Vapour-liquid equilibrium studies at atmospheric to moderate pressures

A study of vapour-liquid equilibria is presented together with current developments. The theory of vapour-liquid equilibria is discussed. Both experimental and prediction methods for obtaining vapour-liquid equilibria data are critically reviewed. The development of a new family of equilibrium stills to measure experimental VLE data from sub-atmosphere to 35 bar pressure is described. Existing experimental techniques are reviewed, to highlight the needs for these new apparati and their major attributes. Details are provided of how apparatus may be further improved and how computer control may be implemented. To provide a rigorous test of the apparatus the stills have been commissioned using acetic acid-water mixture at one atmosphere pressure. A Barker-type consistency test computer program, which allows for association in both phases has been applied to the data generated and clearly shows that the stills produce data of a very high quality. Two high quality data sets, for the mixture acetone-chloroform, have been generated at one atmosphere and 64.3oC. These data are used to investigate the ability of the new novel technique, based on molecular parameters, to predict VLE data for highly polar mixtures. Eight, vapour-liquid equilibrium data sets have been produced for the cyclohexane-ethanol mixture at one atmosphere, 2, 4, 6, 8 and 11 bar, 90.9oC and 132.8oC. These data sets have been tested for thermodynamic consistency using a Barker-type fitting package and shown to be of high quality. The data have been used to investigate the dependence of UNIQUAC parameters with temperature. The data have in addition been used to compare directly the performance of the predictive methods - Original UNIFAC, a modified version of UNIFAC, and the new novel technique, based on molecular parameters developed from generalised London's potential (GLP) theory.

Studies in three phase gas-liquid-solid fluidised systems

The work is a logical continuation of research started at Aston some years ago when studies were conducted on fermentations in bubble columns. The present work highlights typical design and operating problems that could arise in such systems as waste water, chemical, biochemical and petroleum operations involving three-phase, gas-liquid-solid fluidisation; such systems are in increasing use. It is believed that this is one of few studies concerned with `true' three-phase, gas-liquid-solid fluidised systems, and that this work will contribute significantly to closing some of the gaps in knowledge in this area. The research work was mainly experimentally based and involved studies of the hydrodynamic parameters, phase holdups (gas and solid), particle mixing and segregation, and phase flow dynamics (flow regime and circulation patterns). The studies have focused particularly on the solid behaviour and the influence of properties of solids present on the above parameters in three-phase, gas-liquid-solid fluidised systems containing single particle components and those containing binary and ternary mixtures of particles. All particles were near spherical in shape and two particle sizes and total concentration levels were used. Experiments were carried out in two- and three-dimensional bubble columns. Quantitative results are presented in graphical form and are supported by qualitative results from visual studies which are also shown as schematic diagrams and in photographic form. Gas and solid holdup results are compared for air-water containing single, binary and ternary component particle mixtures. It should be noted that the criteria for selection of the materials used are very important if true three-phase fluidisation is to be achieved: this is very evident when comparing the results with those in the literature. The fluid flow and circulation patterns observed were assessed for validation of the generally accepted patterns, and the author believes that the present work provides more accurate insight into the modelling of liquid circulation in bubble columns. The characteristic bubbly flow at low gas velocity in a two-phase system is suppressed in the three-phase system. The degree of mixing within the system is found to be dependent on flow regime, liquid circulation and the ratio of solid phase physical properties. Evidence of strong `trade-off' of properties is shown; the overall solid holdup is believed to be a major parameter influencing the gas holdup structure.

Gas-liquid-solid flow modelling in a bubble column

An alternative approach to the modelling of solid-liquid and gas-liquid-solid flows for a 5:1 height to width aspect ratio bubble column is presented here. A modified transport equation for the volume fraction of a dispersed phase has been developed for the investigation of turbulent buoyancy driven flows (Chem. Eng. Proc., in press). In this study, a modified transport equation has been employed for discrete phase motion considering both solid-liquid and gas-liquid-solid flows. The modelling of the three-phase flow in a bubble column was achieved in the following case: injecting a slug of solid particles into the column for 10 s at a velocity of 0.1 m s-1 and then the gas phase flow was initiated with a superficial gas velocity of 0.02 cm s-1. © 2003 Elsevier B.V. All rights reserved.

Models of gas-liquid solubilities

A recent method for phase equilibria, the AGAPE method, has been used to predict activity coefficients and excess Gibbs energy for binary mixtures with good accuracy. The theory, based on a generalised London potential (GLP), accounts for intermolecular attractive forces. Unlike existing prediction methods, for example UNIFAC, the AGAPE method uses only information derived from accessible experimental data and molecular information for pure components. Presently, the AGAPE method has some limitations, namely that the mixtures must consist of small, non-polar compounds with no hydrogen bonding, at low moderate pressures and at conditions below the critical conditions of the components. Distinction between vapour-liquid equilibria and gas-liquid solubility is rather arbitrary and it seems reasonable to extend these ideas to solubility. The AGAPE model uses a molecular lattice-based mixing rule. By judicious use of computer programs a methodology was created to examine a body of experimental gas-liquid solubility data for gases such as carbon dioxide, propane, n-butane or sulphur hexafluoride which all have critical temperatures a little above 298 K dissolved in benzene, cyclo-hexane and methanol. Within this methodology the value of the GLP as an ab initio combining rule for such solutes in very dilute solutions in a variety of liquids has been tested. Using the GLP as a mixing rule involves the computation of rotationally averaged interactions between the constituent atoms, and new calculations have had to be made to discover the magnitude of the unlike pair interactions. These numbers have been seen as significant in their own right in the context of the behaviour of infinitely-dilute solutions. A method for extending this treatment to "permanent" gases has also been developed. The findings from the GLP method and from the more general AGAPE approach have been examined in the context of other models for gas-liquid solubility, both "classical" and contemporary, in particular those derived from equations-of-state methods and from reference solvent methods.

Simultaneous chemical reaction and distillation of formaldehyde

The thesis is concerned with the development and testing of a mathematical model of a distillation process in which the components react chemically. The formaldehyde-methanol-water system was selected and only the reversible reactions between formaldehyde and water giving methylene glycol and between formaldehyde and methanol producing hemiformal were assumed to occur under the distillation conditions. Accordingly the system has been treated as a five component system. The vapour-liquid equilibrium calculations were performed by solving iteratively the thermodynamic relationships expressing the phase equilibria with the stoichiometric equations expressing the chemical equilibria. Using optimisation techniques, the Wilson single parameters and Henry's constants were calculated for binary systems containing formaldehyde which was assumed to be a supercritical component whilst Wilson binary parameters were calculated for the remaining binary systems. Thus the phase equilibria for the formaldehyde system could be calculated using these parameters and good accuracy was obtained when calculated values were compared with experimental values. The distillation process was modelled using the mass and energy balance equations together with the phase equilibria calculations. The plate efficiencies were obtained from a modified A.I.Ch.E. Bubble Tray method. The resulting equations were solved by an iterative plate to plate calculation based on the Newton Raphson method. Experiments were carried out in a 76mm I.D., eight sieve plate distillation column and the results were compared with the mathematical model calculations. Overall, good agreement was obtained but some discrepancies were observed in the concentration profiles and these may have been caused by the effect of limited physical property data and a limited understanding of the reactions mechanism. The model equations were solved in the form of modular computer programs. Although they were written to describe the steady state distillation with simultaneous chemical reaction of the formaldehyde system, the approach used may be of wider application.

Computational fluid dynamical studies of structured distillation packings

In recent years structured packings have become more widely used in the process industries because of their improved volumetric efficiency. Most structured packings consist of corrugated sheets placed in the vertical plane The corrugations provide a regular network of channels for vapour liquid contact. Until recently it has been necessary to develop new packings by trial and error, testing new shapes in the laboratory. The orderly repetitive nature of the channel network produced by a structured packing suggests it may be possible to develop improved structured packings by the application of computational fluid dynamics (CFD) to calculate the packing performance and evaluate changes in shape so as to reduce the need for laboratory testing. In this work the CFD package PHOENICS has been used to predict the flow patterns produced in the vapour phase as it passes through the channel network. A particular novelty of the approach is to set up a method of solving the Navier Stokes equations for any particular intersection of channels. The flow pattern of the streams leaving the intersection is then made the input to the downstream intersection. In this way the flow pattern within a section of packing can be calculated. The resulting heat or mass transfer performance can be calculated by other standard CFD procedures. The CFD predictions revealed a circulation developing within the channels which produce a loss in mass transfer efficiency The calculations explained and predicted a change in mass transfer efficiency with depth of the sheets. This effect was also shown experimentally. New shapes of packing were proposed to remove the circulation and these were evaluated using CFD. A new shape was chosen and manufactured. This was tested experimentally and found to have a higher mass transfer efficiency than the standard packing.

Use of computational fluid dynamics in the design of bubble column reactors

Investigations into the modelling techniques that depict the transport of discrete phases (gas bubbles or solid particles) and model biochemical reactions in a bubble column reactor are discussed here. The mixture model was used to calculate gas-liquid, solid-liquid and gasliquid-solid interactions. Multiphase flow is a difficult phenomenon to capture, particularly in bubble columns where the major driving force is caused by the injection of gas bubbles. The gas bubbles cause a large density difference to occur that results in transient multi-dimensional fluid motion. Standard design procedures do not account for the transient motion, due to the simplifying assumptions of steady plug flow. Computational fluid dynamics (CFD) can assist in expanding the understanding of complex flows in bubble columns by characterising the flow phenomena for many geometrical configurations. Therefore, CFD has a role in the education of chemical and biochemical engineers, providing the examples of flow phenomena that many engineers may not experience, even through experimentation. The performance of the mixture model was investigated for three domains (plane, rectangular and cylindrical) and three flow models (laminar, k-e turbulence and the Reynolds stresses). mThis investigation raised many questions about how gas-liquid interactions are captured numerically. To answer some of these questions the analogy between thermal convection in a cavity and gas-liquid flow in bubble columns was invoked. This involved modelling the buoyant motion of air in a narrow cavity for a number of turbulence schemes. The difference in density was caused by a temperature gradient that acted across the width of the cavity. Multiple vortices were obtained when the Reynolds stresses were utilised with the addition of a basic flow profile after each time step. To implement the three-phase models an alternative mixture model was developed and compared against a commercially available mixture model for three turbulence schemes. The scheme where just the Reynolds stresses model was employed, predicted the transient motion of the fluids quite well for both mixture models. Solid-liquid and then alternative formulations of gas-liquid-solid model were compared against one another. The alternative form of the mixture model was found to perform particularly well for both gas and solid phase transport when calculating two and three-phase flow. The improvement in the solutions obtained was a result of the inclusion of the Reynolds stresses model and differences in the mixture models employed. The differences between the alternative mixture models were found in the volume fraction equation (flux and deviatoric stress tensor terms) and the viscosity formulation for the mixture phase.

Phase equilibrium studies at normal pressures

A total pressure apparatus has been developed to measure vapour-liquid equilibrium data on binary mixtures at atmospheric and sub-atmospheric pressures. The method gives isothermal data which can be obtained rapidly. Only measurements of total pressure are made as a direct function of composition of synthetic liquid phase composition, the vapour phase composition being deduced through the Gibbs-Duhem relationship. The need to analyse either of the phases is eliminated. As such the errors introduced by sampling and analysis are removed. The essential requirements are that the pure components be degassed completely since any deficiency in degassing would introduce errors into the measured pressures. A similarly essential requirement was that the central apparatus would have to be absolutely leak-tight as any leakage of air either in or out of the apparatus would introduce erroneous pressure readings. The apparatus was commissioned by measuring the saturated vapour pressures of both degassed water and ethanol as a function of temperature. The pressure-temperature data on degassed water measured were directly compared with data in the literature, with good agreement. Similarly the pressure-temperature data were measured for ethanol, methanol and cyclohexane and where possible a direct comparison made with the literature data. Good agreement between the pure component data of this work and those available in the literature demonstrates firstly that a satisfactory degassing procedure has been achieved and that secondly the measurements of pressure-temperature are consistent for any one component; since this is true for a number of components, the measurements of both temperature and pressure are both self-consistent and of sufficient accuracy, with an observed compatibility between the precision/accuracy of the separate means of measuring pressure and temperature. The liquid mixtures studied were of ethanol-water, methanol-water and ethanol-cyclohexane. The total pressure was measured as the composition inside the equilibrium cell was varied at a set temperature. This gave P-T-x data sets for each mixture at a range of temperatures. A standard fitting-package from the literature was used to reduce the raw data to yield y-values to complete the x-y-P-T data sets. A consistency test could not be applied to the P-T-x data set as no y-values were obtained during the experimental measurements. In general satisfactory agreement was found between the data of this work and those available in the literature. For some runs discrepancies were observed, and further work recommended to eliminate the problems identified.

Phase equilibrium studies at moderate pressures

The theory of vapour-liquid equilibria is reviewed, as is the present status or prediction methods in this field. After discussion of the experimental methods available, development of a recirculating equilibrium still based on a previously successful design (the modified Raal, Code and Best still of O'Donnell and Jenkins) is described. This novel still is designed to work at pressures up to 35 bar and for the measurement of both isothermal and isobaric vapour-liquid equilibrium data. The equilibrium still was first commissioned by measuring the saturated vapour pressures of pure ethanol and cyclohexane in the temperature range 77-124°C and 80-142°C respectively. The data obtained were compared with available literature experimental values and with values derived from an extended form of the Antoine equation for which parameters were given in the literature. Commissioning continued with the study of the phase behaviour of mixtures of the two pure components as such mixtures are strongly non-ideal, showing azeotopic behaviour. Existing data did not exist above one atmosphere pressure. Isothermal measurements were made at 83.29°C and 106.54°C, whilst isobaric measurements were made at pressures of 1 bar, 3 bar and 5 bar respectively. The experimental vapour-liquid equilibrium data obtained are assessed by a standard literature method incorporating a themodynamic consistency test that minimises the errors in all the measured variables. This assessment showed that reasonable x-P-T data-sets had been measured, from which y-values could be deduced, but that the experimental y-values indicated the need for improvements in the design of the still. The final discussion sets out the improvements required and outlines how they might be attained.

The behaviour of polymer quenchants

The internationally accepted Wolfson Heat Treatment Centre Engineering Group test was used to evaluate the cooling characteristics of the most popular commercial polymer quenchants: polyalkylene glycols, polyvinylpyrrolidones and polyacrylates. Prototype solutions containing poly(ethyloxazoline) were also examined. Each class of polymer was capable of providing a wide range of cooling rates depending on the product formulation, concentration, temperature, agitation, ageing and contamination. Cooling rates for synthetic quenchants were generally intermediate between those of water and oil. Control techniques, drag-out losses and response to quenching in terms of hardness and residual stress for a plain carbon steel, were also considered. A laboratory scale method for providing a controllable level of forced convection was developed. Test reproducibility was improved by positioning the preheated Wolfson probe 25mm above the geometric centre of a 25mm diameter orifice through which the quenchant was pumped at a velocity of 0.5m/s. On examination, all polymer quenchants were found to operate by the same fundamental mechanism associated with their viscosity and ability to form an insulating polymer-rich-film. The nature of this film, which formed at the vapour/liquid interface during boiling, was dependent on the polymer's solubility characteristics. High molecular weight polymers and high concentration solutions produced thicker, more stable insulating films. Agitation produced thinner more uniform films. Higher molecular weight polymers were more susceptible to degradation, and increased cooling rates, with usage. Polyvinylpyrrolidones can be cross-linked resulting in erratic performance, whilst the anionic character of polyacrylates can lead to control problems. Volatile contaminants tend to decrease the rate of cooling and salts to increase it. Drag-out increases upon raising the molecular weight of the polymer and its solution viscosity. Kinematic viscosity measurements are more effective than refractometer readings for concentration control, although a quench test is the most satisfactory process control method.

Mass transfer and chemical reaction on a distillation plate

A multistage distillation column in which mass transfer and a reversible chemical reaction occurred simultaneously, has been investigated to formulate a technique by which this process can be analysed or predicted. A transesterification reaction between ethyl alcohol and butyl acetate, catalysed by concentrated sulphuric acid, was selected for the investigation and all the components were analysed on a gas liquid chromatograph. The transesterification reaction kinetics have been studied in a batch reactor for catalyst concentrations of 0.1 - 1.0 weight percent and temperatures between 21.4 and 85.0 °C. The reaction was found to be second order and dependent on the catalyst concentration at a given temperature. The vapour liquid equilibrium data for six binary, four ternary and one quaternary systems are measured at atmospheric pressure using a modified Cathala dynamic equilibrium still. The systems with the exception of ethyl alcohol - butyl alcohol mixtures, were found to be non-ideal. Multicomponent vapour liquid equilibrium compositions were predicted by a computer programme which utilised the Van Laar constants obtained from the binary data sets. Good agreement was obtained between the predicted and experimental quaternary equilibrium vapour compositions. Continuous transesterification experiments were carried out in a six stage sieve plate distillation column. The column was 3" in internal diameter and of unit construction in glass. The plates were 8" apart and had a free area of 7.7%. Both the liquid and vapour streams were analysed. The component conversion was dependent on the boilup rate and the reflux ratio. Because of the presence of the reaction, the concentration of one of the lighter components increased below the feed plate. In the same region a highly developed foam was formed due to the presence of the catalyst. The experimental results were analysed by the solution of a series of simultaneous enthalpy and mass equations. Good agreement was obtained between the experimental and calculated results.

Modelling a biochemical reaction with computational fluid dynamics

Earlier investigations (Cartland Glover et al., 2004) into the use of computational fluid dynamics (CFD) for the modelling of gas-liquid and gas-liquid-solid flow allowed a simple biochemical reaction model to be implemented. A single plane mesh was used to represent the transport and reaction of molasses, the mould Aspergillus niger and citric acid in a bubble column with a height to diameter aspect ratio of 20:1. Two specific growth rates were used to examine the impact that biomass growth had on the local solids concentration and the effect this had on the local hydrodynamics of the bubble column.