Closed-loop stable model predictive control of integrating systems with dead time

Model predictive control (MPC) applications in the process industry usually deal with process systems that show time delays (dead times) between the system inputs and outputs. Also, in many industrial applications of MPC, integrating outputs resulting from liquid level control or recycle streams need to be considered as controlled outputs. Conventional MPC packages can be applied to time-delay systems but stability of the closed loop system will depend on the tuning parameters of the controller and cannot be guaranteed even in the nominal case. In this work, a state space model based on the analytical step response model is extended to the case of integrating time systems with time delays. This model is applied to the development of two versions of a nominally stable MPC, which is designed to the practical scenario in which one has targets for some of the inputs and/or outputs that may be unreachable and zone control (or interval tracking) for the remaining outputs. The controller is tested through simulation of a multivariable industrial reactor system. (C) 2012 Elsevier Ltd. All rights reserved.

CHARACTERIZATION OF LYOPHILIZED LIPOSOMES PRODUCED WITH NON-PURIFIED SOY LECITHIN: A CASE STUDY OF CASEIN HYDROLYSATE MICROENCAPSULATION

A commercial casein hydrolysate was microencapsulated in liposomes produced with non-purified soy lecithin, cryoprotected with two different disaccharides and lyophilized. The encapsulation efficiency of casein hydrolysate ranged from 30 to 40%. The powders were analyzed by differential scanning calorimetry (DSC), scanning electron micrography (SEM), infrared spectroscopy (FTIR) and wide angle X-ray diffraction (WAXD). DSC data revealed the presence of an exothermal transition in empty lyophilized liposomes, which was ascribed to the presence of a quasicrystalline lamellar phase (intermediary characteristics between the L-beta and L-c phases). The addition of peptides to the liposomal system caused the disappearance of this exothermic phenomenon, as they were located in the polar headgroup portion of the bilayer, causing disorder and preventing the formation of the quasicrystalline phase. Infrared data indicated the presence of the peptides in the lyophilized formulations and showed that the cryoprotectants interacted effectively with the polar heads of phospholipids in the bilayer.

Liquid-liquid equilibria for systems composed of rice bran oil and alcohol-rich solvents: Application to extraction and deacidification of oil

The liquid-liquid equilibria of systems composed of rice bran oil, free fatty acids, ethanol and water were investigated at temperatures ranging from 10 to 60 degrees C. The results of the present study indicated that the mutual solubility of the compounds decreased with an increase in the water content of the solvent and a decrease in the temperature of the solution. The experimental data set was correlated by applying the UNIQUAC model. The average variance between the experimental and calculated compositions was 0.35%, indicating that the model can accurately predict behavior of the compounds at different temperatures and degrees of hydration. The adjustment of interaction parameters enables both the simulation of liquid-liquid extractors for deacidification of vegetable oil and the prediction of phase compositions for the oil and alcohol-rich phases that are generated during cooling of the stream exiting the extractor (when using ethanol as the solvent). (C) 2012 Elsevier Ltd. All rights reserved.

Dilute Acid Hydrolysis of Sugar Cane Bagasse at High Temperatures: A Kinetic Study of Cellulose Saccharification and Glucose Decomposition. Part I: Sulfuric Acid as the Catalyst

The kinetics of sugar cane bagasse cellulose saccharification and the decomposition of glucose under extremely low acid (ELA) conditions, (0.07%), 0.14%, and 0.28% H2SO4, and at high temperatures were investigated using batch reactors. The first-order rate constants were obtained by weight loss, remaining glucose, and fitting glucose concentration profiles determined with HPLC using the Saeman model. The maximum glucose yields reached 67.6% (200 degrees C, 0.07% H2SO4, 30 min), 69.8% (210 degrees C, 0.14% H2SO4, 10 min), and 67.3% (210 degrees C, 0.28% H2SO4, 6 min). ELA conditions produced remarkable glucose yields when applied to bagasse cellulose. The first-order rate constants were used to calculate activation energies and extrathermodynamic parameters to elucidate the reaction mechanism under ELA conditions. The effect of acid concentration on cellulose hydrolysis and glucose decomposition was also investigated. The observed activation energies and reaction orders with respect to hydronium ion for cellulose hydrolysis and glucose decomposition were 184.9 and 124.5 kJ/mol and 1.27 and 0.75, respectively.

Evaluation of the Adenanthera pavonina seed proteinase inhibitor (ApTI) as a bioinsecticidal tool with potential for the control of Diatraea saccharalis

Diatraea saccharalis, is a major sugarcane pest, causing damage to the stalks of sugarcane plants. In this study, a trypsin inhibitor (ApTI) was purified from Adenanthera pavonina seeds and was tested for its insect growth regulatory effect. ApTI showed a dose-dependent effect on average larval weight and survival. 0.1% ApTI produced approximately 67% and 50% decreases in weight and survival larval, respectively. The results from dietary utilization experiments with D. saccharalis larvae showed a reduction in the efficiency of conversion of ingested food and digested food, and an increase in approximate digestibility and metabolic cost. The level of trypsin was significantly decreased (ca. 55%) in the midgut of larvae reared on a diet containing 0.05% ApTI and the trypsin activity in ApTI-fed larvae demonstrated sensitivity to ApTI. The action of ApTI on the development of D. saccharalis larvae shows that this protein may have great toxic potential. (C) 2011 Elsevier Ltd. All rights reserved.

Experimental analyses of the poly(vinyl chloride) foams' mechanical anisotropic behavior

Assessing a full set of mechanical properties is a rather complicate task in the case of foams, especially if material models must be calibrated with these results. Many issues, for example anisotropy and heterogeneity, influence the mechanical behavior. This article shows through experimental analyses how the microstructure affects different experimental setups and it also quantifies the degree of anisotropy of a poly(vinyl chloride) foam. Monotonic and cyclic experimental tests were carried out using standard compression specimens and non-standard tensile specimens. Results are complemented and compared with the aid of a digital image correlation technique and scanning electron microscopy analyses. Mechanical properties (e.g., elastic and plastic Poisson's ratios) are evaluated for compression and tensile tests, for two different material directions (normal and in-plane). The material is found to be transversely isotropic. Differences in the results of the mechanical properties can be as high as 100%, or even more depending on the technique used and the loading direction. Also, the experimental analyses show how the material's microstructure behavior, like the evolution of the herein identified yield fronts and a spring back phenomenon, can influence the phenomenological response and the failure mechanisms as well as the hardening curves. POLYM. ENG. SCI., 52:2654-2663, 2012. (C) 2012 Society of Plastics Engineers

Spray Congealing of Pharmaceuticals: Study on Production of Solid Dispersions Using Box-Behnken Design

This work aimed at evaluating the spray congealing method for the production of microparticles of carbamazepine combined with a polyoxylglyceride carrier. In addition, the influence of the spray congealing conditions on the improvement of drug solubility was investigated using a three-factor, three-level Box-Behnken design. The factors studied were the cooling air flow rate, atomizing pressure, and molten dispersion feed rate. Dependent variables were the yield, solubility, encapsulation efficiency, particle size, water activity, and flow properties. Statistical analysis showed that only the yield was affected by the factors studied. The characteristics of the microparticles were evaluated using X-ray powder diffraction, scanning electron microscopy, differential scanning calorimetry, and hot-stage microscopy. The results showed a spherical morphology and changes in the crystalline state of the drug. The microparticles were obtained with good yields and encapsulation efficiencies, which ranged from 50 to 80% and 99.5 to 112%, respectively. The average size of the microparticles ranged from 17.7 to 39.4 mu m, the water activities were always below 0.5, and flowability was good to moderate. Both the solubility and dissolution rate of carbamazepine from the spray congealed microparticles were remarkably improved. The carbamazepine solubility showed a threefold increase and dissolution profile showed a twofold increase after 60 min compared to the raw drug. The Box-Behnken fractional factorial design proved to be a powerful tool to identify the best conditions for the manufacture of solid dispersion microparticles by spray congealing.

Water-assisted Flow of Heavy Oil in a Vertical Pipe: Pilot-scale Experiments

The use of the core-annular flow pattern, where a thin fluid surrounds a very viscous one, has been suggested as an attractive artificial-lift method for heavy oils in the current Brazilian ultra-deepwater production scenario. This paper reports the pressure drop measurements and the core-annular flow observed in a 2 7/8-inch and 300 meter deep pilot-scale well conveying a mixture of heavy crude oil (2000 mPa.s and 950 kg/m3 at 35 C) and water at several combinations of the individual flow rates. The two-phase pressure drop data are compared with those of single-phase oil flow to assess the gains due to water injection. Another issue is the handling of the core-annular flow once it has been established. High-frequency pressure-gradient signals were collected and a treatment based on the Gabor transform together with neural networks is proposed as a promising solution for monitoring and control. The preliminary results are encouraging. The pilot-scale tests, including long-term experiments, were conducted in order to investigate the applicability of using water to transport heavy oils in actual wells. It represents an important step towards the full scale application of the proposed artificial-lift technology. The registered improvements in terms of oil production rate and pressure drop reductions are remarkable.

Liquid-Liquid Equilibrium Data for the System Lard plus Oleic Acid plus Ethanol + Water at 318.2 K: Cholesterol Distribution Coefficients

This research reports liquid liquid equilibrium data for the system lard (swine fat), cis-9-octadecenoic acid (oleic acid), ethanol, and water at 318.2 K, as well as their correlation with the nonrandom two-liquid (NRTL) and universal quasichemical activity coefficient (UNIQUAC) thermodynamic equations, which have provided global deviations of 0.41 % and 0.53 %, respectively. Additional equilibrium experiments were also performed to obtain cholesterol partition (or distribution) coefficients to verify the availability of the use of ethanol plus water to reduce the cholesterol content in lard. The partition experiments were performed with concentrations of free fatty acids (commercial oleic acid) that varied from (0 to 20) mass % and of water in the solvent that varied from (0 to 18) mass %. The percentage of free fatty acids initially present in lard had a slight effect on the distribution of cholesterol between the phases. Furthermore, the distribution coefficients decreased by adding water in the ethanol; specifically, it resulted in a diminution of the capability of the solvent to remove the cholesterol.

Microparticulated Hydrochlorothiazide Solid Dispersion: Enhancing Dissolution Properties via Spray Drying

The aim of the present study was to obtain microparticles of hydrochlorothiazide, a diuretic drug that practically insoluble in water, by spray drying and to investigate the influence of process parameters using a three-level, three-factor Box-Behnken design. Process yields, moisture content, particle size, flowability, and solubility were used to evaluate the spray-dried microparticles. The data were analyzed by response surface methodology using analysis of variance. The independent variables studied were outlet temperature, atomization pressure, and drug content. The formulations were prepared using polyvinylpyrrolidone and colloidal silicon dioxide as the hydrophilic carrier and drying aid, respectively. The microparticle yield ranged from 18.15 to 59.02% and resulted in adequate flow (17 to 32 degrees), moisture content between 2.52 to 6.18%, and mean particle size from 45 to 59 mu m. The analysis of variance showed that the factors studied influenced the yields, moisture content, angle of repose, and solubility. Thermal analysis and X-ray diffractometry evidenced no drug interactions or chemical modifications. Photomicrographs obtained by scanning electron microscopy showed spherical particles. The solubility and dissolution rates of hydrochlorothiazide were remarkably improved when compared with pure drug. Therefore, the results confirmed the high potential of the spray-drying technique to obtain microparticulate hydrochlorothiazide with enhanced pharmaceutical and dissolution properties.

Reforming of a model biogas on Ni and Rh-Ni catalysts: Effect of adding La

Ni catalysts supported on gamma-Al2O3 modified by Rh and La were prepared and evaluated on the reforming of a model biogas. The catalysts were characterized by EDS, XRD, TPR, XANES and surface area estimation (BET). The results showed that in the original Ni catalyst, the Ni interacted strongly with the alumina support, exhibiting high reduction temperatures in TPR tests. In the catalytic tests, the addition of Rh on Ni catalysts improved CH4 conversion but also increased carbon deposition, possible by causing the segregation of Ni species under the reaction conditions. The presence of La on Ni catalysts reduced the carbon deposition by favoring the gasification of carbon species. Addition of synthetic air to the process improved the CH4 conversion and also decreased the carbon formation. The catalysts Ni, Rh-NiLa, and Rh showed good results in the conversion of model sulfur-free biogas, which suggests that they are promising catalysts to be tested in conversion of real biogas. (C) 2012 Elsevier B.V. All rights reserved.

Production of xylanase and beta-xylosidase from autohydrolysis liquor of corncob using two fungal strains

Agroindustrial residues are materials often rich in cellulose and hemicellulose. The use of these substrates for the microbial production of enzymes of industrial interest is mainly due to their high availability associated with their low cost. In this work, corncob (CCs) particles decomposed to soluble compounds (liquor) were incorporated in the microbial growth medium through autohydrolysis, as a strategy to increase and undervalue xylanase and beta-xylosidase production by Aspergillus terricola and Aspergillus ochraceus. The CCs autohydrolysis liquor produced at 200 A degrees C for 5, 15, 30 or 50 min was used as the sole carbon source or associated with untreated CC. The best condition for enzyme synthesis was observed with CCs submitted to 30 min of autohydrolysis. The enzymatic production with untreated CCs plus CC liquor was higher than with birchwood xylan for both microorganisms. A. terricola produced 750 total U of xylanase (144 h cultivation) and 30 total U of beta-xylosidase (96-168 h) with 0.75% untreated CCs and 6% CCs liquor, against 650 total U of xylanase and 2 total U of beta-xylosidase in xylan; A. ochraceus produced 605 total U of xylanase and 56 total U of beta-xylosidase (168 h cultivation) with 1% untreated CCs and 10% CCs liquor against 400 total U of xylanase and 38 total U of beta-xylosidase in xylan. These results indicate that the treatment of agroindustrial wastes through autohydrolysis can be a viable strategy in the production of high levels of xylanolytic enzymes.

Microencapsulation of Ketoprofen in Blends of Acrylic Resins by Spray Drying

Microparticles of ketoprofen entrapped in blends of acrylic resins (Eudragit RL 30D and RS 30D) were successfully produced by spray drying. The effects of the proportion ketoprofen : polymer (1: 1 and 1: 3) and of spray-drying parameters (drying gas inlet temperatures of 80 and 100 degrees C; microencapsulating composition feed flow rates of 4 and 6 g/min) on the microparticles properties (drug content, encapsulation efficiency, mean particle size, moisture content, and dissolution behavior) were evaluated. Differential scanning calorimetry (DSC) thermograms and X-ray diffractograms of the spray-dried product, the free drug, and the physical mixture between the free drug and spray-dried composition (blank) were carried out. Microparticles obtained at inlet temperature of 80 degrees C, feed flow rate of 4 g/min, and ketoprofen : acrylic resin ratio of 1: 3 presented an encapsulation efficiency of 88.1%, moisture content of 5.8%, production yield around 50%, and a higher reduction in dissolution rate of the entrapped ketoprofen. Sigmoidal shape dissolution profiles were presented by the spray-dried microparticles. The dissolution profiles were relatively well described by the Weibull model, a showing high coefficient of determination, R-2, and a mean absolute error between experimental and estimated values of between 4.6 and 10.1%.

Co-metabolic models of Streptococcus thermophilus in co-culture with Lactobacillus bulgaricus or Lactobacillus acidophilus

To shed light on the interactions occurring in fermented milks when using co-cultures of Streptococcus thermophilus with Lactobacillus bulgaricus (StLb) or Lactobacillus acidophilus (StLa), a new co-metabolic model was proposed and checked either in the presence of Inulin as a prebiotic or not. For this purpose, the experimental data of concentrations of substrates and fermented products were utilized in balances of carbon, reduction degree and ATP. S. thermophilus exhibited always quicker growth compared to the other two microorganisms, while the percentage of lactose fermented to lactic acid, that of galactose metabolized, and the levels of diacetyl and acetoin formed strongly depended on the type of co-culture and the presence of inulin. The StLb co-culture led to higher acetoin and lower diacetyl levels compared to StLa, probably because of more reducing conditions or limited acetoin dehydrogenation. Inulin addition to StLa suppressed acetoin accumulation and hindered that of diacetyl, suggesting catabolite repression of alpha-acetolactate synthase expression in S. thermophilus. Both co-cultures showed the highest ATP requirements for biomass growth and maintenance at the beginning of fermentation, consistently with the high energy demand of enzyme induction during lag phase. Inulin reduced these requirements making biomass synthesis and maintenance less energy-consuming. Only a fraction of galactose was released from lactose, consistently with the galactose-positive phenotype of most dairy strains. The galactose fraction metabolized without inulin was about twice that in its presence, which suggests inhibition of the galactose transport system of S. thermophilus by fructose released from partial inulin hydrolysis. (C) 2012 Elsevier B.V. All rights reserved.

Alkaline sulfite/anthraquinone pretreatment followed by disk refining of Pinus radiata and Pinus caribaea wood chips for biochemical ethanol production

BACKGROUND: Alkaline sulfite/anthraquinone (ASA) cooking of Pinus radiata and Pinus caribaea wood chips followed by disk refining was used as a pretreatment for the production of low lignified and high fibrillated pulps. The pulps produced with different delignification degrees and refined at different energy inputs (250, 750 and 1600 Wh) were saccharified with cellulases and fermented to ethanol with Saccharomyces cerevisiae using separated hydrolysis and fermentation (SHF) or semi-simultaneous saccharification and fermentation (SSSF) processes. RESULTS: Delignification of ASA pulps was between 25% and 50%, with low glucans losses. Pulp yield was from 70 to 78% for pulps of P. radiata and 60% for the pulp of P. caribaea. Pulps obtained after refining were evaluated in assays of enzymatic hydrolysis. Glucans-to-glucose conversion varied from 20 to 70%, depending on the degree of delignification and fibrillation of the pulps. The best ASA pulp of P. radiata was used in SHF and SSSF experiments of ethanol production. Such experiments produced maximum ethanol concentration of 20 g L-1, which represented roughly90% of glucose conversion and an estimated amount of 260 L ethanol ton(-1) wood. P. caribaea pulp also presented good performance in the enzymatic hydrolysis and fermentation but, due to the low amount of cellulose present, only 140 L ethanol would be obtained from each ton of wood. CONCLUSION: ASA cooking followed by disk refining was shown to be an efficient pretreatment process, which generated a low lignified and high-fibrillated substrate that allowed the production of ethanol from the softwoods with high conversion yields. (C) 2012 Society of Chemical Industry