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.

Computer simulation of liquid flow patterns on distillation trays

This thesis describes work carried out to improve the fundamental modelling of liquid flows on distillation trays. A mathematical model is presented based on the principles of computerised fluid dynamics. It models the liquid flow in the horizontal directions allowing for the effects of the vapour through the use of an increased liquid turbulence, modelled by an eddy viscosity, and a resistance to liquid flow caused by the vapour being accelerated horizontally by the liquid. The resultant equations are similar to the Navier-Stokes equations with the addition of a resistance term.A mass-transfer model is used to calculate liquid concentration profiles and tray efficiencies. A heat and mass transfer analogy is used to compare theoretical concentration profiles to experimental water-cooling data obtained from a 2.44 metre diameter air-water distillation simulation rig. The ratios of air to water flow rates are varied in order to simulate three pressures: vacuum, atmospheric pressure and moderate pressure.For simulated atmospheric and moderate pressure distillation, the fluid mechanical model constantly over-predicts tray efficiencies with an accuracy of between +1.7% and +11.3%. This compares to -1.8% to -10.9% for the stagnant regions model (Porter et al. 1972) and +12.8% to +34.7% for the plug flow plus back-mixing model (Gerster et al. 1958). The model fails to predict the flow patterns and tray efficiencies for vacuum simulation due to the change in the mechanism of liquid transport, from a liquid continuous layer to a spray as the liquid flow-rate is reduced. This spray is not taken into account in the development of the fluid mechanical model. A sensitivity analysis carried out has shown that the fluid mechanical model is relatively insensitive to the prediction of the average height of clear liquid, and a reduction in the resistance term results in a slight loss of tray efficiency. But these effects are not great. The model is quite sensitive to the prediction of the eddy viscosity term. Variations can produce up to a 15% decrease in tray efficiency. The fluid mechanical model has been incorporated into a column model so that statistical optimisation techniques can be employed to fit a theoretical column concentration profile to experimental data. Through the use of this work mass-transfer data can be obtained.

Mathematical modelling and control of agitated extraction columns

Liquid-liquid extraction has long been known as a unit operation that plays an important role in industry. This process is well known for its complexity and sensitivity to operation conditions. This thesis presents an attempt to explore the dynamics and control of this process using a systematic approach and state of the art control system design techniques. The process was studied first experimentally under carefully selected. operation conditions, which resembles the ranges employed practically under stable and efficient conditions. Data were collected at steady state conditions using adequate sampling techniques for the dispersed and continuous phases as well as during the transients of the column with the aid of a computer-based online data logging system and online concentration analysis. A stagewise single stage backflow model was improved to mimic the dynamic operation of the column. The developed model accounts for the variation in hydrodynamics, mass transfer, and physical properties throughout the length of the column. End effects were treated by addition of stages at the column entrances. Two parameters were incorporated in the model namely; mass transfer weight factor to correct for the assumption of no mass transfer in the. settling zones at each stage and the backmixing coefficients to handle the axial dispersion phenomena encountered in the course of column operation. The parameters were estimated by minimizing the differences between the experimental and the model predicted concentration profiles at steady state conditions using non-linear optimisation technique. The estimated values were then correlated as functions of operating parameters and were incorporated in·the model equations. The model equations comprise a stiff differential~algebraic system. This system was solved using the GEAR ODE solver. The calculated concentration profiles were compared to those experimentally measured. A very good agreement of the two profiles was achieved within a percent relative error of ±2.S%. The developed rigorous dynamic model of the extraction column was used to derive linear time-invariant reduced-order models that relate the input variables (agitator speed, solvent feed flowrate and concentration, feed concentration and flowrate) to the output variables (raffinate concentration and extract concentration) using the asymptotic method of system identification. The reduced-order models were shown to be accurate in capturing the dynamic behaviour of the process with a maximum modelling prediction error of I %. The simplicity and accuracy of the derived reduced-order models allow for control system design and analysis of such complicated processes. The extraction column is a typical multivariable process with agitator speed and solvent feed flowrate considered as manipulative variables; raffinate concentration and extract concentration as controlled variables and the feeds concentration and feed flowrate as disturbance variables. The control system design of the extraction process was tackled as multi-loop decentralised SISO (Single Input Single Output) as well as centralised MIMO (Multi-Input Multi-Output) system using both conventional and model-based control techniques such as IMC (Internal Model Control) and MPC (Model Predictive Control). Control performance of each control scheme was. studied in terms of stability, speed of response, sensitivity to modelling errors (robustness), setpoint tracking capabilities and load rejection. For decentralised control, multiple loops were assigned to pair.each manipulated variable with each controlled variable according to the interaction analysis and other pairing criteria such as relative gain array (RGA), singular value analysis (SVD). Loops namely Rotor speed-Raffinate concentration and Solvent flowrate Extract concentration showed weak interaction. Multivariable MPC has shown more effective performance compared to other conventional techniques since it accounts for loops interaction, time delays, and input-output variables constraints.

BTX extraction by sulfolane in a mixer-settler cascade

The literature relating to the extraction of the aromatics, benzene, toluene and xylene (BTX) using different commercial solvents, and to mixer-settler design and performance, has been reviewed. Liquid-liquid equilibria of the ternary systems: hexane-benzene-sulfolane, n-heptane-toluene-sulfolane, and octane-xylene-sulfolane were determined experimentally at temperatures of 30oC, 35oC, and 40oC. The work was then extended to a multicomponent system. The data were correlated by using Hand's method and were found to be in a good agreement with theoretical predictions using the UNIFAC method. A study was made of the performance of a 10-stage laboratory mixer-settler cascade for the extraction of BTX from a synthetic reformate utilizing sulfolane as a solvent. Murphree stage efficiency decreased with stage number but 99% extraction was achievable within 4 stages. The effects of temperature, phase ratio, and agitator speed were investigated. The efficiency increased with agitator speed but > 1050 rpm resulted in secondary haze formation. An optimum temperature of 30oC was selected from the phase equilibria; the optimum solvent: feed ratio was 3:1 for 4 stages. The experimental overall mass transfer coefficients were compared with those predicted from single drop correlations and were in all cases greater, by a factor of 1.5 to 3, due to the surface renewal associated with drop break-up and coalescence promoted by agitation. A similar investigation was performed using real reformate from the Kuwait Oil Company. The phase ratios were in the range 0.5 to 1 to 3.25 to 1, the agitator speed 1050 rpm, and the operating temperature 30oC. A maximum recovery of 99% aromatics was achieved in 4 stages at a phase ratio of 3.25 to 1. A backflow model was extended to simulate conditions in the mixer-settler cascade with this multicomponent system. Overall mass transfer coefficients were estimated by obtaining the best fit between experimental and predicted concentration profiles. They were up to 10% greater than those with the synthetic feed but close agreement was not possible because the distribution coefficient and phase ratio varied with stage number. Sulfolane was demonstrated to be an excellent solvent for BTX recovery and a mixer-settler cascade was concluded to be a technically viable alternative to agitated columns for this process.

Solids mixing and segregation in a gas spout-fluid bed-effect of the distributor design

This work is concerned with the assessment of a newer version of the spout-fluid bed where the gas is supplied from a common plenum and the distributor controls the operational phenomenon. Thus the main body of the work deals with the effect of the distributor design on the mixing and segregation of solids in a spout-filled bed. The effect of distributor design in the conventional fluidised bed and of variation of the gas inlet diameter in a spouted bed were also briefly investigated for purpose of comparison. Large particles were selected for study because they are becoming increasingly important in industrial fluidised beds but have not been thoroughly investigated. The mean particle diameters of the fraction ranged from 550 to 2400 mm, and their specific gravity from 0.97 to 2.45. Only work carried out with binary systems is reported here. The effect of air velocity, particle properties, bed height, the relative amount of jetsam and flotsam and initial conditions on the steady-state concentration profiles were assessed with selected distributors. The work is divided into three sections. Sections I and II deal with the fluidised bed and spouted bed systems. Section III covers the development of the spout-filled bed and its behaviour with reference to distributor design and it is shown how benefits of both spouting and fluidising phenomena can be exploited. In the fluidisation zone, better mixing is achieved by distributors which produce a large initial bubble diameter. Some common features exist between the behaviour of unidensity jetsam-rich systems and different density flotsam-rich systems. The shape factor does not seem to have an affect as long as it is only restricted to the minor component. However, in the case of the major component, particle shape significantly affects the final results. Studies of aspect ratio showed that there is a maximum (1.5) above which slugging occurs and the effect of the distributor design is nullified. A mixing number was developed for unidensity spherical rich systems, which proved to be extremely useful in quantifying the variation in mixing and segregation with changes in distributor design.

The chromatographic separation of carbohydrate mixtures

The separation performance of a semicontinuous counter-current chromatographic refiner (SCCR7), consisting of twelve 5.4 cm id x 75cm long columns packed with calcium charged cross-linked polysytrene resin (KORELA VO7C), was optimised. An industrial barley syrup was used containing 42% fructose, 52% glucose and 6% maltose and oligosaccharides. The effects of temperature, flow rates and concentration on the distribution coefficients were evaluated and quantified by deriving general relationships. The effects of flow rates, feed composition and concentration on the separation performance of the SCCR7 were identified and general relationships between them and the switch time, which was found to be the controlling parameter, were developed. Fructose rich (FRP) and glucose rich (GRP) product purities of 99.9% were obtained at 18.6% w/v feed concentrations. When a 66% w/v feed concentration was used and product splitting technique was employed, the throughput was 32.1 kg sugar solids/m3 resin/hr. The GRP contained less than 4.5% fructose, the FRP was over 95% pure, and the respective concentrations were 22.56 and 11.29% w/v. Over 94% of the glucose and 95.78% of the fructose in the feed were recovered in the GRP and FRP respectively. By recycling the dilute product split fractions, the GRP and FRP concentrations were increased to 25.4 and 12.96% w/v; the FRP was 90.2% pure and the GRP contained 6.69% w/v fructose. A theoretical link between batch and semicontinuous chromatographic equipments has been determined. A computer simulation was developed predicting successfully the purging concentration profiles at `pseudo-equilibrium', and also certain system design parameters. An important further aspect of the work has been to study the behaviour of chromatographic bioreactor-separators. Such batch systems of 5.4cm id and lengths varying between 30 and 230cm, were used to investigate the effect of scaling up on the conversion of sucrose into dextran and fructose in the presence of the dextransucrase enzyme. Conversions of over 80% were achieved at 4 hr sucrose residence times. The crude dextransucrase was purified using centrifugation, ultrafiltration and cross-flow microfiltration techniques. Better enzyme stability was obtained by first separating the non-solid impurities using cross-flow microfiltration, and then removing the cells from the enzyme immediately before use by continuous centrifugation.

Flow patterns, performance and scale-up of distillation trays

This work is concerned with the nature of liquid flow across industrial sieve trays operating in the spray, mixed, and the emulsified flow regimes. In order to overcome the practical difficulties of removing many samples from a commercial tray, the mass transfer process was investigated in an air water simulator column by heat transfer analogy. The temperature of the warm water was measured by many thermocouples as the water flowed across the single pass 1.2 m diameter sieve tray. The thermocouples were linked to a mini computer for the storage of the data. The temperature data were then transferred to a main frame computer to generate temperature profiles - analogous to concentration profiles. A comprehensive study of the existing tray efficiency models was carried out using computerised numerical solutions. The calculated results were compared with experimental results published by the Fractionation Research Incorporation (FRl) and the existing models did not show any agreement with the experimental results. Only the Porter and Lockett model showed a reasonable agreement with the experimental results for cenain tray efficiency values. A rectangular active section tray was constructed and tested to establish the channelling effect and the result of its effect on circular tray designs. The developed flow patterns showed predominantly flat profiles and some indication of significant liquid flow through the central region of the tray. This comfirms that the rectangular tray configuration might not be a satisfactory solution for liquid maldistribution on sieve trays. For a typical industrial tray the flow of liquid as it crosses the tray from the inlet to the outlet weir could be affected by the mixing of liquid by the eddy, momentum and the weir shape in the axial or the transverse direction or both. Conventional U-shape profiles were developed when the operating conditions were such that the froth dispersion was in the mixed regime, with good liquid temperature distribution while in the spray regime. For the 12.5 mm hole diameter tray the constant temperature profiles were found to be in the axial direction while in the spray regime and in the transverse direction for the 4.5 mm hole tray. It was observed that the extent of the liquid stagnant zones at the sides of the tray depended on the tray hole diameter and was larger for the 4.5 mm hole tray. The liquid hold-up results show a high liquid hold-up at the areas of the tray with low liquid temperatures, this supports the doubts about the assumptions of constant point efficiency across an operating tray. Liquid flow over the outlet weir showed more liquid flow at the centre of the tray at high liquid loading with low liquid flow at both ends of the weir. The calculated results of the point and tray efficiency model showed a general increase in the calculated point and tray efficiencies with an increase in the weir loading, as the flow regime changed from the spray to the mixed regime the point and the tray efficiencies increased from approximately 30 to 80%.Through the mixed flow regime the efficiencies were found to remain fairly constant, and as the operating conditions were changed to maintain an emulsified flow regime there was a decrease in the resulting efficiencies. The results of the estimated coefficient of mixing for the small and large hole diameter trays show that the extent of liquid mixing on an operating tray generally increased with increasing capacity factor, but decreased with increasing weir loads. This demonstrates that above certain weir loads, the effect of eddy diffusion mechanism on the process of liquid mixing on an operating tray to be negligible.

Ionic and molecular diffusion in cementitious materials

The work described in this thesis is an attempt to provide improved understanding of the effects of several factors affecting diffusion in hydrated cement pastes and to aid the prediction of ionic diffusion processes in cement-based materials. Effect of pore structure on diffusion was examined by means of comparative diffusion studies of quaternary ammonium ions with different ionic radii. Diffusivities of these ions in hydrated pastes of ordinary portland cement with or without addition of fly ash were determined by a quasi-steady state technique. The restriction of the pore geometry on diffusion was evaluated from the change of diffusivity in response to the change of ionic radius. The pastes were prepared at three water-cement ratios, 0.35, 0.50 and 0.65. Attempts were made to study the effect of surface charge or the electrochemical double layer at the pore/solution interface on ionic diffusion. An approach was to evaluate the zeta potentials of hydrated cement pastes through streaming potential measurements. Another approach was the comparative studies of the diffusion kinetics of chloride and dissolved oxygen in hydrated pastes of ordinary portland cement with addition of 0 and 20% fly ash. An electrochemical technique for the determination of oxygen diffusivity was also developed. Non-steady state diffusion of sodium potassium, chloride and hydroxyl ions in hydrated ordinary portland cement paste of water-cement ratio 0.5 was studied with the aid of computer-modelling. The kinetics of both diffusion and ionic binding were considered for the characterization of the concentration profiles by Fick's first and second laws. The effect of the electrostatic interactions between ions on the overall diffusion rates was also considered. A general model concerning the prediction of ionic diffusion processes in cement-based materials has been proposed.

Innovative measurement methodology in the study of weathering of automotive coatings

An initial aim of this project was to evaluate the conventional techniques used in the analysis of newly prepared environmentally friendly water-borne automotive coatings and compare them with solvent-borne coatings having comparable formulations. The investigation was carried out on microtuned layers as well as on complete automotive multi-layer paint systems. Methods used included the very traditional methods of gloss and hardness and the commonly used photo-oxidation index (from FTIR spectral analysis). All methods enabled the durability to weathering of the automotive coatings to be initially investigated. However, a primary aim of this work was to develop methods for analysing the early stages of chemical and property changes in both the solvent-borne and water-borne coating systems that take place during outdoor natural weathering exposures and under accelerated artificial exposures. This was achieved by using dynamic mechanical analysis (DMA), in both tension mode on the microtomed films (on all depths of the coating systems from the uppermost clear-coat right down to the electron-coat) and bending mode of the full (unmicrotomed) systems, as well as MALDI-Tof analysis on the movement of the stabilisers in the full systems. Changes in glass transition temperature and relative cross-link density were determined after weathering and these were related to changes in the chemistries of the binder systems of the coatings after weathering. Concentration profiles of the UV-stabilisers (UVA and HALS) in the coating systems were analysed as a consequence of migration in the coating systems in separate microtomed layers of the paint samples (depth profiling) after weathering and diffusion co-efficient and solubility parameters were determined for the UV stabilisers in the coating systems. The methods developed were used to determine the various physical and chemical changes that take place during weathering of the different (water-borne and solvent-borne) systems (photoxidation). The solvent-borne formulations showed less changes after weathering (both natural and accelerated) than the corresponding water-borne formulations due to the lower level of cross-links in the binders of the water-borne systems. The silver systems examined were more durable than the blue systems due to the reflecting power of the aluminium and the lower temperature of the silver coatings.

A new rapidly absorbed paracetamol tablet containing sodium bicarbonate. II. Dissolution studies and in vitro/in vivo correlation

The objective of this study was to compare the in vitro dissolution profile of a new rapidly absorbed paracetamol tablet containing sodium bicarbonate (PS) with that of a conventional paracetamol tablet (P), and to relate these by deconvolution and mapping to in vivo release. The dissolution methods used include the standard procedure described in the USP monograph for paracetamol tablets, employing buffer at pH5.8 or 0.05 M HCl at stirrer speeds between 10 and 50 rpm. The mapping process was developed and implemented in Microsoft Excel® worksheets that iteratively calculated the optimal values of scale and shape factors which linked in vivo time to in vitro time. The in vitro-in vivo correlation (IVIVC) was carried out simultaneously for both formulations to produce common mapping factors. The USP method, using buffer at pH5.8, demonstrated no difference between the two products. However, using an acidic medium the rate of dissolution of P but not of PS decreased with decreasing stirrer speed. A significant correlation (r=0.773; p<.00001) was established between in vivo release and in vitro dissolution using the profiles obtained with 0.05 M HCl and a stirrer speed of 30 rpm. The scale factor for optimal simultaneous IVIVC in the fasting state was 2.54 and the shape factor was 0.16; corresponding values for mapping in the fed state were 3.37 and 0.13 (implying a larger in vitro-in vivo time difference but reduced shape difference in the fed state). The current IVIVC explains, in part, the observed in vivo variability of the two products. The approach to mapping may also be extended to different batches of these products, to predict the impact of any changes of in vitro dissolution on in vivo release and plasma drug concentration-time profiles.

Integrated Omics for the global mapping of biomolecules in LDL

Circulating low density lipoproteins (LDL) are thought to play a crucial role in the onset and development of atherosclerosis, though the detailed molecular mechanisms responsible for their biological effects remain controversial. The complexity of biomolecules (lipids, glycans and protein) and structural features (isoforms and chemical modifications) found in LDL particles hampers the complete understanding of the mechanism underlying its atherogenicity. For this reason the screening of LDL for features discriminative of a particular pathology in search of biomarkers is of high importance. Three major biomolecule classes (lipids, protein and glycans) in LDL particles were screened using mass spectrometry coupled to liquid chromatography. Dual-polarity screening resulted in good lipidome coverage, identifying over 300 lipid species from 12 lipid sub-classes. Multivariate analysis was used to investigate potential discriminators in the individual lipid sub-classes for different study groups (age, gender, pathology). Additionally, the high protein sequence coverage of ApoB-100 routinely achieved (≥70%) assisted in the search for protein modifications correlating to aging and pathology. The large size and complexity of the datasets required the use of chemometric methods (Partial Least Square-Discriminant Analysis, PLS-DA) for their analysis and for the identification of ions that discriminate between study groups. The peptide profile from enzymatically digested ApoB-100 can be correlated with the high structural complexity of lipids associated with ApoB-100 using exploratory data analysis. In addition, using targeted scanning modes, glycosylation sites within neutral and acidic sugar residues in ApoB-100 are also being explored. Together or individually, knowledge of the profiles and modifications of the major biomolecules in LDL particles will contribute towards an in-depth understanding, will help to map the structural features that contribute to the atherogenicity of LDL, and may allow identification of reliable, pathology-specific biomarkers. This research was supported by a Marie Curie Intra-European Fellowship within the 7th European Community Framework Program (IEF 255076). Work of A. Rudnitskaya was supported by Portuguese Science and Technology Foundation, through the European Social Fund (ESF) and "Programa Operacional Potencial Humano - POPH".