Interest in aqueous systems containing alcohols and esters stems from the use of these compounds in food technology as aromas and extractants. In this work, liquid-liquid equilibrium (LLE) data are determined for the type I ternary systems ethyl acetate + ethanol + water and butyl acetate + ethanol + water, and the type II system ethyl acetate + butyl acetate + water at 25, 35 and 45°C. The experimental data are correlated by the NRTL and UNIQUAC equations using two approaches: a) system-by-system correlation; and b) joint correlation of the combined data for the three systems, affording common binary interaction parameters. Both models satisfactorily correlate the data. The binary interaction parameters obtained, in combination with those for further systems, will be useful for predicting the activity coefficients and LLE data of diverse multicomponent systems.
Modeling and numerical solutions of vapor phase epitaxy are limited because of convergence ability and a large number of iterations. To overcome these limitations, for the first time two Newton-like methods have been applied to models of vapor phase epitaxy for GaAs and InxGa1–xP: The Newton-Raphson method (NRM) and the power-law formalism method (PLFM). We compare the performances of the two methods in terms of the ability of convergence and the iteration numbers. The results indicate that PLFM is always significantly superior to NRM. All calculations by PLFM successfully converge from a rough estimated initial values for equilibrium partial pressures, where NRM can not. These results suggest that the limitation in the numerical calculations of the vapor growth epitaxy can be widely extended by the application of PLFM.
A modified-Soave-Redlich-Kwong (MSRK) equation of state with an exponent-type mixing rule for the energy parameter and a conventional mixing rule for the size parameter is applied to correlate the phase equilibria for four binary mixtures of water + hydrocarbon (benzene, hexane, decane, and dodecane) systems at high temperatures and pressures. It is noted that good correlation results are obtained by using the mixing rules with interaction parameters between unlike molecules.
As a basis for the development of energy storage systems utilizing crystallization/dissolution of chemical substances, an experimental study is performed for crystallization of ammonium sulfamate from an aqueous solution confined in a rectangular vessel. A molded polycrystal adhering to one of the vertical walls in the vessel was made to grow by cooling the opposite wall. The behavior of natural convection in the solution was visualized using granulated tracers. In addition, local changes in solution temperature were also measured. In the neighborhood of the growing polycrystal, upward flows develope through the decerase in concentration of solution due to crystal growth, as well as by the increase in temperature due to the latent heat of crystallization. Dilute solution transferred upward is retained at the top of the vessel to form a horizontal rolling cell there. After that, ascending dilute solution is retained above the cell, and forms a second cell. Finally, horizontal multi-layers are established in the liquid phase. Moreover, the effects of cooling rate and flow structure on the crystal growth is discussed.
The minimum impeller speed needed to obtain complete liquid-liquid dispersion in baffled vessels is examined experimentally for six-blade disk turbines, flat paddles, pitched paddles and four-blade propellers of three different sizes. The minimum impeller speed for complete liquid-liquid dispersion is detected by the method developed by using a multimeter. From the data obtained in this work, the impeller position above the vessel base to get the minimum power input for complete liquid-liquid dispersion is determined. The correlation for the minimum impeller speed for complete liquid-liquid dispersion in baffled vessels is also proposed.
It is well known that the use of certain surfactants and counterions can cause drag reduction in pipe flow. This phenomenon can be applied to a district heating and cooling system. In such a system, however, heat transfer reduction correspondingly occurs as drag reduction does. This should be a major problem as far as heat transfer application is concerned. In our study in this regard, we focused on drag reduction in practical heat exchanger tubes and determined the effect of drag reduction caused by a surfactant solution of Ethoquad O/12. We used three rough tubes with different groove pitches and heights in our experiments to evaluate the effect of the roughness shape. From the results, we estimated the magnitude of the heat transfer reduction.
A new approach to bubble column scale-up based on the quality of mixedness derived from the information entropy concept is presented. Using a step response method for studying mixing in the liquid phase, the carbon dioxide tracer concentrations absorbed in deionized water in a bubble column of 0.289 m in ID have been measured by an electrical conductivity probe under steady flow conditions. The superficial gas velocity was set at 0.0178 m·s–1, 0.0305 m·s–1 and 0.0381 m·s–1 (bubbly flow regime) under clear liquid heights of 0.56 m and 1.84 m, respectively. Following an original algorithm based on the stepwise change of the measured tracer concentrations with time in respective pertinently divided beds, a quality of mixedness concept has been evaluated for the above mentioned operating conditions. It is found that the change of quantity with introduced dimensionless time in this study does not depend on the superficial gas velocity and clear liquid height. The authors argue that for the case of physical absorption of carbon dioxide in deionized water in the bubbly flow regime, the quality of mixedness is dominated by mass transfer from the bubbles to the surrounding liquid and in turn to turbulent mixing on the scale of a mean bubble diameter, which is associated with the liquid transported in the wakes of the rising bubbles. In the present study, the dimensionless quality of mixedness can be related distinctly to a dimensionless time which is defined as the elapsed time divided by the contact time (the Sauter-mean bubble diameter divided by the bubble rise velocity) based on the classical penetration theory. The derived relationship provides significant new information about bubble column scale-up. In addition, a comparison between the quality of mixedness in the upper and lower sections has been illustrated.
A new method for simultaneous measurement of weight, temperature and surface area of an evaporating pendant drop in dry air has been proposed by using a precise analytical balance, a microcomputer with A-D converter, and a microscope with image acquisition system. Unsteady simultaneous measurements of weight, temperature and surface area of an alumina slurry drop and one containing dissolved poly(vinyl alcohol) (PVA) have been made for a wide range of free stream temperatures T∞ = 323–393 K and initial concentrations of PVA CPA0 = 0–10 wt% at free stream velocity U∞ = 0.72 m/s and initial concentration of fine alumina particles CA0 = 50 wt%. The dimensionless diffusion fluxes and Nusselt numbers of an alumina slurry drop are compared with those for a pure water drop and show a fairly good agreement with those for a water drop during the constant rate period of evaporation. The dimensionless diffusion fluxes of an alumina slurry drop containing dissolved PVA are affected by the initial concentrations of PVA and free stream temperatures and show a large deviation from those for a water drop, while Nusselt numbers show a fairly good agreement with those for a water drop.
The thermal conductivity of H2O + CoCl2 solutions was measured over the temperature range 293 to 473 K using a parallel-plate apparatus. Data cover the pressure range from 0.1 to 100 MPa. Measurements were made on ten isotherms, namely: 293, 313, 333, 353, 373, 393, 413, 433, and 473 K. The concentrations studied were 2.5, 5, 10, 15, 20, and 25 wt % CoCl2. The uncertainty of thermal conductivity measurements was estimated to be ±1.6%. The pressure effect on thermal conductivity behavior was similar for H2O and H2O + CoCl2. In the temperature range of our experiments, isotherms of thermal conductivity were almost linear function of pressure at all temperatures for each concentrations. Along each isobar a given concentration the thermal-conductivity of H2O + CoCl2 solutions exhibits a maximum at temperatures between 405 and 419 K. The measured values of thermal conductivity are compared with the experimental and correlation results of other investigators. A new correlation which yields the correct temperature, pressure, and concentration behavior of thermal conductivity is proposed. This maximum is displaced to higher temperature when the pressure is increased at each compositions. For fixed pressure the maximum is displaced to lower temperature when the composition is increased.
To estimate mass transfer rate during bubble formation at an orifice, a theoretical model is proposed for soluble gas bubble formation in liquid by modifying the non-spherical bubble formation model. The absorption rate from pure SO2 gas bubble to water is experimentally measured as well as bubble shape and growth rate. Mass transfer from the gas-liquid interface during bubble growth is described well by the penetration theory. Experimental bubble shape, bubble volume at its detachment from an orifice, growth rate and mass transfer rate are estimated well by the present model.
Dehydrohalogenation of 2-bromooctane in the organic phase with dodecane solvent by using phase transfer catalysts (PTC) was carried out in a batch reactor with potassium hydroxide solvent in the aqueous phase. A synergetic effect of PTC was observed for the combination of tetrahexyl ammonium bromide ((Hex)4NBr) and polyethylene glycols (PEG) in the third phase. The observed reaction rate constant (kobs), which is determined from the first order kinetics, depends on the average molecular weight of PEG, and remarkably increases with the increasing KOH concentration in the aqueous phase. If the optimum combination of (Hex)4NBr and PEG with average molecular weight of 200 (PEG200) is used, the amount of quaternary ammonium salt can be significantly saved (for example, by one-nineteenth). The volume of the third phase and the concentration of water in the third phase (CH2O) were measured and related to the reaction rate constant as well as the distribution coefficient (KA). Catalysts which exist in the third phase can be reused without any loss of catalytic activity.
An industrial scale process is proposed for the synthesis of ethyl tert-butyl ether (abbreviated as ETBE) from bioethanol and tert-butyl alcohol (TBA), and simulated by using ASPEN PLUS, a sequential modular simulation software package. The IB-rich gaseous product from the first reactive distillation column is used to react with pure ethanol (EtOH) in the second reactive distillation column. The overall conversion of tert-butyl alcohol (TBA) and the overall ETBE selectivity are 98.9 and 99.9%, respectively.
Experiments on ternary distillation were made for a nitrogen-argon-oxygen system in a wetted-wall column under total reflux conditions for wide ranges of vapor concentrations and flow rates (especially turbulent flow region), and simultaneous heat and mass transfer was examined. Heights of transfer units for the intermediate component, argon, show discontinuity near the zero driving force region. The observed diffusion fluxes of each component in ternary distillation are found to be proportional to their concentration driving forces, whereas the observed mass fluxes are not. This is due to the convective mass fluxes caused by mass fluxes of the other components. The observed diffusion fluxes in the ternary distillation of air show good agreement with the previously developed binary correlation using Wilke’s effective diffusion coefficients. The separation performance of cryogenic air distillation under total reflux conditions in a wetted-wall column is predicted by using the correlation for ternary diffusion fluxes. Predicted separation performance shows good agreement with the observed data. The effect of interaction between diffusion fluxes in air distillation is also discussed.
Potassium sulfate was crystallized in a seeded batch cooling crystallizer with no temperature control or natural cooling. Above a critical seed concentration, uni-modal product of grown seeds was obtained even under a natural cooling mode with practically no nucleation. This ideal growth of seed crystals is contrary to the common belief that a natural cooling mode produces small size products with enormous secondary nucleation. The critical seed concentration can be determined easily with data from a laboratory crystallizer on the seed chart, in which the product mean mass size normalized with the seed mean mass size is plotted as a function of seed concentration with seed size as a parameter. A simple and practical method to design a batch crystallizer to be operated with no nucleation has been proposed.
The kinetic behavior of the extraction of aluminum and beryllium with dinonylnaphthalene sulfonic acid (DNNSA), bis(2-ethylhexyl)phosphoric acid (D2EHPA) and their mixture was studied using a stirred transfer cell. The extraction rate obtained with DNNSA is 5–50 times larger than that obtained with D2EHPA. The rate-determining step in the extraction with D2EHPA is the reaction between metal ion and dimeric D2EHPA. The diffusion steps for the DNNSA reverse micelles in the organic phase and for the metal ions in the aqueous phase, however, govern the overall rate of extraction with DNNSA. The extraction rate obtained with the DNNSA-D2EHPA mixed micelles is greater than the sum of those obtained with each extractant. This increased rate is also expressed satisfactorily by the diffusion steps as in the case of DNNSA micelles. The synergistic effect on the extraction rate for beryllium is explained by an increase in the distribution ratio of the metal caused by inclusion of D2EHPA molecules into DNNSA micelles. A larger acceleration effect is observed for aluminum, suggesting reactive extraction by D2EHPA at the micro interface of reverse micelles in addition to the bulk interface.
Morphology and purity of crystalline particles of m-chloronitrobenzene (m-CNB) from a batch suspension crystallizer were experimentally examined for the m-CNB and o-CNB eutectic system. There are two types in product particles, agglomerates and non-agglomerates. The agglomerates are constituted by several elementary crystals whose sizes are almost equal to the number-based mean size of non-agglomerates. The purity of agglomerates is lower than non-agglomerates and decreases with increasing size. This is caused by entrainment of mother liquor in the bridges during agglomeration.
To design a novel reverse micellar system for protein extraction, binary and ternary reverse micellar systems composed of sodium bis(2-ethylhexyl) sulfosuccinate (AOT), di(2-ethylhexyl)phosphoric acid (DEHPA) and di(2-ethylhexyl) phosphorothioic acid (DEPTA) in isooctane are examined for the water solubilization and the extraction characteristics of proteins. The AOT-DEHPA-DEPTA ternary surfactant system is found to be suitable for protein extraction. The size of the mixed reverse micelle was determined by the small angle X-ray scattering method. It appears that both the water content and the micelle size for the ternary system are larger than those for the AOT and DEPTA single systems. Hemoglobin was successfully extracted by the ternary system, and back-extraction can be realized by use of a weaker alkaline solution (pH 9.5) with the addition of a small amount of n-octanol in the organic phase.
Room temperature grinding of four kinds of powder materials chosen based on their grindability was conducted using a planetary ball mill, in which the powder is charged in different amounts besides media balls. The median diameter of the ground materials was monitored to experimentally determine the size reduction rate. The size reduction rate of each material is proportional to specific impact energy of the balls simulated by the PEM (or called DEM). The gradient of the straight lines for each material in the prescribed relation is correlated to a net work index, which is calculated by substituting the impact energy of balls into the term of energy in Bond’s equation. The relation between gradient and net work index is also expressed by a straight line in normal coordinates. Therefore, the size reduction rate can be estimated by introducing a specific impact energy simulated by the PEM.
This paper discusses the decrease in current generated by the impact between particles and a metal plate with time. Final currents decrease to about one-tenth of the initial ones. In order to explain this fact, we have investigated the material transfer from particles to the metal surface and work hardening of the metal plate. EDS analysis has revealed that the amount of transferred chemical elements increases with the passage of time, and then tends towards a constant value. It is also found that the surface of the metal plate is hardened through impact of particles, and therefore the yield pressure increases with time. The current decrease can be explained by a proposed model which takes into account the change of yield pressure and the material transfer with time.
For the batch crystallization process, the tracking of temperature trajectory, which involves severe nonlinear and non-stationary features, is somewhat difficult to achieve. In this paper, three model-based control strategies, globally linearizing control, generic model control and multi-model based model predictive control, are applied to a batch crystallization process. Simulation results show that all three model-based controllers can provide superior trajectory tracking, disturbance rejection capability and robustness to the modelling errors in the process model as compared with conventional PI controller.
An auto-tuning procedure for PID controllers for a more general class of unstable process that has second-order dynamics is presented. These second-order dynamics are represented by a model having both stable and unstable poles together with an apparent dead time. A biased relay feedback test is used to generate a constant limit cycle for identifying this model. Criterion to distinguish a second-order model from the first-order one is devised. Upon finishing the identification, simple tuning rules are provided to tune the parameters of PID controllers. These simple tuning rules are derived from the authors’ previous work regarding controller design for open loop unstable processes.
An architecture for running multiple ART2 neural networks in parallel is presented. Each of the networks can treat different sizes of clusters. As the result, these multiple networks can show higher performance for detecting new classes. A proposed method is demonstrated for the detection of model changes for time-series models.
The breeding of a recombinant yeast having glucoamylase activity, Saccharomyces cerevisiae SR93, has already been reported by the authors, and further improvement of this yeast is attempted to significantly increase the conversion rate of starch into ethanol. It is generally known that the disruption of the MAT locus, which produces a repressor protein, enhances the expression of glucoamylase gene. A glucoamylase-producing yeast with the disrupted MAT locus, Saccharomyces cerevisiae SR96, is bred to convert starch into ethanol rapidly. Disruption of the MAT locus is performed by inserting the LEU2 gene into the MAT locus of S. cerevisiae SR93 and was confirmed by Southern blot analysis. The induction effect of starch and the repression effect of glucose on the glucoamylase synthesis are examined experimentally. The glucoamylase activity per unit cell concentration increases about 1.6-fold due to the disruption of the MAT locus. The specific growth rate, the glucoamylase synthesis rate, and the ethanol production rate of S. cerevisiae SR96 are much higher than S. cerevisiae SR93, and the direct alcohol fermentation of starch using S. cerevisiae SR96 gave the highest ethanol production rate in the various incubation systems.
The on-line estimation method of an “inherent” respiratory quotient (RQinh) from a conventional “apparent” one (RQapp) based on exit-gas analysis was proposed. The value of RQinh is a reasonable indicator for fermentation under alkaline conditions where the difference between RQinh and RQapp can not be negligible. The theoretical reassessment of the relation between RQinh and RQapp was made taking account of the direct reaction of CO2 and OH– in liquid phase. The practical usefulness of the estimated RQinh value was verified in the fermentation of alkaliphilic Bacillus sp. employed for enzyme production on an industrial scale.
Continuous Ambulatory Peritoneal Dialysis (CAPD) is one of the standard treatments for kidney disease patients. A washing solution, called dialysate, is put into the peritoneal cavity to remove waste products and excess amounts of water in CAPD. The dialysate is exchanged four to five times a day by the patient. However, it is not easy to prescribe CAPD therapy, which may have precluded popularization of CAPD therapy. Popovich et al. constructed a mathematical model (P-P model) that applies to the prescription of the treatment schedule. It requires, however, a number of iterative calculations to obtain an exact numerical solution because the model is a set of nonlinear simultaneous ordinary differential equations. In this paper, the authors derived a new approximated analytical solution by employing a time-discrete technique, assuming all the parameters to be constant within each piecewise period of time for the P-P model. We have also described an algorithm of a numerical calculation with the new solution for determining a set of unknown parameters in the P-P model. We compare the validation of the new solution for clinical use with another analytical solution (Vonesh’s solution). The new analytical solution consists of a forward solution (FW solution), that is the solution for the plasma and dialysate concentrations from ti to ti+1 (ti < ti+1), and a backward solution (BW solution) from ti to ti–1 (ti–1 < ti). The unknown parameters were determined by employing the Newton–Raphson method, a trial-and-error method and the modified Powell method in combination with FW and BW solutions. The new analytical solution show an excellent agreement with the exact numerical solution for entire dwelling time. Moreover, optimized parameters with the new analytical solution show much smaller discrepancy than those with Vonesh’s solution. Although the proposed method requires a slightly longer calculation time than Vonesh’s, it can simulate concentrations in plasma and dialysate for an entire single exchange in CAPD using the clinical data measured at arbitrary time. The proposed method may be useful for determining unknown parameters as well as for prescribing CAPD treatment.
In summer or on humid days, municipal solid waste, which is a raw material of RDF, rotts easily and causes bad odor, which makes the operation circumstance troublesome. In this study, CaO addition to the waste before the RDF production process is proposed, and the effect of CaO addition on the rotted material is experimentally examined. A mixture of soybean protein and distilled water was used as a model refuse. Escherichia coli was adopted as an indicator of rotting. The samples were put in a glove box for a few days, and then a constant amount of CaO powder was added to the samples. The changes in cell number of E. coli and pH with time were measured. CaO addition is effective for rotting suppression. However, as CaO addition is delayed, the higher content of CaO is required for rotting suppression. In the case of higher moisture content, the higher CaO content is required for rotting prevention.