancada à Produção”. 11/04/2008.

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Artigos Publicados em Revistas Indexadas Abril-Junho 2008

Bases de dados: ISI Web of Knowledge, Sci Finder Scholar, Compendex, SciELO, Scopus, Scirus.

Abril

Bioethanol production optimization: a thermodynamic analysis Álvarez, V.H.; Ccopa-Rivera, E.A.; Costa, A.C.; Maciel Filho, R.; Wolf-Maciel, M.R.; Aznar, M. Applied Biochemistry and Biotechnology, 148 (2008), 141-149. ISSN: 0273-2289. doi:10.1007/s12010-008-8132-4 In this work, the phase equilibrium of binary mixtures for bioethanol production by continuous extractive process was studied. The process is composed of four interlinked units: fermentor, centrifuge, cell treatment unit, and flash vessel (ethanol-congener separation unit). A proposal for modeling the vapor–liquid equilibrium in binary mixtures found in the flash vessel has been considered. This approach uses the Predictive Soave–Redlich–Kwong equation of state, with original and modified molecular parameters. The congeners considered were acetic acid, acetaldehyde, furfural, methanol, and 1-pentanol. The results show that the introduction of new molecular parameters r and q in the UNIFAC model gives more accurate predictions for the concentration of the congener in the gas phase for binary and ternary systems. Evaluation of batch adsorption of chromium ions on natural and crosslinked chitosan membranes Baroni, P.; Vieira, R.S.; Meneghetti, E.; Silva, M.G.C.; Beppu, M.M. Journal of Hazardous Materials, 152 (2008), 1155-1163. ISSN: 0304-3894. doi:10.1016/j.jhazmat.2007.07.099 Removal of chromium ions from aqueous solutions by using natural and crosslinked chitosan membranes was achieved using batch adsorption experiments. The effect of pH (6.0 and 2.0), concentration of chromium ions and crosslinking agents (glutaraldehyde: GLA and epichlorohydrin: ECH) on the adsorption properties of chitosan membranes was analyzed. The experimental equilibrium data was fitted to Langmuir and Freundlich models. Through the model curves, it was possible to observe that the amount of chromium ions adsorbed was significantly higher for crosslinked membranes compared to non-crosslinked chitosan. The maximum adsorbed amount was about 1400 mg g−1 for ECH-crosslinked chitosan at pH 6.0. The adsorption rates for crosslinked chitosan membranes with glutaraldehyde and epichlorohydrin were similar for natural chitosan. Desorption study using NaCl (1 mol L−1) solution was performed on chitosan membranes, in order to recover chromium ions and to determine the suitable number of cycles for repeated use of these membranes without considerable decrease in their adsorption capacity. The desorption results showed that chromium ions could be more effectively removed at pH 2.0 than pH 6.0, mainly for ECH-crosslinked chitosan. Kinetic modeling and parameter estimation in a tower bioreactor for bioethanol production Ccopa-Rivera, E.A.; Costa, A.C.; Lunelli, B.H.; Wolf-Maciel, M.R.; Maciel Filho, R. Applied Biochemistry and Biotechnology, 148 (2008), 163-173. ISSN: 0273-2289. doi: 10.1007/s12010-007-8062-6 In this work, a systematic method to support the building of bioprocess models through the use of different optimization techniques is presented. The method was applied to a tower bioreactor for bioethanol production with immobilized cells of Saccharomyces cerevisiae. Specifically, a step-by-step procedure to the estimation problem is proposed. As the first step, the potential of global searching of real-coded genetic algorithm (RGA) was applied for simultaneous estimation of the parameters. Subsequently, the most significant parameters were identified using the Plackett–Burman (PB) design. Finally, the quasi-Newton algorithm (QN) was used for optimization of the most significant parameters, near the global optimum region, as the initial values were already determined by the RGA global-searching algorithm. The results have shown that the performance of the estimation procedure applied in a deterministic detailed model to describe the experimental data is improved using the proposed method (RGA–PB–QN) in comparison with a model whose parameters were only optimized by RGA.

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Empirical models for end-use properties prediction of LDPE: application in the flexible plastic packaging industry Costa, M.C.B.; Jardini, A.L.; Wolf-Maciel, M.R.; Embiruçu, M.; Maciel Filho, R. Materials Research, 11 (2008), 23-30. ISSN: 1516-1439. doi: 10.1590/S1516-14392008000100005 The objective of this work is to develop empirical models to predict end use properties of low density polyethylene (LDPE) resins as functions of two intrinsic properties easily measured in the polymers industry. The most important properties for application in the flexible plastic packaging industry were evaluated experimentally for seven commercial polymer grades. Statistical correlation analysis was performed for all variables and used as the basis for proper choice of inputs to each model output. Intrinsic properties selected for resin characterization are fluidity index (FI), which is essentially an indirect measurement of viscosity and weight average molecular weight (MW), and density. In general, models developed are able to reproduce and predict experimental data within experimental accuracy and show that a significant number of end use properties improve as the MW and density increase. Optical properties are mainly determined by the polymer morphology. Monoglycerides and diglycerides synthesis in a solvent-free system by lipase-catalyzed glycerolysis Fregolente, P.B.L.; Fregolente, L.F.V.; Pinto, G.M.F.; Batistella, C.B.; Wolf-Maciel, M.R.; Maciel Filho, R. Applied Biochemistry and Biotechnology, 146 (2008), 165-172. ISSN: 0273-2289. doi: 10.1007/s12010-008-8133-3 Five lipases were screened (Thermomyces lanuginosus free and immobilized forms, Candida antarctica B, Candida rugosa, Aspergillus niger, and Rhizomucor miehei) to study their ability to produce monoglycerides (MG) and diglycerides (DG) through enzymatic glycerolysis of soybean oil. Lipase from C. antarctica was further studied to verify the enzyme load (wt% of oil mass), the molar ratio glycerol/oil, and the water content (wt% of glycerol) on the glycerolysis reaction. The best DG and MG productions were in the range 45-48% and 28-30% (w/w, based on the total oil), respectively. Using immobilized lipases, the amount of free fatty acids (FFA) produced was about 5%. However, the amount of FFA produced when using free lipases, with 3.5% extra water in the system, is equivalent to the MG yield, about 23%. The extra water content provides a competition between hydrolysis and glycerolysis reactions, increasing the FFA production Analysis of kinetic and operational parameters in a structured model for acrylic acid production through experimental design Lunelli, B.H.; Ccopa-Rivera, E.; Toledo, E.C.V.; Wolf-Maciel, M.R.; Maciel Filho, R. Applied Biochemistry and Biotechnology, 148 (2008), 175-187. ISSN: 0273-2289. doi: 10.1007/s12010-007-8060-8 In biotechnological processes, a great number of factors can influence the income productivity and conversion. Normally, it is not evident which of these factors are the most important and how they interact. In this work, multivariate analysis techniques are used as experimental design coupled to a detailed deterministic model to identify the parameters with the most significant impact on the model to represent well the acrylic acid production process. It is proposed as an alternative process, having sugarcane as feedstock, to the petrochemical-based ones that have significant environmental impacts for their production. To increase the competitiveness of renewable acrylic-acid-based process, it is necessary to find out working conditions near the optimal region, which is not an easy task, as the process is multivariable and non-linear. The mapping of the dynamics of the developed process is made using techniques of factorial design together with the methodology of Plackett–Burman. It is shown that it is possible to increase the process performance by choosing optimized conditions for the reactor operation. Liquid-liquid equilibrium of ternary systems 1-butyl-3-methylimidazolium hexafluorophosphate + aromatic + aliphatic Maduro, R.M.; Aznar, M. Fluid Phase Equilibria, 265 (2008), 129-138. ISSN: 0378-3812. doi:10.1016/j.fluid.2008.01.007 Liquid-liquid equilibrium data for the ternary systems nonane + benzene + [bmim][PF6], nonane + toluene + [bmim][PF6], nonane + m-xylene + [bmim][PF6], undecane + benzene + [bmim][PF6], undecane + toluene + [bmim][PF6], undecane + m-xylene + [bmim][PF6]) were determined at 298.15 K. Binodal curves were obtained by the cloud point method, while tie-line compositions were obtained by density and UV spectrophotometry measurements. In all cases the two-phase region is large and wide. The values of distribution coefficients and selectivities indicate that the ionic liquid [bmim][PF6] is a good solvent for

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the extraction of aromatic from aliphatic compounds. The consistency of the tie-line data was ascertained by applying the Othmer-Tobias correlation. The experimental LLE data were correlated through the well-known NRTL model for the activity coefficient, with estimation of new interaction energy parameters, using the Simplex minimization method and a composition-based objective function. The results, analyzed in terms of root mean square deviations between experimental and calculated compositions, were considered satisfactory. Synthesis and characterization of a starch-modified hydrogel as potential carrier for drug delivery system Reis, A.V.; Guilherme, M.R.; Moia, T.A.; Mattoso, L.H.C.; Muniz, E.C.; Tambourgi, E.B. Journal of Polymer Science Part A: Polymer Chemistry, 46 (2008), 2567-2574. ISSN: 0887-624X. doi:10.1002/pola.22588 Synthesis and characterization of a new hydrogel were carried out using a chemically modified starch (starch-M) consisting of coupling C=C bounds coming from glycidil methacrylate (GMA) onto the polysaccharide structure. 13C NMR, 1H NMR, and FT-IR spectroscopies were used to confirm the incorporation of such groups onto the starch-M. The hydrogel was prepared by a crosslinking polymerization of starch-M using sodium persulfate as an initiating agent. The starch-M hydrogel shows morphology clearly different from that of the raw starch film due to the presence of voids on its surface. The swelling process of the starch-M hydrogel was not significantly affected by changes on the temperature or on pH of the surrounding liquid, indicating the such behavior can be then understood by a diffusional process, resulting from its physical-chemical interactions with the solvent. The values of the diffusional exponent n were on the order of 0.45-0.49 for the range of pHs investigated, demonstrating that the water transport mechanism of starch-M hydrogel is more dependent on Fickian diffusion, that is, controlled by water diffusion. Such starch-M hydrogel is a promising candidate to be used in transporting and in preserving acid-responsive drugs, such as corticoids, for the treatment of colon-specific diseases, for example, Crohn's disease. Cytotoxicity and genotoxicity of bovine pericardium preserved in glycerol Rodas, A.C.D.; Maizato, M.J.S.; Leirner, A.A.; Pitombo, R.N.M.; Polaiewicz, B.; Beppu, M.M.; Higa, O.Z. Artificial Organs, 32 (2008), 272-276. ISSN: 0160-564X. doi:10.1111/j.1525-1594.2008.00542.x Bovine pericardium is a widely utilized biomaterial. Usually, after harvesting, it is advantageous that the pericardium be immersed in glycerol to improve its shelf life. This can induce some degree of toxicity in the material. The studies were performed in compliance with the rules of ISO 10993 and OECD 487, in the biological evaluation of medical devices. The material was prepared without previous washing. After sterilization by gamma radiation the pericardium was immersed in RPMI 1640 culture medium to fulfill the extraction condition. The same extract was employed in the cytotoxic and genotoxic tests. The procedures were carried out with Chinese hamster ovary cell line and to determine the cytotoxicity, a colorimetric method with the tetrazolium compound MTS was used. For the genotoxicity, following the in vitro micronucleus assay, the test was developed with and without metabolic activation. The Cytotoxicity Index was graphically estimated at the extract concentration of 78%. In the genotoxicity test, the average value of cell proliferation index was found to be 1.62 ± 0.02 with S9 metabolic activator and 1.91 ± 0.01 without S9 metabolic activator. Both values are similar to the negative control value in the micronucleus assay. We observed that although the pericardium preserved in glycerol shows a certain level of cytotoxicity, it does not show any genotoxicity.

Maio Application of a thermodynamic consistency test to binary mixtures containing an ionic liquid Álvarez, V.H.; Aznar, M. The Open Thermodynamics Journal, 2 (2008), 25-38. ISSN: 1874-396X. doi:10.2174/1874396X00802010025 A thermodynamic consistency test developed for high pressure binary vapor-liquid mixtures is applied to mixtures containing a supercritical solvent and an ionic liquid. Several authors have reported vapor-liquid equilibrium data on the binary systems supercritical CO2 + 1-butyl-3-methyl imidazolium hexafluorophosphate {[bmim][PF6]}, supercritical CO2 + 1-butyl-3-methyl imidazolium nitrate {[bmim][NO3]}, supercritical CO2 + 1-butyl-3-methyl imidazolium tetrafluoroborate {[bmim][BF4]} and supercritical CHF3 + 1-butyl-3-methyl imidazolium hexafluorophosphate {[bmim][PF6]}, but some of these data differ dramatically. The Peng-Robinson equation of state, coupled with the Wong-Sandler mixing

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rules, has been used for modeling the vapor-liquid equilibrium of these binary mixtures. Then, the proposed thermodynamic consistency test has been applied. The results show that the consistency test can be applied with confidence, determining consistency or inconsistency of the experimental data. Formulation of a protein-free medium based on IPL-41 for the sustained growth of Drosophila melanogaster S2 cells Batista, F.R.X.; Pereira, C.A.; Mendonça, R.Z.; Moraes, A.M. Cytotechnology, 57 (2008), 11-22. ISSN: 0920-9069. doi:10.1007/s10616-008-9153-0 An animal protein-free medium was developed for Drosophila melanogaster S2 (S2AcGPV2) cells genetically modified to produce the rabies virus G glycoprotein (GPV). IPL-41, used as a basal medium, was supplemented with yeastolate, carbohydrates, amino acids and lipids aiming initially to reduce and further to eliminate the need of fetal bovine serum. The S2AcGPV2 cells were fully capable of growing in serum-free supplemented IPL-41 medium containing 6 g L−1 yeastolate ultrafiltrate, 10 g L−1 glucose, 3.5 g L−1 glutamine, 0.5 g L−1 fructose, 2 g L−1 lactose, 0.6 g L−1 tyrosine, 1.48 g L−1 methionine and 1% (v/v) lipid emulsion, reaching 19 × 106 cells mL−1. Maximum specific growth rate and cell productivity were 0.025 h−1 and 0.57 × 105 cells mL−1 h−1, respectively. Glucose and lactose were consumed during cell culture, but not fructose. Lactate concentration generally decreased during cell culture, while ammonium concentration reached 167 mg L−1, however, without noticeable deleterious effects on cell growth. GPV concentration values achieved were, however, modest in the proposed medium formulation. Kinetic response of a Drosophila melanogaster cell line to different medium formulations and culture conditions Bovo, R.; Galesi, A.L.L.; Jorge, S.A.C.; Piccoli, R.A.M.; Moraes, A.M.; Pereira, C.A.; Augusto, E.F.P. Cytotechnology , 57 (2008), 23-35. ISSN: 0920-9069. doi:10.1007/s10616-008-9146-z In the past few years, Drosophila melanogaster cells have been employed for recombinant protein production purposes, and a comprehensive knowledge of their metabolism is essential for process optimization. In this work, the kinetic response of a Schneider S2 cell line, grown in shake flasks, in two different culture media, the serum-free SF900-II® and the serum-supplemented TC-100, was evaluated. Cell growth, amino acids and glucose uptake, and lactate synthesis were measured allowing the calculation of kinetic parameters. The results show that S2 cells metabolism was able to adjust to different environmental situations, as determined by medium formulation, as well as by the particular situation resulting from the culture conditions. Cells attained a 163% higher final cell concentration (1.4 × 107 cells mL−1) in SF900 II® medium, when compared to serum-supplemented TC-100 medium. Also, a maximum specific cell growth rate 52% higher in SF900 II® medium, when compared to serum-supplemented TC-100 one, was observed. Glutamine was the growth limiting factor in SF900 II® medium, while glucose, sometimes associated with glutamine, controlled growth in serum-supplemented TC-100 medium based formulation. The different pattern of lactate production is an example of the versatility of the metabolism of these cells. This by-product was produced only in glutamine limitation, but the amount synthesized depended not only on the excess glucose, but on other medium components. Therefore, in serum-supplemented TC-100 medium a much smaller lactate amount was generated. Besides, glucose was identified not only as a growth limiting factor, but also as a viability limiting factor, since its depletion accelerated cell death. Experimental study and ERAS modeling of the excess molar enthalpy of acetonitrile + 1-heptanol or 1-octanol mixtures at 298.15, 313.15 and 323.15 K and atmospheric pressure Checoni, R.F.; D’Agostini, L.; Francesconi, A.Z. Journal of Chemical Thermodynamics, 40 (2008), 759-765. ISSN: 0021-9614. doi:10.1016/j.jct.2008.01.017 As a continuation of our studies on excess functions of binary systems, experimental data of excess molar enthalpy (HmE) of acetonitrile + 1-heptanol or 1-octanol mixtures have been determined as a function of composition at 298.15, 313.15 and 323.15 K at atmospheric pressure using a modified 1455 PARR mixture calorimeter. The HmE is positive for both systems over the whole composition range. The applicability of the ERAS model to correlate HmE of the mixtures studied was tested. The agreement between experimental and calculated values is satisfactory.

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Growth of recombinant Drosophila melanogaster Schneider 2 cells producing rabies virus glycoprotein in bioreactor employing serum-free medium Galesi, A.L.L.; Aguiar, M.A.; Astray, R.M.; Augusto, E.F.P.; Moraes, A.M. Cytotechnology, 57 (2008), 73-81. ISSN: 0920-9069. doi:10.1007/s10616-008-9139-y Drosophila melanogaster Schneider 2 (S2) cells have been increasingly used as a suitable expression system for the production of different recombinant proteins, and the employment of bioreactors for large-scale culture is an important tool for this purpose. In this work, Drosophila S2 cells producing the rabies virus glycoprotein RVGP were cultivated in bioreactor, employing a serum-free medium, aiming an improvement in cell growth and in glycoprotein production. To overcome cell growth limitation commonly observed in stirred flasks, different experiments in bioreactor were performed, in which some system modifications were carried out to attain the desired goal. The study showed that this cell line is considerably sensitive to hydrodynamic forces, and a high cell density (about 16.0 × 106 cells mL−1) was only obtained when Pluronic F68® percentage was increased to 0.6% (w/v). Despite ammonium concentration affected RVGP production, and also cell growth, an elevated amount of the target protein was obtained, attaining 563 ng 10−7 cells. Effects of extrusion conditions on the properties of recycled poly(ethylene terephthalate)/nanoclay nanocomposites prepared by a twin-screw extruder (p NA) Giraldi, A.L.F.M.; Bizarria, M.T.M.; Silva, A.A.; Velasco, J.I.; d'Ávila, M.A.; Mei, L.H.I. Journal of Applied Polymer Science , 108 (2008), 2252-2259. ISSN: 0021-8995. doi:10.1002/app.27280 The effects of extrusion conditions on the mechanical properties of recycled poly(ethylene terephthalate) (rPET)/clay nanocomposites were studied. Nanocomposites of recycled PET containing 2.5 and 5.0 wt % of montmorillonite modified with organophilic quaternary ammonium salt (DELLITE 67G) were prepared by melt compounding using a corotating twin-screw type extruder at two different screw rotation speeds: 250 and 150 rpm. The highest value of Young's modulus was found for low screw rotation speed (150 rpm). Morphological analysis using transmission electron microscopy (TEM) revealed the presence of fully exfoliated clay platelets in samples prepared at 150 rpm. It was concluded that the screw rotation speed should be optimized when preparing recycled PET/clay nanocomposites by melt compounding. Biomass production and carbon dioxide fixation by Aphanothece microscopica Nägeli in a bubble column photobioreactor Jacob-Lopes, E.; Lacerda, L.M.C.F.; Franco, T.T. Biochemical Engineering Journal, 40 (2008), 27-34. ISSN: 1369-703X. doi:10.1016/j.bej.2007.11.013 The objective of the present study was to evaluate the growth kinetics of Aphanothece microscopica Nägeli under different conditions of temperature, light intensity and CO2 concentration. The growth kinetics of the microorganism and carbon biofixation were evaluated using a central composite design, considering five different temperature levels (21.5, 25, 30, 35 and 38.5°C), light intensities (0.96, 3, 6, 9 and 11klux) and carbon dioxide concentrations (3, 15, 25, 50 and 62%). The results obtained showed the effects of temperature, light intensity and CO2 concentration (p<0.05) on the photosynthetic metabolism of the microorganism. Response surface methodology was adequate for process optimization, providing a carbon fixation rate to the order of 109.2mg/L.h under conditions of 11klux, 35ºC and 15% carbon dioxide, representing an increase of 58.1% as compared to the conditions tested initially. Biosorption of chromium(VI) using a Sargassum sp. packed-bed column Vieira, M.G.A.; Oisiovici, R.M.; Gimenes, M.L.; Silva, M.G.C. Bioresource Technology, 99 (2008), 3094-3099. ISSN: 0960-8524. doi:10.1016/j.biortech.2007.05.071 Chromium(VI) is present in several industrial wastewaters and it can cause health and environmental hazards above certain concentrations. Equilibrium studies have shown the feasibility of using Sargassum sp. algae for chromium removal from aqueous solutions by biosorption. However, for the design and operation of chromium biosorption processes, dynamic flow studies are required. The objective of the study was to examine chromium(VI) removal from an aqueous solution using a packed-bed column with Sargassum sp. algae as a biosorbent. The dynamic behavior of the biosorption column was investigated through experiments and the influence of operating conditions, such as initial chromium concentration, flow rate and amount of biosorbent, on the column removal capacity have been analyzed using the factorial design methodology. The capacity of removal obtained at optimum conditions was 19.06 mg of metal/g biosorbent.

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Entrainment of heterogeneous particles from gas-fluidized bed Tannous, K.; Donida, M.W.; Obata, L.A. Particulate Science and Technology, 26 (2008), 222-234. ISSN: 0272-6351. doi:10.1080/02726350802028884 The entrainment of heterogeneous particles in a gas-fluidized bed for particle mixtures of categories A and B according to the Geldart classification was conducted in this study. The experiments were carried out in an acrylic column of 0.092 m diameter. The distributors were perforated plates of up to 5.9% free area fraction. Measurements of pressure gradients were made using 24 pressure taps. Glass beads with particle diameters from 60 to 400 µm were used. The mixtures were described using the Rosin-Rammler-Bennet granulometric distribution model. The transport disengaging height (TDH) heights were obtained using the Geldart methodology. A 25 experimental design was applied relating the dispersion index, mean diameter, solid mass, superficial gas velocity, and free area fraction of the distributor to obtain the TDH heights. Slugging and transition for turbulence regimes characterized the behaviors of fluidized beds. The results showed that TDH heights for heterogeneous particles were dependent on the solid mass and superficial gas velocity.

Junho Parameter estimation for VLE calculation by global minimization: the genetic algorithm Álvarez, V.H.; Lariço, R.; Ianos, Y.; Aznar, M. Brazilian Journal of Chemical Engineering, 25 (2008), 409-418. ISSN: 0104-6632. doi: 10.1590/S0104-66322008000200018 Vapor-liquid equilibrium calculations require global minimization of deviations in pressure and gas phase compositions. In this work, two versions of a stochastic global optimization technique, the genetic algorithm, the freeware MyGA program, and the modified mMyGA program, are evaluated and compared for vapor-liquid equilibrium problems. Reliable experimental data from the literature on vapor liquid equilibrium for water + formic acid, tert-butanol + 1-butanol and water + 1,2-ethanediol systems were correlated using the Wilson equation for activity coefficients, considering acid association in both liquid and vapor phases. The results show that the modified mMyGA is generally more accurate and reliable than the original MyGA. Next, the mMyGA program is applied to the CO2 + ethanol and CO2 + 1-n-butyl-3-methylimidazolium hexafluorophosphate systems, and the results show a good fit for the data. Modeling of phase equilibrium of binary mixtures composed by polystyrene and chlorofluorocarbons, hydrochlorofluorocarbons, hydrofluorocarbons and supercritical fluids using cubic and non-cubic equations of state Arce, P.F.; Aznar, M. Journal of Supercritical Fluids, 45 (2008), 134-145. ISSN: 0896-8446. doi:10.1016/j.supflu.2007.07.019 The understanding of the polymer + solvent interactions is of fundamental importance in the development of new products and processes in several important industrial sectors, such as special paints, cosmetics, packing, manufacture of polymeric membranes, etc. Although the nature of these physical interactions is well known, the thermodynamic modeling of polymer + solvent systems in industrial applications presents difficulties, mainly due to the necessity to characterize not only the polymeric phase, in terms of properties that are easily measurable, but also the interaction of the polymer with the other components of low molar mass, through conveniently chosen parameters. In this work, the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) and Sanchez-Lacombe (SL) equations of state (EoS) are used in order to model the gas solubilities of binary systems composed by polystyrene and chlorofluorocarbons, hydrochlorofluorocarbons hydrofluorocarbons and supercritical fluids, which experimental data were obtained from the literature. The results were compared with those obtained by the traditional Peng-Robinson (PR) EoS. In each thermodynamic model, a one fluid-type van der Waals (vDW) mixing rule with conventional combination rules and a temperature-dependent binary interaction parameter were used. Solubilities correlated by the PC-SAFT EoS are in good agreement with the experimental data when compared with those obtained with the SL and PR EoS.

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Fluid phase behavior modeling of CO2 + molten polymer systems using cubic and theoretically based equations of state Arce, P.F.; Mattedi, S.; Aznar, M. Polymer Engineering & Science, 48 (2008), 1157-1167. ISSN: 0032-3888. doi:10.1002/pen.21069 Phase equilibrium data of CO2 + molten polymer systems are of great relevance for chemical engineers because there are necessary for the optimal design of polymer final-treatment processes. This kind of processes needs information about gas solubilities in polymers at several temperatures and pressures. In this work, CO2 solubilities in molten polymers were modeled by the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) equation of state (EoS). For comparison, the solubilities were also calculated by the Lattice Gas Theory (LGT) EoS, and by the well-known Peng-Robinson (PR) cubic EoS. In order to adjust the interactions between segments of mixtures, there were used classical mixing rules, with one adjustable temperature-dependent binary parameter for the PC-SAFT and PR EoS, and two adjustable binary parameters for the LGT EoS. The results were compared with experimental data obtained from literature. The results in terms of solubility pressure deviations indicate that the vapor-liquid behavior for CO2 + polymer systems is better predicted by the PC-SAFT model than by LGT and PR models. Modeling and simulation of the soybean oil meal desolventizing–toasting process Paraíso, P.R.; Cauneto, H.; Zemp, R.J.; Andrade, C.M.G. Journal of Food Engineering, 86 (2008), 334-341. ISSN: 0260-8774. doi:10.1016/j.jfoodeng.2007.10.010 The desolventizer–toaster (DT) is an important plant equipment in the processing of soybean oil meal, its main purpose being the separation of hexane from the soybean oil meal. The DT must recover as much hexane as possible and produce a good nutritional quality meal with low energy consumption. The aim of this study is to develop a mathematical model for the DT to be used for optimization of operational conditions. The DT was modeled as a column with stages. For each stage complete mass and energy balances were considered, as well as thermodynamic equilibrium between the liquid and vapor phases. The equilibrium data were obtained from operational data of an actual plant. To check the suitability of the proposed model the behavior of the DT under different operating conditions was investigated: influence of hexane concentration of the cake on the meal moisture and the live steam consumption; the influence of the cake inlet temperature on live steam consumption; and the influence of the hexane content of the cake on the indirect steam consumption. Adsorption of antiphospholipid antibodies on affinity magnetoliposomes Pinho, S.C.; Zollner, R.L.; Cuyper, M.; Santana, M.H.A. Colloids and Surfaces B: Biointerfaces, 63 (2008), 249-253. ISSN: 0927-7765. doi:10.1016/j.colsurfb.2007.12.008 Phosphatidylcholine-based magnetoliposomes containing specific ligands for biological molecules, so-called affinity magnetoliposomes, may prove to be useful as adsorbents in applications such as diagnosis or anchoring and delivery of drugs at specific sites in the human body. In the present study, the performance of affinity magnetoliposomes to adsorb anticardiolipin antibodies from a previously characterized pool of patients with autoimmune diseases is described. The magnetic vesicles were prepared by enrobing nanometer-sized colloidal magnetite particles with a phospholipid bilayer composed of dimirystoylphosphatidylcholine and the affinity lipid ligand cardiolipin. Adsorption of antibodies onto the affinity magnetoliposomes assayed using a high-gradient magnetophoresis system, in which the magnetoliposomes were first magnetically captured on stainless steel fibers, and which were subsequently overflowed either with a pool of sera from autoimmune patients or sera of healthy individuals as a control. The spectrophotometric assay showed stronger changes in absorbance spectra when the affinity magnetoliposomes containing cardiolipin were added to sera of autoimmune patients than when they were added to sera of healthy individuals. The breakthrough curves obtained from a frontal analysis of the adsorption in the magnetophoresis system showed a 10% difference for total adsorbed IgG when sera of autoimmune and healthy individuals were assayed on magnetoliposomes containing cardiolipin. Evaluation of a sugarcane bagasse acid hydrolysis technology Rodrigues, F.A.; Guirardello, R. Chemical Engineering & Technology 31 (2008), 883-892. ISSN: 0930-7516. doi:10.1002/ceat.200700454 Conceptual process synthesis (CPS) is an important issue in chemical processing industries. In this paper, the general steps of the life cycle of an acid hydrolysis industrial project are evaluated. Chemical route synthesis, process development (experiments for kinetics and fluid dynamics) and process engineering (definition of basic equipment for economic evaluation) are all investigated. A mathematical model was

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used to generate the most favorable operating conditions for glucose and furfural production from sugarcane bagasse. The material and energy balances were performed by UNISimTM software. The suspension mass fraction and the thermal energy consumption are key issues to account for the profitable operation of the plant. Análisis termodinámico de un sistema de cogeneración con gasificación del licor negro Santos, P.R.; Fábrega, FM.; D’Ángelo, J.V.H. Información Tecnológica, 19 (2008), 47-56. ISSN: 0718-0764. http://www.citchile.cl/revista/v19n4/art07.pdf Se presenta el análisis termodinámico de un proceso de cogeneración de energía con gasificación del licor negro, utilizando balances de exergía para identificar y cuantificar las principales irreversibilidades presentes. Se realizó una simulación del proceso de cogeneración con um simulador comercial, a partir de la cual fue posible realizar el balance de exergía del sistema. Se evaluó la influencia de la composición de los gases obtenidos en el gasificador sobre las pérdidas exergéticas en el proceso. Las condiciones operacionales del gasificador de licor negro que contribuyen a reducir la concentración de estos compuestos responsables de las pérdidas de exergía, son la baja temperatura (700°C) y la baja presión (200 kPa). El análisis mostró útil para determinar de viabilidad técnica del proceso alternativo de generación de energía a través de la gasificación del licor negro. Optimization of the jet steam instantizing process of commercial maltodextrins powders Takeiti, C.Y.; Kieckbusch, T.G.; Collares-Queiroz, F.P. Journal of Food Engineering, 86 (2008), 444-452. ISSN: 0260-8774. doi:10.1016/j.jfoodeng.2007.10.018 Several food powders are submitted to agglomeration in order to enhance their appearance, flowability, and above all, their wettability. This work evaluates the wet agglomeration process of maltodextrins of different degrees of dextrose-equivalent, DE 5–20, following a sequential strategy of experimental designs in order to produce granules with low dissolution time. Initially, a 2(5−1) fractional factorial design was carried out with the independent variables steam pressure (1.5–1.9 bar), feed powder rate (1.6–2.0 g/s), drying air temperature (100–120°C), sucrose and glucose addition (0–10% w/w). The results indicate that an increase in the DE degree increases the number of significant independent variables (p 0.05). The same levels used in the (25−1) fractional factorial design performed previously were adopted in a 23 central composite design that was composed of 11 experimental runs. The surface response analysis indicated that the region of interest for lower dissolution time was found with a steam pressure of 1 bar, feed powder rate at 1.8 g/s and two possible drying air temperatures (93°C or 127°C). The dissolution times of the agglomerates were substantially lower than of the original powder. The different characteristics obtained for the agglomerated maltodextrins could be attributed to the influence of their molecular mass and, consequently, of the glass transition temperature. Mathematical modeling of handmade recycled paper drying kinetics and sorption isotherms Vieira, M.A.G.; Rocha, S.C.S. Brazilian Journal of Chemical Engineering, 25 (2008), 299-312. ISSN: 0104-6632. doi: 10.1590/S0104-66322008000200009 The objective of this work is to analyze and compare the natural and forced convective drying of handmade recycled paper. Drying of recycled cellulose pulp was carried out under laboratory environment conditions and in a convective dryer with forced air circulation and controlled conditions of air temperature and velocity. The tests were conducted following a two-factor central composed factorial design of experiments, with six runs at the central point. The drying results were analyzed and fitted to mathematical models of Fick, Henderson and Pabis (Fick’s modified equation), Page and He (considering the nonlinear Fick effect). The model of Page represented best the experimental data and the one of Henderson and Pabis resulted in an adequate fit for the paper drying kinetics. Sorption isotherms were determined for the dried paper and the models of GAB (Guggenheim-Anderson-de Boer) and GDW (Generalised D’Arcy and Watt) resulted in excellent fits of the experimental data. The water sorption mechanism was suggested by the analysis of the calculated parameters of the GDW model.

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Teses e Dissertações Abril-Junho 2008

Mestrado: 703. Fabian Andrey Díaz-Mateus. Desenvolvimento de modelo computacional para craqueamento térmico. Orientador: Prof.Dr. Rubens Maciel Filho. Defesa: 22/04/2008. 704. Carla Fabiana Scatolim Rombaldo. Síntese de carvão ativado e óleo combustível a partir da borracha de pneu usado. Orientadores: Prof. Dr. Antonio Carlos Luz Lisbôa e Prof. Dr. Aparecido dos Reis Coutinho (UNIMEP). Defesa: 25/04/2008. 705. Fernando Gasi. Avaliação da eficácia de materiais têxteis no desempenho esportivo. Orientador: Prof. Dr. Edison Bittencourt. Defesa: 28/04/2008. 706. Carlos Antonio Berto Jr. Sistema de monitoramento de falhas em tubulações por meio de processamento digital de sinais. Orientadores: Prof. Dr. Elias Basile Tambourgi e Prof. Dr. Sérgio Ricardo Lourenço (UFABC). Defesa: 16/05/2008. 707. Lílian Rodrigues Braga. Desenvolvimento e caracterização de sachê absorvedor de oxigênio para uso em embalagens alimentícias. Orientador: Profa. Dra. Leila Peres. Defesa: 27/05/2008. 708. Michelle Fernanda Faita. Hidrogenação parcial do benzeno em fase líquida: influência da natureza e da morfologia dos suportes alumina e nióbia no desempenho de catalisadores de rutênio. Orientador: Prof. Dr. Antonio José Gómez Cobo. Defesa: 28/05/2008. 709. Juliana Cristina do Nascimento. Desenvolvimento de software e análise de reatores de polimerização de eteno em solução. Orientador: Prof. Dr. Ruben Maciel Filho. Defesa: 28/05/2008. 710. Melina Savioli Lopes. Caracterização das correntes do processo de destilação molecular aplicado a frações pesadas de petróleo e desenvolvimento de correlações da curva PEV. Orientadores: Prof. Dr. Ruben Maciel Filho e Profa. Dra. Maria Regina Wolf Maciel. Defesa: 29/05/2008. 711. Sílvia Dal’Boit. Predição de equilíbrio líquido-vapor através de redes neurais artificiais. Orientador: Prof. Dr. Roger Josef Zemp. Defesa: 23/06/2008. 712. Gabriela Cantarelli Lopes. Desenvolvimento de modelo numérico tridimensional e elíptico para o estudo de escoamentos no interior de dutos cilíndricos. Orientadores: Prof. Dr. José Roberto Nunhez e Dr. Everton Moraes Matos. Defesa: 27/06/2008. Doutorado: 368. Leonardo Machado da Rosa. Aplicação de técnicas CFD para o cálculo de escoamento em meio reativo em riser. Orientador: Prof. Dr. Milton Mori. Defesa: 04/04/2008. 369. Leda Battestin Quast. Estudo do efeito da adição de gorduras alternativas na cristalização da manteiga de cacau. Orientadores: Prof. Dr. Theo Guenter Kieckbusch e Dr. Valdecir Luccas (ITAL). Defesa: 15/04/2008. 370. Vanessa Mendes Santos Cavalcanti. Extração de espilantol de Spilanthes acmella var oleraceae com dióxido de carbono supercrítico. Orientadores: Prof. Dr. Frederico Guaré Cruz (UFBA), Prof. Dr. Martin Aznar e Prof. Dr. Alexandre Beisl Vieira de Melo (UFBA). Defesa: 24/04/2008.

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371. Paula Aparecida Delgado. Desenvolvimento de processo enzimático para redução de sedimentos em extratos de café solúvel. Orientador: Profa. Dra. Telma Teixeira Franco. Defesa: 09/05/2008. 372. Celso Fernandes Joaquim Jr. Desenvolvimento e otimização de misturador estático com o uso da fluidodinâmica computacional (CFD). Orientadores: Prof. Dr. José Roberto Nunhez e Prof. Dr. Efraim Cekinski (EE Mauá). Defesa: 29/05/2008. 373. Consuelo Cristina Gomes Silva. Aplicação de métodos de otimização para o cálculo do equilíbrio químico e de fases combinados para processos com gás de síntese. Orientadores: Prof. Dr. Reginaldo Guirardello e Prof. Dr. Gustavo Paim Valença. Defesa: 06/06/2008. 374. Juliana Belincanta. Homopolimerização e copolimerização via radical livre controlada por radicais nitróxidos. Orientador: Prof. Dr. Liliane Maria Ferrareso Lona. Defesa: 16/06/2008. 375. Daniela Medeiros Devienne Drummond. Otimização do setor de prensagem por meio de planejamento de produção em uma indústria de papel. Orientadores: Prof. Dr. Reginaldo Guirardello, Profa. Dra. Maria Teresa Moreira Rodrigues e Prof. Dr. Ignácio E. Grossmann (Carnegie Mellon University, USA). Defesa: 18/06/2008.

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Notas curtas

Utilização de Recursos Renováveis No mês de abril, o Dr. Joachim Venus (na foto), do Departamento de Bioengenharia do Instituto Leibniz de Engenharia Agrícola Potsdam-Bornim (Alemanha), ministrou um curso sobre a utilização de recursos renováveis para a obtenção de ácidos orgânicos por fermentação. A vinda do Dr. Venus foi organizada pela Profa. Dra Telma Franco, do Departamento de Processos Químicos, no âmbito do Projeto Alfa de cooperação Brasil-Alemanha.

Dr. Joachim Venus

Curso “Agitação e Mistura em Processos Industriais” Nos dias 5 e 6 de junho foi oferecido, no Conselho Regional de Química, em São Paulo, o curso “Agitação e Mistura em Processos Industriais”, sob responsabilidade do Prof. Dr. José Roberto Nunhez, do Departamento de Processos Químicos. O curso, que conta com os professores José Roberto Nunhez (FEQ), Efraim Cekinski (E.E. Mauá), Celso Fernandes Joaquim Jr. (Kroma) e José Geraldo da Cruz Pradella (Instituto Butantã), teve uma carga de 16 h e esteve direcionado a profissionais de nível técnico e superior que atuam nas áreas de projetos e processos industriais. O curso foi realizado pela Associação Brasileira de Engenharia Química (ABEQ).

Nova sinalização na FEQ Foi implantado um novo sistema de sinalização interna, com totens na porta de cada bloco e na entrada principal da faculdade. O projeto gráfico integrado do sistema de sinalização permite uma localização rápida e precisa dos departamentos, setores administrativos e laboratórios de pesquisa.

A Coordenadoria de Relações Internacionais da Unicamp, CORI, apresentou no dia 10 de junho os ganhadores das Bolsas Santander de Mobilidade Internacional para 2008. Na FEQ foram selecionados os alunos Guilherme José Castilho e Victor Hugo Álvarez, da pós-graduação, e Atahualpa Moura Mendes, da graduação. Parabéns aos alunos contemplados!

A Rede de Nanocosméticos, criada em 2005 pelo Ministério da Ciência e Tecnologia, foi objeto de matéria na revista Pesquisa FAPESP 146. Dentre os vários grupos que compõem a rede, o grupo coordenado pela Profa. Dra. Maria Helena Andrade Santana, do Departamento de Processos Biotecnológicos, foca suas pesquisas no desenvolvimento de nano partículas de ácido hialurônico e lipossomas de tipo elástico, que atuam como cápsulas transportadoras de princípios ativos em cremes que atuam uma camada abaixo da pele. Como os poros da pele têm, em media, 30 nanômetros, e as partículas de lipossoma devem ter cerca de 100 nanômetros para poder carregar uma quantidade significativa do princípio ativo, a partícula deve ser elástica para poder se deformar e passar pelos poros sem perder a sua integridade; também deve ser recoberta com polímeros hidrofílicos para proteger a superfície do lipossoma do atrito ao passar pelo poro.

MINTER/DINTER aprovado na CAPES A CAPES aprovou o oferecimento de uma turma especial pelo curso de pós-graduação da FEQ no âmbito dos programas MINTER/DINTER junto à Universidade Estadual do Amazonas (UEA). Segundo este programa, os docentes da FEQ deverão ministrar disciplinas na UEA e os alunos devem permanecer pelo menos 5 meses (no caso de mestrado) e 9 meses (no caso de doutorado) na UNICAMP desenvolvendo suas pesquisas. Parte da pesquisa pode ser desenvolvida na UEA.

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Projetos aprovados no PNPD O Programa Nacional de Pós-Doutorado – Ação em Áreas Estratégicas divulgou os projetos aprovados nos editais MCT/FINEP/CNPq 034/2007 e MEC/CAPES. Três professoras da FEQ tiveram projetos aprovados: � Profa. Dra. Maria Regina Wolf Maciel. � Profa. Dra. Marisa Masumi Beppu. Síntese,

caracterização e aplicação de plastificantes.

� Profa. Dra. Meuris Gurgel Carlos da Silva. Adsorção/dessorção de metais pesados (Ni e Zn) em argila.

Contrapartida a Projetos FAPESP O Conselho Universitário aprovou a concessão de recursos orçamentários como contrapartida aos projetos Fapesp obtidos ou com recursos liberados em 2007. Doze professores da FEQ foram contemplados, com um total de R$ 109.705,30, que equivalem a 5,29% do total de recursos liberados pela FAPESP para a FEQ em 2007. Parabéns aos professores contemplados! � Prof. Dr. Cesar Costapinto Santana � Prof. Dr. Elias Basile Tambourgi � Profa. Dra. Liliane Lona � Profa. Dra. Maria Helena Andrade Santana � Profa. Dra. Maria Regina Wolf Maciel � Prof. Dr. Martín Aznar � Profa. Dra. Meuris Gurgel Carlos da Silva � Prof. Dr. Rubens Maciel Filho � Profa. Dra. Sandra Cristina Santos Rocha � Profa. Dra. Sônia Maria Alves Bueno � Profa. Dra. Telma Teixeira Franco � Prof. Dr. Theo Guenter Kieckbusch

CAPES aprova projetos Pró-Engenharias Três professores da FEQ tiveram projetos aprovados pela CAPES no âmbito do programa Pró-Engenharias. São eles: � Prof. Dr. Cesar Costapinto Santana.

Processos cromatográficos contínuos e descontínuos para separações de produtos biotecnológicos (UNICAMP, UFRJ, UFC)

� Profa. Dra. Maria Regina Wolf Maciel. Rede de pesquisa em engenharia de biocombustíveis (UNICAMP, UFPR).

� Prof. Dr. Reginaldo Guirardello. Produção de biodiesel em coluna de destilação reativa (UNICAMP, UEM, URI, UNIOESTE).

Aluno de graduação da FEQ conquista prêmio na Petrobrás O aluno de graduação Luís Fernando Paolucci, funcionário da Petrobrás (Replan), ganhou o Prêmio Apoena na categoria rentabilidade e lucratividade pelo terceiro ano consecutivo (2006, 2007 e 2008).

A empresa júnior PROPEQ estabeleceu uma nova parceria institucional com a Dow Chemical do Brasil. O estabelecimento de boas parcerias possui uma importância estratégica imensa para a PROPEQ para a capacitação dos alunos de graduação, projetos comerciais e captação de recursos. A Dow é líder mundial no fornecimento de soluções inovadoras em plásticos, além de atuar na busca de alternativas para a potencialização do agronegócio e na produção de uma gama extremamente diversificada de produtos químicos. Daniel Assumpção, diretor de relações institucionais, conta que a PROPEQ foi procurada pela Dow em busca de mecanismos de aproximação com a Universidade, alunos de graduação e pesquisa de ponta. Chegou-se à conclusão de que a forma de maximizar o alcance de tais objetivos seria a parceria institucional com a PROPEQ. Além da presença durante a Semana de Engenharia Química, a empresa garante benefícios como veiculação de marca em todo o material gráfico e de divulgação da PROPEQ, estreitamento de relacionamento com membros da FEQ através de visitas à planta por parte dos alunos de graduação, palestras e cursos de capacitação, em especial em aspectos práticos de Engenharia Química desenvolvidos na indústria. Segundo Daniel, este tipo de aproximação é igualmente válida quando se trata da relação entre o meio acadêmico como um todo e a indústria. Além de a parceria trazer a empresa para ministrar aulas relacionadas a disciplinas da graduação vinculadas às suas linhas de produção, existe espaço para que os próprios professores da FEQ possam utilizar os benefícios que a empresa pode proporcionar, a fim de agregar conhecimento aos alunos ou mesmo desenvolver linhas de pesquisa. Este tipo de parceria é de mútua importância e garante à PROPEQ uma inserção mais efetiva no mercado.