ALBERT

Notes: Industrial product quality control is a typical mathematical programming and optimization problem. Unfortunately, complete and precise models are not always available for many industrial processes. A fuzzy relation modelling approach is proposed to describe approximate relationships among system variables and reconcile empirical equations. Symmetric fuzzy decision-making is transformed into a non-linear function maximization problem. The approach is applied to optimization of a wood chip refining process. It is used either to improve pulp quality within the refiner operation range, or to reduce operation costs while maintaining an acceptable pulp quality.

Notes: A high temperature coal pyrolysis reactor was developed and its operation demonstrated on a scale of 8 t/h. Pyrolysis is performed in a circulating fluidized bed reactor at 850-950°C. The developed process was integrated into smokeless fuel production technology and tested. Experimental data and reactor performance are presented.

Notes: The thermal decomposition of hydromagnesite has been studied using thermogravimetric analysis. The experiments were conducted in a nitrogen atmosphere with pellets of hydromagnesite in the temperature range 300 to 550°C, and also with powder samples under non-isothermal conditions at a heating rate of 10°C/min. It is found that the reaction proceeds in two stages: dehydration followed by decomposition. The dehydration reaction is controlled by external mass transfer whilst the decomposition reaction is controlled by both external and internal mass transfer. The activation energy for the dehydration reaction was found to be 2.67 × 107 J/kmol. From the non-isothermal analysis the activation energy for the decomposition of magnesium carbonate was found to be 1.62 × 108 J/kmol.

Notes: The kinetics of methane pyrolysis were studied in a tubular flow reactor in the temperature range 1200 to 1500°C at atmospheric pressure. To avoid excessive carbon formation the reaction time was short and the methane feed was diluted with hydrogen. Ethene, ethyne, benzene and hydrogen were the main gaseous products. Ethane was observed as a product at very low conversions of methane. More than 90% selectivity was obtained for C2 products. The ratio of ethyne to ethene increased with increasing temperature. The yield of C2 products is limited by gas-phase equilibrium at lower temperatures. Formation of carbon was strongly depressed by hydrogen at higher temperatures. The maximum yield of ethyne was found to increase from about 10% to about 50% when the temperature was increased from 1200 to 1500°C, with hydrogen dilution H2: CH4 = 2: 1. A mechanistic reaction model was used to simulate the pyrolysis of methane at the actual conditions. A sensitivity analysis was performed to evaluate the elementary reactions which influence the formation and consumption of the species in the model system.

Notes: Fluid catalytic cracking, a common secondary process employed in the petroleum industry, is used to convert heavier feedstocks into products such as liquefied Petroleum Gas (LPG), motor gasoline, diesel etc. The present study focuses on developing a three lump fraction kinetic model to estimate the yield of C5 up to 370°C cut (motor gasoline and middle distillates). A Micro Activity Test (MAT) apparatus was used to estimate the parameters in the kinetic model. The study is useful in evolving a procedure to simulate plant performance using experimental data obtained in the MAT apparatus for a particular catalyst and feedstock in terms of the product yield pattern.

Notes: Packings with vertical walls, especially structured packings, are distinguished by their high efficiency and low pressure drop per mass transfer unit. Yet for these types of packings there is still no universal relationship for calculating gas-film-controlled mass transfer coefficients. The present work proposes such an equation. For arranged and structured packings the new equation fits the experimental data, both new results and those taken from the literature, with a mean error of 9%.

Notes: Acidic zeolite LZ-M-8 was used to catalyse the hydrolysis reaction of inulin into fructose. Fructose contents of 96% and 75% were obtained when commercial inulin and Jerusalem artichoke extract were used respectively as substrates. Zeolite LZ-M-8 was found to be extremely selective towards inulin hydrolysis as compared to fructose decomposition. Formation of hydroxymethyl furfural (HmF) was not detected and it was confirmed that zeolite LZ-M-8 does not adsorb HMF. The catalytic activity of the zeolite remained intact upon repeated use of the catalyst. The superiority of the zeolite over other catalysts used in inulin hydrolysis was demonstrated experimentally.

Notes: An account is given of the patented technique of the rotational particle separator for separating solid and liquid particles of diameter 0.1 μm and larger from gases. Attention is focused on the working principle, fluid mechanical constraints, particle design, separation performance, power consumption, dimensions, filter cleaning and costs. Furthermore, an overview is given of current developments to introduce this technique in industrial dust removal, in electricity generation and in the consumer goods market. The article concludes with a summary of the feature which distinguish this technique from existing filtering methods.

Notes: Ethyl tert-butyl ether (ETBE) is an alternative fuel oxygenate that can be produced in the liquid phase by addition of ethanol to isobutene catalyzed by sulfonic acid ion exchange resins. A generalized Langmuir-Hinshelwood rate expression is formulated in terms of the liquid phase activities of the reactants that is quasi-autocatalytic due to ethanol. This microkinetic model is combined with the generalized Maxwell-Stefan equations for a detailed investigation of the influence of multicomponent mass transfer limitations inside the macropores of the heterogeneous catalyst. The model is used for revision of experimental rate data for ETBE synthesis in the literature. The analysis reveals that reverse diffusion of isobutene can occur by strong interaction with ethanol and the catalyst effectiveness factor can exceed unity.

Notes: An experimental investigation in a tube wall reactor with catalyst-coated inner wall is presented. Yields of formaldehyde of more than 70% can be obtained in the selective methanol dehydrogenation over alkalialuminate. Models for the reactor and the system of most important homogeneous reactions are derived. Different models describing the catalytic action are proposed. The results can only be explained by a new type of catalytic reaction, not described so far in the literature. Reducing gases like hydrogen and methanol lead to a volatilization of material from alkalialuminate which apparently catalyzes the dehydrogenation in the gas phase. Calculations and experimental evidence lead to the conclusion that this material should be sodium atoms. These are engaged in the homogeneous radical chain reaction by regulating the concentration of hydrogen atoms.

Notes: The determination of the composition of multi-component mixtures is the basis by which a number of technical and physical problems in the field of power and process engineering are modelled. In order to calculate chemical states of equilibrium in the gas phase, a calculation method will be presented which is founded on a minimization of the Gibbs enthalpy. This method is characterized by a high reliability in convergency, considerable independence of starting vectors and by a moderate requirement for programming. These characteristics are achieved by a transformation of variables which results in numerically more favourable solutions to the non-linear equation system. Calculated equilibrium compositions (including dissociation and ionisation) for a stochiometric mixture of hydrogen and oxygen in a temperature range of 300-12000 K and a pressure of 105 Pa as well as the application of the method will be demonstrated.

Notes: A phenomenological approach to evaluating the agglomeration rate of growing crystals is presented. Crystals larger than the Kolmogoroff microscale collide because of the fluctuating velocity field. Bridges between the crystals form as a result of competition between crystalline growth and the turbulent velocity fluctuations on the opposite sides of the agglomerate.Crystals smaller than the Kolmogoroff microscale collide because of viscous laminar microshear stresses within the same turbulent eddy, are kept close together by Van der Waals forces and are joined together by crystalline bridges that grow between them. The strength of these bridges depends on the supersaturation level during the moments following the collision.These two sets of phenomena lead to two different preferential generation mechanisms for agglomerates. One example involving important agglomeration effects is developed for each case: the crystallization of adipic acid belongs to the first group (large crystals), whereas the precipitation of calcium oxalate monohydrate is typical of the second case (small crystals).

Notes: The batch crystallization of potassium chloride from aqueous solution is investigated without impurities, with zinc chloride I (30, 100, 1000 ppm), with sodium hexametaphosphate II (100 ppm) and potassium hexacyanoferrate (II) III (100, 500, 1000, 16 × 25 ppm). The dominant particle size of the pure system LN, D = 427 μm increases by 40% by addition of I and by 250% by addition of II. While I does not affect the habit II changes it from cubes to octahedrons. In cases of low concentration, III leads to dendrites.It is shown that addition of III decelerates growth and increases the metastable zone width. Hence a high supersaturation is formed, the solution impoverishes fast while III gets incorporated and therefore a strong nucleation starts in a relatively pure solution. By quasi-continuously adding 16 × 25 ppm of III the dominant particle size increases by 160% with little fines. In this case the content of III in the product is relatively low.

Notes: The safe operation of a batch polymerisation reactor assumes sufficient knowledge about all the possible reactions. An investigation has been made in order to predict, with the aid of a mathematical model based on a detailed reaction mechanism, the runaway ability of a styrene batch suspension polymerisation reactor. The results of the simulation were compared with the experimental data obtained from a bench-scale test cell.

Notes: This article presents gas kinetic calculation methods for the energy transport in hydrogen/ air and methane/ air mixture. The total molecular heat conductivity as well as its various shares are calculated and discussed for a temperature range of 400 to 3500 K and for a pressure of 105 Pa. The variation of the air/ fuel ratio under the conditions of chemical equilibrium is also investigated. As opposed to our previous article, an extension of the Chapman-Knskog method which goes beyond the classical 1st approximation for elastic collisions is applied for the evaluation of suitable calculation methods. This is carried out following the method for strong relaxing thermal nonequilibrium according to Brun. The equations applied in this work are simplified formulations for the proximity to equilibrium. The method for the evaluation of the parameters of the inelastic collision and some chosen results are presented. A discussion of the various shares of the molecular heat conductivity emphasizes the considerable influence of the diffusion and the thermal diffusion processes in fuel/ air mixtures compared to the Fourier heat conductivity.

Notes: Venturi jet scrubbers are widely used in chemical industries as an efficient gas-liquid contacting equipment. They are simple in design, have no moving parts, operate with circulating liquid and are reliable in service. Moreover, due to high relative velocity of liquid and gas, considerable overall mass transfer can be produced. In spite of their wide application, readily usable design data are not available in literature, particularly for units producing a gas flow by their own pumping action. The purpose of this paper is to introduce the equipment and its application for H2S removal. The effects of various parameters such as gas and liquid flow rates as well as pressure on hydrodynamics and mass transfer performance of the equipment are investigated. Results of experiments have been shown graphically.

Notes: In condensers with high condensation rates or in falling film evaporators the falling film at the vertical tube wall shows a turbulent flow pattern. For optimal dimensioning of these apparatuses the knowledge and the description of the heat transfer in this turbulent falling film is necessary. Especially in fluids with a low thermal conductivity in liquid phase (i.e. hydrocarbons) the main heat transfer resistance is in the falling film, also if there are several components in gas phase. For calculating the heat transfer usually dimensionless Nusselt equations were used. These equations mainly base on experimental results which were found with water vapour as test fluid. It is shown that these equations fail for fluids with low thermal conductivity resp. high Prandtl numbers. Based on a Nusselt equation for turbulent tube flow a new equation for turbulent film flow is derived. A comparison between calculated and measured data for Prandtl numbers up to 50 shows good agreement.

Notes: An approach to feedforward distillation control based on inverse computation of nonlinear stage models is presented. The feedforward model calculates dynamic trajectories of manipulated variables from measured disturbances and product purity set points independently of the control configuration. Because the model includes the dominant dynamics and nonlinearities of the column, dynamic decoupling of the control loops is achieved. A superimposed linear controller only has to compensate model uncertainties and disturbances that cannot be measured. The proposed approach improves the control performance. Simulation studies show the applicability of the method to multicomponent distillation as well as to distillation trains. Experiments on a pilot plant scale binary distillation column verify the simulation results.

Notes: The mass spectrometer is capable of making rapid, repetitive multicomponent analyses with measurement times as short as a second or less. Mass spectrometers used to be too expensive to be used for process analyses, but simpler and cheaper versions have been developed during the last decade. Mass spectrometers are commonly used within the petrochemical industry, but their use for fuel gas streams is not so widespread. This paper describes tests on a quadrupole mass spectrometer in three different gasification projects. Calibration methods and analysis accuracies obtained are accounted for. On the basis of the tests, it can be concluded that the quadrupole mass spectrometer is very suitable for continuous analysis of complex process streams. An important result is that the separation of CO and N2, an analysis problem that is traditionally regarded as difficult, worked very well. The analysis frequency was approximately once per minute, which should be enough for most control loops.

Notes: The vapour-liquid equilibria of the binary systems perfluoromethylcyclohexane-pentafluorobenzene, benzene-pentafluorobenzene, benzene-methylperfluorobutanoate and perfluoromethylcyclohexane-methylperfluorobutanoate have been measured at 333.07 K and 343.12 K using a dynamic circulation still of the Sieg-Röck type. The thermodynamic consistency of the measurements was tested by two different methods. New UNIFAC interaction parameters [1] were calculated for the following groups: ACH-ACF, ACF-CF2, CF2-COO, ACCH2-ACF, ACH-CF2. The abbreviations stand for the following increments: ACH = aromatic CH group, ACF = aromatic CF group, CF2 = aliphatic CF2 group, COO = ester group and ACCH2 = side chain CH group.

Notes: An experimental set-up is presented for the measurement of reaction rates in the liquid phase synthesis of tertiary amyl methyl ether (TAME) from methanol and a mixture of 2-methyl-1-butene and 2-methyl-2-butene using an acidic ion exchange resin (Lewatit SPC 118) as catalyst. The reaction was performed in a continuous-flow recycle reactor at a temperature of 333.15 K and a pressure of 1.6 MPa. Determination of the age distribution (Fcurve) of the reactor showed that mixed flow is approached at a recycle ratio of R = 10. Experiments were performed to reveal the limits of operating conditions where the various resistances do not affect the rate. In agreement with estimation of Reynolds numbers, hindrance by external mass transfer can be excluded at a volumetric flow rate of 10 ml/min and a recycle ratio of R = 10. The maximum temperature increase of the whole particle resulting from limitation of external heat transfer was estimated to be about 3 K. Variation of the size of resin particles revealed the existence of a critical methanol concentration, above which reaction rates can be determined without influence of internal mass transport phenomena. The maximum temperature increase in the particle was estimated to be 0.3 K.

Notes: This paper represents an attempt to explicitly map the conceptual activities which constitute a process design task into a series of well-posed, complete and general numerical procedures. In spite of the fact that there is substantial number of design manuals and design procedures which process engineers can consult to choose the most proper approach to a particular problem, there is a remarkable lack of generality on the one side (procedures which apply to the design of a wastewater treatment process cannot be used even in principle to design a fluidized bed system), and an obvious receptivity on the other side (all procedures involve mass and energy balances at some point). With the advance of numerical techniques, virtually every procedure has been computerized, so that engineers can avail themselves of a multitude of computer tools in the majority of their process design activities: as a result of the lack of coordination among different producers though, the situation for what codes are concerned is very confusing: there are many codes which perform nominally the same task, giving (sometimes substantially!) different results when applied to the very same problem; each code sue its won set of property tables, its own I/O format, etc. Finally, with very few exceptions, these codes are not mutually compatible, i.e. the output from any of them cannot be used as the input to any of the other, not only because of the respective formats, but rather because the quantities taken to represent a certain physical process are not the same in different codes.This is a very unsatisfactory state of affairs, both for the final user and for the software producer. Unfortunately, this seems to be a problem for which commercial, technical and historical reasons make it very difficult to find a solution in the short term. The author is convinced that an early exposure to this problem and to a new approach to its solution can only benefit our engineering students, and has therefore endeavored, together with his coworkers, to devise a “modular approach” to the solution of process simulation problems. The material presented here has been originated by a series of lectures and seminars developed in the last three years for master and doctoral level students in Mechanical Engineering. The result of this “distillation” process maybe yet unripe, as they are definitely not complete: but the implications, also in terms of practical application, are very promising, and the approach deserves more attention in the future.The order of presentation of the material is historical/logical: it beings with the old fashioned slide-rule calculations and proceeds towards the most recent developments of AI base methods. The path is made clear from the very beginning: we are trying to extract from the various engineering activities all the essential knowledge which pertains to the engineer himself, with the final goal of transferring this body of knowledge - in some form suitable to machine communication - to a “universal-process simulator”, which can then be applied with a high degree of confidence to variety of particular process simulations.

Notes: A method for the prediction of velocity and path length components for two-dimensional particle motion is developed for stagnant and slowly moving gas. The numerical algorithm appears much more straightforward and more efficient than those previously developed on the basis of simplified analytical methods. In the case of particle motion in a flowing gas, several limitations of the method occur. The method of limit estimation is briefly described.

Notes: The growth of a thin liquid film surrounded by gas pocket(s), undergoing absorption with a zero-order chemical reaction, has been simulated by an apt mathematical model in order to study the influence of various parameters involved. The solution has been obtained semi analytically using Goodman's integral method and solving the resulting differential equation by a fourth-order Runge-Kutta numerical integration algorithm. The computations reveal the strong dependence of film growth on reaction rate, diffusivity, and molar volume whereas the effect of gas-pocket volume and initial film thickness are moderate.

Notes: Heat transfer from a buried pipe carrying a flowing liquid is analysed using a 3-dimensional geometry, transient modeling and numerical methods. The pipe is buried horizontally in soil whose initial surface temperature is assumed to be below that of the bulk soil and the pipe, and also below the freezing temperature of the liquid. The problem is solved using string-intersected-boundaries and a three-level alternating-direction-implicit finite-difference method. It is possible to predict the time taken for the fluid anywhere in the pipe to fall to its freezing point. The minimum burial depth needed so that the pipe does not freeze is also predicted. The simulation was run on an ordinary mainframe computer with very small computation times. The package developed can be used by designers such as pipeline, plant and water distribution engineers.

Notes: A general procedure for the determination of empirical rates and kinetic parameters of irreversible, constant volume reactions is presented which is clearly superior to the conventional methods of kinetic analysis. By nonlinear regression of the integrated potential rate equation for stoichiometrically independent reactions of n the order, the empirical pre-exponential factor, activation energy, and reaction order are obtained. The regression equation relates explicitly the final concentration of the reference component not only to the time parameter of the reaction but also to the initial concentration. This includes an integral method for the determination of reaction orders in concentration. Two limiting cases are treated - the stoichiometric mixture of reactants and a mixture with one reactant in large excess. By analysis of standard Hougen-Watson rate models the dependence of empirical reaction orders on experimental conditions and simulated rate parameters is evaluated. By grouping the data into ranges of monotonous concentration change, conversion rates and rate parameters of reactions with changing volumes are calculated in a less rigorous deduction. The simplified interpretation of published experimental data is demonstated for the total oxidation of methane on Pd-catalysts and the dehydrogenation of cyclohexanol on ZnO.

Notes: Catalyst surface characterizations have been carried out to investigate the role of dispersion on catalyst activity and to probe the occurrence of oscillations in coking levels with cycle number generally observed during multiple deactivation and regeneration schemes. The titrations were done, cycle by cycle, at 430°C after oxidation and at the same temperature (430°C) after reduction at 500°C. Results show the usually observed trend - that the dispersions after oxidation are higher than those after reduction. The average decline in dispersion from oxidation to reduction was calculated to be 39.25%. It was observed that the cycles with high toxic coke removal were characterised by high deactivation times. The deactivation times were still high even for cycles subsequent to those with low dispersion. At high dispersions the catalyst had short deactivation times, that is the small crystallites deactivate faster than large ones. The nature of reducebale coke and the efficiency of its removal is a much more determinant factor of catalyst activity than the level of metal disperision. Thus prolonged toxic coke reduction at the high temperature of 500°C, though resulting in an apparent lowering of dispersion, does not affect the quality of the catalyst. The dispersion before reduction could be retained on oxidation. Hence reduction at 500°C did not introduce sintering.

Notes: A nonlinear unsteady state optimal control problem for a classical, constant diameter ethane thermal cracking reactor is formulated and solved. The process is represented by a pseudo steady state mathematical model, consisting of mass and heat balance, pressure drop, and coking equations. The performance index is of an economical nature, representing the global benefit of reactor operation over a constant operating time. As control variables, the space and time dependent skin tube temperature, the time dependent steam to hydrocarbon ratio, and the time dependent feed flow rate were considered. The results are in agreement with the process physicochemical and technological fundamentals.

Notes: A chain growth model for heterogeneous secondary reactions is developed for the pyrolysis of large wood particles and the parameters determined by nonlinear optimization. The model takes both the volatile retention time and cracking and repolymerization reactions of the vapours with the decomposing solid as well as sutocatalysis into consideration. The extent of the secondary reactions is strongly influenced by the time and the ratio of the autocatalytic (propagation) reaction rate to noncatalytic (initiation) reaction rate. The wood which has a higher value of the autocatalytic/noncatalytic ratio also has a higher exothermic heat of reaction and yields a higher amount of final char residue. This fact confirms the heterogeneous secondary reactions lead to carbon enrichment of the final residue and are accompanied with an exothermic heat of reaction. The lower activation energies of the initiation and propagation reactions as compared to primary reactions (competitive reaction model consisting of weight loss and char forming reactions) confirm autocatalysis in large particles. The sealed reactor studies of small quantities of fine wood samples show that heterogeneous secondary reactions and not lower heating rates in large particles are the main source of char formed during the thermal decomposition of large wood particles. The model predictions are in agreement with the weight loss and temperature versus time curves over a wide range of particle size and furnace temperatures.

Notes: Reasons are given why the axial dispersion in a gas flowing through a packed bed may be influenced by the elasticity - or compressibility - of the fluid. To support this hypothesis, experiments have been done in a packed column at pressures from 0.13 to 2.0 MPa. The elasticity E of a gas is proportional to the pressure P and the compressibility to 1/P. The axial dispersion coefficients as determined were found to be a function of the pressure in the packed bed in the turbulent flow region of 3 〈 Rep 〈 150 if the Bodenstein number is plotted as a function of the particle Reynolds number. This is shown to be an artifact. The pressure influence is eliminated, if Bom, ax is plotted versus the ratio of the kinetic forces over the elastic forces ϱu2/E. Regrettably, Bom, ax seems to be independent of ϱu2/E. For the moment we only can conclude that Bom, ax in the turbulent region is a unique function of the velocity of the gas which flows through the packed bed. Although the fact that a constant Bo value is obtained when plotted against ϱu2/E, the experimental results are so intriguing we wanted to make them public already now. The experimental work proceeds.

Notes: The results of simulations of direct concentration control of a distillation column in industrial scale are presented. Both controlled variables, the two product concentrations, are determined by on-line gas chromatographs and are characterised by high dead times of about 30 min. For the resulting scanning control of the product concentrations corresponding decentralised PI controllers were developed and applied. The control of the product concentrations developed presents a conventional DV structure and was exemplarily tested for disturbances in feed flow and feed concentrations. The calculations carried out exhibit a good time behaviour of the whole system. On this occasion it can be stated that the control quality could be clearly improved if a steady-state decoupling by output transformation was employed. In this case the results achieved are totally comparable to those of internal model control (IMC), which was in use at the production plant for over two years.

Notes: The kinetics of the liquid phase hydrogenation of 4-tert-butylphenol to form cis- and trans- 4-tert-butylcyclohexanol at 1.0-10.0 MPa and 40°C in isopropanol over a Rh catalyst has been studied. The kinetic behavior of this parallel system is described by a proposed reaction network. Keto-enol tautomeric transformation of adsorbed 4-tert-butyltetrahydrophenol and 4-tert-butylcyclohexanone is thought to be a key step, which governs the stereoselectivity of the overall complex reaction of alkylphenol hydrogenation.

Notes: The gas-phase hydrogenation of buta-1,3-diene to but-1-ene, trans- and cis-but-2-ene and butane has been performed over 0.5% Pd/γ-Al2O3 catalyst. The reaction has been investigated at atmospheric pressure and 0°C over a wide range of conversions. The kinetic model based on the present day knowledge of reaction mechanism has been advanced. The parameters of the kinetic model have been estimated through statistical data fitting. The kinetic model provides a fairly good description of selectivity in the whole range of conversions.

Notes: The following article concerns emulsification reaction in a continuous screw loop reactor. The influence of hydrodynamics on the emulsification process as well as the influence of some specific substances were examined. We produced oil/water model emulsions under different test conditions and we determined the correlations between the mixing behavior of the reactor and the characteristic features of the obtained emulsion. Special consideration was given to the droplet size and its distribution. Variable operating conditions of the reactor are the residence time and the rotational speed of the screw, both of which have a decisive influence on the recycle factor and the number of passages through the rotor/stator system. In addition we determined the dependence of the obtained droplet size distribution on the viscosity of the continuous and dispersed phase, on the interfacial surface tension and on the phase proportions. The influence of the specific type of emulsifying agent and its concentration has been examined as well. The positive effect of the mixing and of the recirculation on the emulsification in the screw loop reactor was particularly evident with low emulsifier concentrations and with emulsifiers with slow adsorption kinetics. The established theories for emulsion formation (Kolmogoroff, Taylor) were used for a quantitative description of the experimental results. The screw loop reactor was compared to an agitated tank reactor and a toothed-ring dispersing machine (Ultra Turrax) based on the comminution energy which is produced per unit volume of emulsion. The agitated tank reactor produced only coarsely dispersed emulsions through the entire rotational speed range, wheras the screw loop reactor and the Ultra Turrax, particularly at high rotational speeds and, therefore, high power densities, showed a similar emulsification and produced much finer dispersed emulsions.

Notes: The performance of an upflow packed-bed biofilm reactor has been analyzed under multisubstrate limitation by considering simultaneous carbon oxidation and nitrification reactions. The fasting shock load of inlet methanol concentration has a much more pronounced effect on the response of the system compared to that of inlet NH4+ -nitrogen concentration. The exit concentration of NH4+ -nitrogen drops very close to zero, thereby showing essentially complete nitrification during methanol fasting condition. Further, the concentration profiles of oxygen within the biofilm show significant variation during methanol fasting and nonfasting conditions whereas during NH4+ -nitrogen fasting conditions the oxygen concentration profile in the biofilm remains essentially unaffected.

Notes: The uncatalyzed esterification of acetic acid is described in the literature as a typical example of reactive distillation. Many rigorous models were validated using this esterification as an example. Process proposals for the production of pure ethyl acetate from ethanol and acetic acid have been determined using short-cut methods with the assumption of chemical equilibrium only. In this publication, the limitations of this esterification are clarified, using a rigorous model that was developed. The reasons why reactive distillation appears to be unfavorable for this esterification are explained. It is, however, theoretically possible to obtain ethyl acetate in high purity with different variants of the process. Different process variants are examined in this work. Construction variables that are important for the design of reactive columns, such as the number of reactive separation stages and the holdup in the column, are analyzed. Furthermore, the influence of variables dependent on the component system, such as the phase equilibrium of the reactive system and the reaction kinetics on the conversion in the column, are described. It can be shown that the short-cut methods published so far for reactive distillation, which assume chemical equilibrium, are inadequate.

Notes: Two devices were developed, mechanical and electrical, to measure the mechanical power relative to superficial gas velocity and stirring speed in a mechanically agitated reactor. Two bubble regimes were demonstrated. The study of gas holdup, obtained from the residence time distribution, and the bubble size, determined by interfacial area measurement, confirm these two regimes of flow. Our results show that the gas holdup, the interfacial area, and the liquid-side mass transfer coefficient are increasing functions of the energy dissipated in the solution.

Notes: An electrochemical technique which involved measuring the limiting current of the cathodic reduction of potassium ferricyanide was used to study the rate of mass transfer inside a cubical cavity machined in the wall of a vertical rectangular duct. Variables studied were side length, physical properties of the solution and flow rate of the solution. The mass transfer coefficient was found to decrease with increasing cavity size; in all cases, the mass transfer coefficient inside the cavity was less than that at the duct wall. Mass transfer data inside the cavity were correlated by the equation Shc = 0.525 (Sc Re de/L)0.33. Comparison of the present results with the results obtained using other cavity geometries shows that cavity geometry plays an important role in determining the rate of mass transfer inside the cavity.

Notes: Transient heat transfer in a mechanically agitated vessel is studied in the case of an anchor and an helical ribbon impeller using Newtonian and shear thinning fluids. Temperature stratification is found more pronounced with the anchor, making this impeller clearly inadequate for heat transfer. The impact of natural convection is evaluated first using the classical Gr/Re2 ratio. It is shown that the use of this criterion in viscous mixing is somewhat misleading. A new Grashof number is then proposed to assess the significance of the viscous and buoyancy effects in non-isothermal, non-Newtonian mixing applications. It is shown that the interpretation of this new number is strongly related to the concept of process viscosity.

Notes: The results of a process analysis and an experimental exploratory study of supercritical water oxidation (SCWO) show that elements of combustion technology are suitable to overcome the technical problems of SCWO. The Film Cooled Hydrothermal Burner (FCHB) which operates at 25 MPa up to 2000 K in the reaction zone keeping wall temperature under stress at 300 to 400 K shows further development potential of the Wallcooled Hydrothermal Burner (WHB) concept for SCWO, a still promising waste treatment process.

Notes: The Subnetwork Corollary provides some sufficient conditions for which a complex reaction network could be determined to have capacity of admitting multiple positive steady-states, if it contains a subnetwork that also admit multiple positive steady-states. A family of reaction networks, involving catalytic reactions in an isothermal continuous flow stirred tank reactor (CFSTR), is determined to have the capacity to exhibit steady-state multiplicity by implementation of the Deficiency One Algorithm and the Subnetwork Corollary. A set of rate constants and two corresponding positive steady-states are constructed for several cases.

Notes: To review mass transfer trays from a process point of view, the dependence of efficiency on the loadings, the loading range and the maximum loadings with an acceptable tray efficiency have to be known. Comparing the results taken from experiments on Dualflex trays and from other types of trays which have been in industrial applications for many years and which are recognized as “industrial standard”, has been evaluated in this review.

Notes: In this contribution, a new method is proposed for determining effective macropore diffusion coefficients in porous media by digitized microphotographs of porous support materials and random walk simulations. The method introduced allows calculation of the effective diffusion coefficient as a function of the mean free path length over a wide variety of values. A versatile method for the preparation of porous substances for light microscopy is described.The frequently applied model of an active shell, which is used to model particle/solid collisions, was found to give incorrect results in conjunction with the application of the first passage time algorithm, which was applied to save computing time in the simulation of gas diffusion. It was possible to show that more realistic results are obtained if a Knudsen layer is used to model particle/solid collisions. Furthermore, in investigating diffusion in two- and three-dimensional representations of capillary tubes, it was found that results of simulations performed to calculate transport properties of fluids in porous media, based on two-dimensional model systems, cannot in any case be transferred to the corresponding three-dimensional systems.

Notes: The rate of the homogenous exothermic hydrolysis reaction of acetic anhydride catalyzed by sulfric acid in solvent acetic acid was estimated from nonisothermal experimental batch reactor transient temperature data. Rate equations based on three different reaction mechanisms of hydrolysis published in the literature were fitted to the experimental rate data. The experimental results on runaway and limit cycle behavior obtained with this reaction were explained by using the mechanism-based rate equations for hydrolysis in the reactor dynamic models, and good agreement was obtained between the predicted and the experimental dynamic data.

Notes: New uses of artificial selective membranes, particularly ion-exchange membranes, improve on traditional methods of treating liquid mixtures before, during or after chemical or biochemical reactions. With the correct choice of ion-exchange membrane in a membrane reactor, reactions can be performed in such a way that the main product is not contaminated by undesired byproducts. Recent examples, mainly in organic chemistry, are given for eight typical ion-exchange membrane reactors: electrodialysis (ED), electrometathesis (EMT), electro-ion substitution (EIS), electro-ion injection-extraction (EIIE), coupled counter-transport (CCT), electro-electrodialysis (EED), electrohydrolysis with bipolar membranes (EHBM), and catalysis with ion-exchange membrane (IEMC).

Notes: In this study, a scale-down approach has been used for the simulation of the imperfect mixing on the growth processes by considering several configurations of continuous stirred tank reactor (CSTR, aerated) and plug flow tubular reactor (PFTR, not aerated). The steady-state concentrations of biomass and enzyme in a continuous culture were calculated as a function of dilution rate using modified Monod growth kinetics. A mathematical model for each combination of two bioreactors was developed to account for growth, substrate utilization (oxygen and glucose) and enzyme synthesis and decay. The model was then used to investigate biomass production and enzyme expression in relation to the volumetric fraction Uf = VPFTR/(VCSTR + VPFTR) and the recirculation ratio R = fr/(f + fr) of the fermentation system. These two mixing parameters were found to be significant factors in the biomass and enzyme production from the fermentation system. This model was also compared with some of the existing models.

Notes: As an alternative to the existing bioheat transfer models a new system of two energy equations is proposed by considering the human body as a deformable porous medium. One equation is developed for the blood and the other for the peripheral skeletal tissue. It includes such significant factors as the vascular geometry and size, the blood flow and direction, thermal diffusion and the local thermal nonequilibrium between the blood and peripheral tissue. Discussion and application of both equations are given.

Notes: A new method for cleaning inner surfaces of pipes was studied both theoretically and experimentally. The method is based on the phenomenon of a sphere rotating in a pipe (levitation), when the translational movement of the sphere is restricted and the sphere is subjected to fluid flow in the pipe. The high rotation velocity causes a vibration process, which may be exploited for cleaning sediments or rust from the inner surfaces of pipes. A simplified theoretical model for the determination of the relationships among the dimensionless parameters governing the rotation phenomenon was developed. The model was validated with experimental data and found to be appropriate for engineering design of the system. Application of the cleaning method was demonstrated by cleaning the sediments and rust off the inner surface of a one-inch nominal diameter pipe.

Notes: An ortho-experiment design and the analysis method of mathematical statistics are adopted to study the conversion of gypsum and potassium chloride to potassium sulfate in the system of K+, Ca2+, NH4+ ‖ Cl-, SO42- in H2O. Optimal reaction parameters and engineering mean are acquired to attain a conversion yield of potassium chloride of 94.52%.

Notes: In the present work, we employ a fuzzy logic controller (FLC) to control the unstable state of a nonlinear biological reaction. The state variable vectors consist of cell density and substrate concentration. The dilution rate is used as a manipulated variable to control the reaction dynamics. An analytic form of FLC employing Zadeh AND logic along with Center of Mass defuzzification method is considered. Simulations reveal that for servo response test, the FLC shows satisfactory performance for natural unsteady states for which a conventional PI controller is known to fail. Further simulations also show that the FLC gives satisfactory regulatory response and is relatively insensitive to the deviations in model parameters.

Notes: A ‘carbon source controlled shift technique’ was developed for fermentation medium optimization in continuous culture with the objective to maximize growth rate and growth-linked product formation of a biological system. An automatic culture medium preparation system was operated together with 2 parallel stirred tank reactors and a HPLC system for on-line analysis of the carbon source concentration in the reactors. A genetic algorithm was applied for experimental design. The concentrations of 7 medium components (mineral salts and vitamins) were optimized automatically within 40 continuous experiments to result in a maximum growth rate of the methylotrophic yeast Candida boidinii and growth-linked production of the formate dehydrogenase enzyme (FDH). The specific growth rate of Candida boidinii and the specific activity of the FDH enzyme at a set-point of 420 mM methanol in the reactor were, thus, improved by 19% to 0.16 h-1 and 26% to 164 U g-1, respectively, compared to the previously used medium, which has already been previously optimized in shake flask experiments. The results of the continuous medium optimization were evaluated with a full second order seven-dimensional polynomial model (regression coefficient 96.8%).

Notes: By applying the macroscopic conservation laws to a simplified jet downstream from a sudden enlargement, a new correlation of the two-phase subcritical pressure recovery is obtained. Comparisons with the set of existing data (air-water and steam-water subcritical flows) show that the predictions obtained by means of this formula are more accurate than the ones given by available analytical models. The proposed correlation presents an important improvement of the pressure recovery predictions in the case of small mass velocities. However, it can not be applied in the conditions of quality too close to one.

Notes: In paper coating make-down, a poor dispersion of pigments in coating colors may lead to coater runnability problems. This is manifested by coat defects at the paper surface, excessive coater blade wear, and an over-consumption of pigments. For this reason, high shear impellers operated at high speed are used, yielding a high energy consumption. A new method to disperse high solids mix at low energy consumption is presented. This method based on the use of a rod impeller scraping the fluid surface in the vessel, is tested on a slurry composed of calcined and delaminated clays up to a solids content of 66.7 wt.% without dispersing aids.

Notes: When in contact with water, organoalkoxysilanes and other alkoxy metal compounds react to organofunctionalized polysiloxanes or heteropolysiloxanes. A new method for the continuous preparation of porous organopolysiloxane spheres was developed. Droplets of the precursor mixture are injected into the vertical reactor column. Movement of the gelating droplets is controlled by flow of the aqueous reaction medium. Advantages are adjustable residence time, minimized coalescence and low reactor height. An example shows typical product characteristics like narrow particle size distribution and macroporosity.

Notes: This paper describes how gain scheduling control is applied to a continuous stirred tank reactor model. The CSTR process, equipped with a cooling system, is modelled. Based on the resulting nonlinear model, a gain scheduling controller is designed. The gain scheduling follows a scheme denoted bias compensation. Compared to earlier reported gain scheduling schemes, the proposed scheme results in a controller that is less complex, which is advantageous in the controller implementation stage. Numerous simulations are performed, using the gain scheduling controller and two choices of control input to the reactor model. The simulation results indicate that a gain scheduling controller performs better than a linear controller. Simulations using different choices of control input to the reactor model indicate that proper process design is crucial for the controlled process performance.

Notes: Two different layouts for the liquid-liquid extraction section of an industrial caprolactam process are evaluated. Laboratory mass transfer measurements on streams obtained from an industrial and a demonstration plant with different extraction sections are interpreted by a model describing the effect of surface contaminants on mass transfer coefficients. Indications of the impact of these layouts on the complexity of the extraction section, quality of products and efficiency of the extraction processes are given.

Notes: A time- and space-dependent model based on the piston-dispersion-exchange model for liquid flow was developed to analyze the performance of two-phase upflow and downflow fixed bed reactors and was applied to the catalytic SO2 oxidation. The hydrodynamic parameters were determined from residence time distribution measurements, using an imperfect pulse method for time-domain analysis of nonideal pulse tracer response. A transient diffusion model of the tracer in the porous particle coupled with the PDE model was used to interpret the obtained RTD curves. Gas-liquid mass transfer parameters were determined by a stationary method based on the least square fit of the calculated concentration profiles in gas phase to the experimental values. It is shown that two-phase downflow fixed bed reactor performs better at low liquid flow rates, while two-phase downflow fixed bed reactor performs better at low liquid flow rates, while two-phase upflow performs better at high liquid flow rates.

Notes: The autoxidation of aqueous sulfide solutions by dioxygen is studied at pH 9 and 14 and at initial sulfide concentrations between 1 and 100 mM. Disulfide as a primarary intermediate is proposed to enhance the sulfide oxidation by autocatalytically forming polysulfies. The postulate is supported by the observed acceleration of the process at increasing pH favoring the presence of disulfide rather than that of sulfur. The final reaction products thiosulfate and sulfate are proposed to result from the hydrolysis of the highly instable intermediate polythiosulfite in parallel parallel reaction pathways, assuming probabilities for breaking the sulfur chain at the α (sulfate) and β (thiosulfate) positions to be responsible for the selectivity. A reaction scheme is proposed, considering all experimental observations.

Notes: Bubble columns are commonly used in industry for polluted gas treatment. Based on the same principle, the droplet column which is not widely known in the literature, uses much higher gas velocities, up to 14 m/s. This study concerns the hydrodynamics and mass transfer in this apparatus, in presence or absence of solid particles. Our results have demonstrated the impact of dusts on mass transfer performance giving rise to an increase in the kL aL coefficient with decreasing particle size. However, no influence of dust on the hydrodynamics of the column has been demonstrated within the studied particle size range.A study of liquid holdups obtained by three different methods is also carried out. Our results are comparable, thus validating the methods used.

Notes: A simple and new model for the prediction of drop velocity as a function of dispersed phase volume fraction has been proposed on the basis of experimental knowledge of onset time of complete separation between two phases as function of the initial hold-up.

Notes: A dynamic model of the liquid fluidized bed containing two or more solid particle species of different size and density is presented. The model incorporates the particle mass transport mechanisms of the convection and the dispersion. The movement of the upper interface of the bed subject to a change in the liquid velocity is specified using the mass balance constraint. The particle velocities and dispersion coefficients are evaluated using correlations. The model is capable of describing the bed expansion, concentration profiles of the individual particle species, the bulk density profile, and the occurrence of layer inversion.

Notes: Experiments were carried out in a conventional circulating fluidised bed to measure the axial pressure profile and total pressure drop, which covered a wide range of operating conditions. Material belonging to the Geldart A (fine material) as well as the Geldart B (course material) categories have been used in the present work. Slip velocity is determined from the total pressure drop and noticed that the slip velocity is much higher than the free fall velocity of single particle for Geldart A type material, while it is approximately equal to the free fall velocity of single particle for the Geldart B type materials.A model is developed for slip velocity taking into account all the hindrance effects: particle-particle, and particle-wall, and particle agglomeration. Predictions of the present model are validated with the data due to present study and the data reported in the literature.

Notes: Two important structural factors that affect distillation efficiencies, the outlet weir heigh and the liquid flowpath length, are investigated. Performance and efficiency data of an industrial scale i-butane/n-butane distillation column equipped with two-pass trays are used as a basis for the calculations. A mathematical development for a new method for predicting the numbers of vapor and liquid phase transfer units is given. This method together with some other NTU calculation methods is used to assess the effect of the outlet weir height on efficiencies. The effect of outlet weir height on the Murphree tray efficiencies is investigated using the observed point efficiencies and different point efficiency to the Murphree tray efficiency relation methods. The effect of varying liquid flowpath lengths on efficiencies is studied by calculating the Murphree tray efficiencies for one-pass and two-pass trays. The results obtained using the NTU calculation method presented in this study show that a certain outlet weir height point efficiency reaches its maximum. Most of the other methods give opposite results giving a minimum for point efficiency at a certain outlet weir length. The results also show that the Murphree tray efficiencies for one-pass trays are higher than for two-pass trays. Obviously, this is caused by the longer liquid flowpath length of one-pass trays. The Murphree tray efficiencies are also calculated for an industrial-scale MTBE purification column. The column is equipped with two-pass trays in the stripping section and with one-pass trays in the rectifying section. The Murphree tray efficiencies of one-pass trays are considerably higher than the two-pass tray Murphree tray efficiencies.

Notes: An algorithm for the computation of design variables in layer crystallisation processes is presented, based on an algebraic solution of the moving boundary equation for heat transfer, as well as on an expression for the concentration profile. The algorithm was applied to the discontinuous crystallisation of a NaCl-H2O solution around the wall of an internally cooled cylindrical tube. Good agreement between simulation results and laboratory experiments was observed. After input of experimentally measurable values of the distribution coefficient, the algorithm enables the prediction of the following process variables along the crystallisation time: layer thickness, temperature, and composition profiles across the layer, as well as the end-values of solid and liquid mass and concentrations. Multistage processes can be studied by the series association of crystallisation cycles, enabling the determination of the optimal number of stages that meets a specific design criterion.

Notes: Dust explosion hazard exists in plants and facilities wherever combustible dusts are hardled. Minimum explosible concentration of dust clouds is an important factor requiring special attention for hazard evaluation if any technological equipment is to be protected by inertisation. The mathematical models available for prediction of this parameter have been analysed for their application to organic dust clouds. Solution of the most general mode for determination of minimum explosible concentration of dust clouds proposed by Mitsui and Tanaka is presented, together with the comparison with experimental data. It has been found that the model is not successful in predicting the minimum explosible concentration for organic dusts. Recommendations on requirement of development of a new model for prediction of minimum explosible concentration of an organic dust such as polyethylen have been given.

Notes: When working with disperse solid matter systems, one uses the effect of vibration in numerous processes. Solid matter mixing with vibration has only occurred in very simple units up to now. By means of the 3D-vibrational mixer from the company Kuston, Kleve, the influence of vibration on bulk materials and new mixing techniques are demonstrated. The 3D-vibrational mixer is suitable for liquids and solids, does not require mixing tools that need to be cleaned, and does not carry out rotary motions which would hinder incoming lines. It is used for mixing small amounts, where the mixing tank can be used simultaneously as the transportation container, so that a transfer is unnecessary.With the aid of 4 linear motors, the vibrational amplitudes and the frequencies can be varied within wide boundaries in all three spatial directions. By analyzing the vibrational system by means of Lissajous figures, it can be demonstrated that the optimal mixing effect occurs in the case of small frequency differences between the three axes. For freeflowing bulk materials, the best possible mixing state, the uniform coincidence mixing, is achieved after 2 min.

Notes: The intermixing of fluidizing gas between the compartments of a compartmented circulating gas fluidized bed fitted with a V-valve and riser combination has been experimentally studied. The intermixing of fluidizing gas that flows co-current (cross flow) as well as counter-current (back flow) to the circulating solids has been investigated. At low aerations, gas cross flow increased proportionally with the increase in solid circulation rate. But at high aerations, gas cross flow increased with aeration even when solid circulation decreased. Studies on back flow of gas revealed some interesting observations. At high fluidizing bed height on upstream side back flow of V-valve, gas has been negligible. But at low upstream bed heights and low aeration in V-valve and riser back flow of V-valve, gas has been substantial.

Notes: Affinity separation can be achieved by batch and fixed bed modes. Mathematical models including film mass transfer, intraparticle diffusion, and reversible reaction are formulated for both fixed bed and batch adsorption processes. Orthogonal collocation method is used to numerically evaluate the performance of batch and fixed bed adsorption. The efficiencies are evaluated in terms of both the solute recovery and adsorbent utilization. The effect of the following parameters is simulated for the comparison purpose: solute concentration, reaction kinetics, ligand content, and particle size. Fixed bed mode is found to be efficient.

Notes: The present paper deals with a novel hydrogen sulphide abatement process applying a combined chemical-biological process. The authors already dealt with this subject in the paper “Biotechnological H2S gas treatment with Thiobacillus ferrooxidans” [1], previously published in Chemical Engineering and Technology. This study, in particular, deals with over all process test runs in a laboratory scale plant with a single-stage immobilised biomass reactor.

Notes: Numerical results are presented for a contraction flow of a non-Newtonian fluid. In this work a new finite-volume algorithm was used and various non-Newtonian fluid models (with and without elasticity) were studied. The results are discussed and compared to experimental results obtained with a dilute polymer solution.

Notes: Calcination and carbonation behaviour of dolomite has been studied in a pressurised thermo balance at pressures in the range of 1.1 to 2.3 MPa and for temperatures ranging from 730 to 840°C. The atmosphere consisted of nitrogen containing up to 20 vol.-% carbon dioxide. The calcination of dolomite has been studied as a function of temperature, particle size, and Pco2. An investigation concerning possible mass transfer restrictions for the experimental system and a model investigation of the calcination rate in CO2 atmosphere has been made. Further, the effect of calcination on the BET surface and the BET surface including the surface structure due to successive temperature cycles has been studied. The temperature for the initialisation of calcination of dolomite in CO2 atmosphere was independent of both Pco2 and the particle size. No conclusive indications on mass transfer restrictions have been detected for the experimental system. A significant difference in calcination rate as a function of particle size existed for decomposition in CO2 atmosphere. A model for homogeneously progressing chemical reaction parallel with a shrinking core chemical reaction together with a mass transfer control mechanism was found to describe the calcination rate in CO2 atmosphere most accurately.

Notes: Experiments on thermal decomposition of calcium carbonate were carried out in a thermogravimetric analyser under non-isothermal conditions of different heating rates (10 to 100°C/ min). A new technique for determining the kinetic parameters from non- isothermal thermogravimetric data was described. The activation energy and frequency factors were determined from the proposed method and also by the widely used Coats and Redfern method. The kinetic compensation effect between the activation energy and frequency factors obtained from both the methods were found to be very consistent and are in very good agreement with the literature values. The activation energy and frequency factors were also determined from isothermal experiments in the temperature range from 680 to 875°C. The activation energy and frequency factors determined from isothermal data using initial rate method were also found to be in very good agreement with the above results. It is also found that the kinetic parameters determined by isothermal analysis were consistent with the values determined by non-isothermal analysis.

Notes: Affinity separations rely on the highly specific binding between a protein in solution and an immobilized ligand to achieve a high degree of protein purification. A mathematical model including convection, diffusion, and rate kinetics is formulated to analyze the design and operation of affinity membrane bioseparation. The model equations are solved by orthogonal collocation method. Danckwerts' boundary conditions are used. The results obtained from model simulation show that the breakthrough of the protein is significantly influenced by Péclet number, feed protein concentration, Ligand number, Damköhler number, membrane thickness, and flow rate. Breakthrough profiles are quantitatively discussed in terms of protein recovery efficiency, ligand utilization efficiency, thickness of unused membrane, and width of the mass transfer zone.

Notes: A dynamic model incorporating biomass growth and liquid hold-up evolution is developed to describe a fixed bed bioreactor operation with cocurrent upflow of water and air flows. The model permits to predict cycle time and optimal operation conditions for high substrate removal and long cycle times. Simulation results are compared with published experimental results and show good model accuracy.

Notes: In this paper the simulation of hybrid processes containing membrane units will be discussed. For this purpose a user-defined module for simulation and design of membrane processes was implemented into the simulation program AspenPlus.The advantages can be summarized as follows:-any combination of membrane processes with all other units already implemented in AspenPlus is possible, including internal recycle streams-utilization of the physical property models and data bases of AspenPlus is possible- cost and sensitivity analysis can be performed.These benefits are demonstrated in detail for a membrane vapor recovery unit for the treatment of tank farm off -gas, for a two-stage reverse osmosis plant for organic/-organic separations and for a combination of distillation and pervaporation for the separation of a dimethylcarbonate/methanol mixture.

Notes: General simple criteria to predict and analyze the influence on trickle-bed reactors behavior of three phenomena, namely, plug flow deviations, external wetting efficiency and external mass transfer resistance, are developed. Criteria predictions are compared with results arising from a comprehensive mathematical model widely employed to describe trickle-bed reactors behavior and with other particular criteria reported in the literature. Present criteria applications to different sets of experimental data exemplify their practical utility for various actual situations and verify their validity. Besides, they constitute simple tools to diagnose detrimental on trickle-bed reactors operation.

Notes: A new continuous-flow recycle microwave reactor suitable for organic synthesis has been developed to handle 0.51 quantities of reagents. The apparatus, which is designed for laboratory use, operates at atmospheric pressure in open- or closed-loop mode. It is fitted with a temperature control system. We describe this novel reactor and illustrate its efficiency with examples of organic syntheses carried out using both homogeneous and heterogeneous reactions.

Notes: Local mass transfer studies have been carried out in an external loop airlift reactor and indicated the existence of significant non-uniformities in aeration capacity in the various sections of the reactor. The traditional assumption of a single well mixed unit with a single kL a value for external loop airlift reactors was found to be poor and cannot represent adequately the reactor as a whole. The liquid head in the gas/liquid separator was found to have a significant negative negative effect on the local mass transfer coefficient kL a. Visualization of flow patterns showed the existence of strong vortices in the riser and downcomer which contributed to a reduction in local aeration capacity. Mass transfer experiments in an aerated tank showed that the aeration capacity can be reduced by half in viscous media but improved significantly in the presence of salts.

Notes: The wetting characteristics of fine powders play an important role in a variety of processes. The most important way of characterising the wettability of a fluid/fluid/solid system is to measure the contact angle. This paper describes a relatively simple method for the determination of the contact angle on powdery materials. The technique involves the measurement of the dynamic contact angle which is formed when a liquid drop is placed on a horizontal porous surface. On the basis of the measured dynamic contact angle as a function of time an “apparent” static contact angle has been defined, which gives a measure of the wettability of porous solid systems by analogy with the wetting of non-porous solids. Determinations with glass beads and NaCl-powders as the test materials indicate that the measured value depends on the particle size of the powder, the porosity and the temperature. It was concluded that the capillary penetration of the liquid droplet into the porous media itself influences the wetting characteristics.

Notes: A mathematical model has been developed to simulate the operation of an absorption-driven multiple-effect evaporator. The model is based on mass and enthalpy balances and heat transfer rate equations of the various components of the system. The model has been validated by comparing model predictions to experimental results from the operation of a four effect absorption-driven falling film evaporator coupled with a two-effect regenerator which operated using solutions of sodium hydroxide as an absorptive medium. The model predictions are in satisfactory agreement with the experimental results.

Notes: Mass transfer with chemical reaction by liquid/liquid phase tranfer catalysis (LLPTC) for an isothermal batch reactor was analyzed. The results for the phase transfer catalyzed reaction system can be generally described by a pseudo first-order hypothesis, whereas the reaction system can be controlled by simultaneous mass transfer of the catalysts between two liquid phases and chemical reaction in the organic phase. The mass transfer limitation is mainly from the mass transfer step of QX from the organic phase to the aqueous phase. The concept of catalyst-effectiveness vs. physically meaningful parameters in a liquid/liquid phase transfer catalyzed reaction is introduced. The catalyst effectiveness is increased as the mass transfer factors increase, the ratio of reaction rate coefficients of aqueous forward reaction to organic increases, and the equilibrium constant in the aqueous solution increases.

Notes: A unified gas/ solid reaction model has been formulated for multi reactions with multi gas and solid species. The transient formulation has been followed by finite-difference method and subsequent solution via an iterative procedure. The simulation produces intermediate results for concentration profiles of various components and pressure and temperature distribution, in addition to various structural parameters within a reacting pellet. The effect of structural parameters is analysed. The general formulation allows homogeneous and heterogeneous reactions. Solid state processes can also be accommodated.

Notes: A solid state electrochemical reactor is described in which reactants can be oxidised at high temperatures over an anode/catalyst using co-fed oxygen gas as well as electrochemically supplied oxygen. The setup permits injection of isotopic pulses in the reactant streams. The composition and isotopic distribution in the products are recorded with a quadrupole mass spectrometer. The use of the system is exemplified by oxidation of methane over a Au + SrFeO3-δ//YSZ anode at 800-850°C. Pulses of 18O2 in the stream of co-fed O2 were used to study the reactivity and products of gaseous oxygen as distinguished from the electrochemically supplied oxygen. The results indicate that the anode used supports oxygen pumping, but is only moderately active for methane oxidation. The products are mainly CO and CO2. The content of 18O in the products is low, indicating that methane oxidation takes place by 16O-rich lattice oxygen. In comparison, a reference Au//YSZ electrode was found to be a slower anode for oxygen pumping, but a better catalyst for the reaction between CH4 and gaseous O2, seemingly involving adsorbed oxygen.

Notes: The flow of two immiscible liquids and the influence of an additional inserted gas phase in horizontal pipes is investigated. The experiments are carried out in a transparent horizontal pipe with an inner diameter of 59 mm and a total length of 48 m. Experimental results are presented for the flow regimes of the two phase and three phase flow of oil, water and gas mixtures. The effect of phase inversion on the pressure drop is measured. The experimental results obtained for the three phase flow of oil, water and air indicate that drag reduction is possible by injecting gas in laminar flowing mixtures of oil and water. In the aerated slug flow regime of oil, water and air a water dominated and an oil dominated flow system can be distinguished. The pressure drop of the three phase flow system is of the magnitude as the pressure drop of the two phase flow of gas and the dominating liquid phase.

Notes: During recent years the air stripping process has been increasingly applied to the cleaning of water contaminated by volatile organic compounds (VOC). The present contribution compares various methods of treating VOC-contaminated water, with a special focus on removal efficiency and economic aspects. In particular, air stripping, a universally used cleaning method, is described in greater detail. Design and operational aspects are worked out for packed stripping towers for the special case of water contaminated with chlorinated hydrocarbons. Experimental results substantiate predictions of various operating conditions, packing types and scale-up effects.

Notes: A critical comparison of the strength and weakness of two optimization strategies for thermochemical process is made, i.e. pinch analysis and exergy analysis. Although both methods have a unique root, i.e. the minimization of the exergy losses, pinch analysis has evolved to become an instrument of direct and optimal design of a heat exchanger network while exergy analysis as such does not give an indication about process optimization. In combination with an adequate simulation code of a process, however, it can help to find the optimum process structure.

Notes: Interfacial properties exert a fundamental influence on fluid/liquid separation processes, with the interfacial tension being an important quantity associated with mass transfer and mutual solubility of participating compounds. A better understanding of transport phenomena is achieved by obtaining interfacial tension data under different conditions of pressure and temperature and as a function of time. Generally, interfacial tension decreases with increasing pressure due to increased adsorption of the compressed fluid at the interface. In the case of considerable mutual solubility, interfacial tension further decreases with time as mass transfer into the bulk phase proceeds. Prediction of colloidal behaviour in a separation process requires acquisition of additional information on the presence of surfactants.

Notes: The generalised thermal parametric sensitivity criterion is applied to the thermal behaviour of the esterification of 2-butanol with propionic anhydride in a batch reactor under isoperibolic conditions. The reaction is catalysed by sulphuric acid, and the study covered the effects of both catalyst concentration and, in the absence of catalyst, jacket temperature. The experimental location of regions of parametric sensitivity agreed well with theoretical predictions. However, the process conditions that meet conventional standards for safe process design fall into the supercritical sensitivity region of the parametric model. This apparently contradictory result is discussed. The usefulness of the parametric sensitivity approach is illustrated by practical examples of scale-up and heat transfer in reactions prone to thermal runaway.

Notes: The optimal layout of a chemical plant is determined by both economic and environmental aspects. The mathematical approach to this problem is given by representing the process through a superstructure, including any foreseeable process topology. It is described by integer variables, whereas real variables arise from the unit models and the thermodynamic calculations. By including process constraints and an objective function, a Mixed Integer Nonlinear Programming (MINLP) optimization problem is postulated. In this paper MINLP algorithms are combined with a technique for the exergy analysis of chemical processes for the preliminary screening of process alternatives. The exergy analysis as a screening technique is advantageous due to a significantly smaller amount of required data and computing time, compared with true optimization, including cost estimation at an earlier stage of process synthesis and analysis. Thus, a broader solution space can be examined. The subsequent cost analysis has then only to be focused on a reduced set of parameters.