Discrete element modelling of fluidised bed spray granulation

A novel discrete element spray granulation model capturing the key features of fluidised bed hydrodynamics, liquid-solid contacting and agglomeration is presented. The model computes the motion of every individual particle and droplet in the system, considering the gas phase as a continuum. Microscale processes such as particle-particle collisions, droplet-particle coalescence and agglomeration are directly taken into account by simple closure models. Simulations of the hydrodynamic behaviour of a batch granulation process are presented to demonstrate the potential of the model for creating insight into the influence of several key process conditions such as fluidisation velocity, spray rate and spray pattern on powder product characteristics.     

Characterisation of fluidised bed granulation processes using in-situ Raman spectroscopy

Previous work by the authors Walker et al. [2007b. Fluidised bed characterisation using Raman spectroscopy: applications to pharmaceutical processing. Chemical Engineering Science 62, 3832–3838] illustrated that Raman spectroscopy could be used to provide 3-D maps of the concentration and chemical structure of particles in motion in a fluidised bed, within a relatively short (120 s) time window. Moreover, we reported that the technique, as outlined, has the potential to give detailed in-situ information on how the structure and composition of granules/powders within the fluidised bed (dryer or granulator) vary with the position and evolve with time. In this study we extended the original work by shortening the time window of the Raman spectroscopic analysis to 10 s, which has allowed the in-situ real-time characterisation of a fluidised bed granulation process. Here we show an important new use of the technique which allows in-situ measurement of the composition of the material within the fluidised bed in three spatial dimensions and as a function of time. This is achieved by recording Raman spectra using a probe positioned within the fluidised bed on a long-travel x–y–z stage. In these experiments the absolute Raman intensity is used to provide a direct measure of the amount of any given material in the probed volume, i.e. a particle density. Particle density profiles have been calculated over the granulation time and show how the volume of the fluidised bed decreases with an increase mean granule size. The Raman spectroscopy analysis indicated that nucleation/coalescence in this co-melt fluidised hot melt granulation system occurred over a relatively short time frame (t<30 s). The Raman spectroscopic technique demonstrated accurate correlation with independent granulation experiments which provided particle size distribution analysis. The similarity of the data indicates that the Raman spectra accurately represent solids ratios within the bed, and thus the techniques quantitative capabilities for future use in the pharmaceutical industry.     

Kinetics of fluidised bed melt granulation III: Tracer studies

Previous work (Proceedings of World Congress on Particle Technology, Sydney 2002, 629-636.) has shown that granule breakage occurs during fluidised bed melt granulation (FBMG) and should not be neglected when it comes to addressing granulation kinetics. In the current work, we have developed and verified tracer experiments in FBMG, in an attempt to decouple the influence of granule size and age on breakage kinetics. The tracer data during granulation shows that granule breakage is occurring at a much slower rate than aggregation, while the breakage-only tracer experiments reveal the breakage selection rate to be independent of size at an approximate value of . The observations allow us to deduce that the aggregation rate for smaller granules is actually faster than larger ones during granulation.     

Kinetics of fluidised bed melt granulation I: The effect of process variables

This paper is the first of a series to study the influence of operating conditions on the kinetics of fluidised bed melt granulation. First, we identify the rate processes responsible for the net growth in granule size in a top-sprayed fluidised bed granulator and propose a sequence of events based on these rate processes. The overall kinetics during the process is identified to be a combination of particle aggregation, binder solidification and granule breakage. By conducting experiments in a small-scale modified commercial fluidised bed granulator, the influence of various operating conditions (binder spray rate, bed temperature, atomising pressure, fluidising air velocity) on the granule growth behaviour was examined. The results indicate the granule growth rate to be directly dependent on the relative amount of binder sprayed into the bed, which essentially determines the speed of the aggregation process. The overall granule growth rate is observed to increase relatively with increased bed temperature for a more viscous PEG4000, while a maximum growth is seen for a lower viscosity PEG1500. A larger droplet size was also seen to have increased the overall growth rate, even though a smaller droplet seems to be able to induce a faster initial growth. The results also reveal the increase in fluidising air velocity to reduce the overall granule growth rate. The final granule size distribution was also observed to become narrower with increased bed temperature and fluidising air velocity. These observations are effectively explained using the proposed sequence of rate events.     

Binder addition methods and binder distribution in high shear and fluidised bed granulation

Fluidised beds and high shear mixers are both important in industrial granulation. The binder addition method (pouring, melt-in, spraying) affects the growth and properties of granules and is therefore of vital importance to the fundamental understanding of this detailed process. Non-uniformity of binder distribution is well known in high shear melt granulation, however, there is limited literature surrounding binder distribution in fluidised bed granulation. It was therefore the aim of the paper to compare the binder distribution using alternative addition methods in both high shear mixer and fluidised bed.In this work two binder addition methods, ‘wet’ and ‘dry’, in a fluidised bed and high hear mixer were used to successfully produce granules with a typical pharmaceutical size, 150-300 μm. The granules were analysed for final binder distribution in different size classes using Patent V blue dye and ultra-violet spectrometry.All binder addition methods supported previous work showing non-uniformity of binder distribution throughout the size classes. High shear mixer results show great similarity in binder content whichever binder addition method was chosen. This is likely to be due to the same mechanisms occurring due to the impeller forces in the process, mean while the fluidised bed results show little similarity. The binder distribution by mass is also investigated and shows that although most studies show a relative higher binder content in the larger size classes that actually the majority of binder can instead be found around the mean size of the batch.     

Kinetics of fluidised bed melt granulation V: Simultaneous modelling of aggregation and breakage

The main purpose of this paper is to quantify the aggregation and breakage rates in fluidised bed melt granulation (FBMG) and to subsequently relate them to various experimental conditions. The earlier paper of this series (2004d, Powder Technology 143-144, 65-83) illustrated a sequence of development and verification work on a breakage model for FBMG, based on the population balance modelling work on tracer experimental studies. A new error-weighted integral technique was also developed, which allows simultaneous extraction of the aggregation and breakage selection rate constant, as well as the attrition constant that reveals the relative amount of attrition during FBMG. Further research is conducted here, as the similar modelling strategy is employed to extract the aggregation and breakage kinetics at different operating conditions. A series of plots revealing the influence of operating conditions (binder spray rates, bed temperature, droplet size and fluidising air flow rate) on these extracted constants are therefore established. The aggregation rate constant plots reveal that the particle aggregation rate is dependent on the amount of binder available per unit time, and hence scales directly with the binder spray rate. The aggregation rate is also observed to increase with increased bed temperature when a higher viscosity binder is used, but reveals a maximum aggregation rate for a less viscous binder. The aggregation rate also increases with larger droplet size and lower fluidising air velocity. The breakage selection rate and attrition constant plot both reveal no direct dependence on binder spray rate, due to the separation in time scale over which the granule breakage occurs. The breakage rate and the extent of granule attrition is also found to decrease with increased bed temperature and increased fluidising air velocity. Due to scatter in the data, it is not possible to deduce any sensible trend on the influence of droplet size on its relative breakage rate and attrition.     

The effect of primary particle surface energy on agglomeration rate in fluidised bed wet granulation

The effect of primary particle surface wettability by a binder solution on the rate of agglomeration in a fluid-bed top-spray granulation process was investigated. A model system consisting of hydrophilic and hydrophobic spherical primary particles with a narrow size distribution, and an aqueous solution of hydroxy propyl-cellulose (HPC) as binder, was used. The surface energy of the primary particles was measured by inverse gas chromatography (IGC) and their wettability was characterised by static and dynamic contact angle. Granulation was carried out in a desktop fluid-bed granulator and the resulting granule size distribution and granule microstructure were analysed. The hydrophobic particles gave a wider granule size distribution (larger maximum granule size) than hydrophilic ones under otherwise identical conditions, and the granules were notably rounder and more compact. However, the fraction of un-granulated fines was also higher in the case of hydrophobic primary particles. SEM analysis of granule microstructure revealed that the hydrophilic particles were coated by the binder solution, which left a smaller amount of binder available to form bonds at particle contacts. On the other hand, all of the binder was found to form solid bridges in the case of hydrophobic primary particles. A population balance model was used to explain the observed granulation behaviour.     

Particle growth mechanisms in fluidised bed granulation—I: The effect of process variables

Two types of product granule have been identified in an experimental study of batch fluidised bed granulation; agglomerates which consist of two or more, and usually several, initial particles; and layered granules, which consist of single primary particles with dried feed material adhering to the surface. Increasing the excess fluidising gas velocity, in the range U-U_mf = 0.15-0.525 m s^?1, resulted in decreased particle growth rates and, depending upon the binder material, a change in product morphology from agglomerates to layered granules. Similar changes resulted from increasing the mean size of the starting material. Thus, a mechanism of particle growth is proposed in which the strength of inter-particle bridges and the extent of fluid drag and inertial forces on particles determine the equilibrium granule form and size. However, if the initial particles are porous this mechanism may break down since liquid may enter intra-particle pores and be unavailable for the initial formation of liquid bonds.     

Comparison of quality parameters of granola produced by wet granulation with commercially available product

This study involves comparing key quality parameters (size, textural) of commercially available breakfast cereal granola with product produced by high shear and fluidised bed granulation processes. Impeller rotational speed was found to be the single most important process parameter which influences granola physical and textural properties in the production of high shear granola. In a fluidised bed granulation process nozzle air pressure and binder spray rate were both found to affect aggregate quality attributes. Overall, the high shear granulation process led to larger, denser, less porous and stronger (less likely to break) aggregates compared with the fluidised bed process.Commercial granola samples were compared with the granola produced in this study and showed a large variation in terms of size and textural properties across the brands investigated. Depending in the type of granola required (for example, to be sold as a stand alone breakfast cereal or as accompaniment to yogurt) different manufacturing processes and process parameters may be recommended. The insights gained from this work can aid in developing processes for the production of granola or similar products to match with consumer and manufacture expectations and requirements.     

A circulating fluidised bed

Induced particle circulation was studied in a 0.3 m diam. air fluidised bed of sand with central draught tubes of 0.2 m and 0.15 m diam. and 0.6 m and 1.2 m in length. A “two-dimensional” bed, 0.3 m in width, of similar cross-section, was also used to study catalyst particle circulation. Superficial gas velocities of up to 0.4 m/s of air were supplied to the base of the draught tube to induce particle circulation rates in the annular downcomer of up to 400 kg/m² s. The circulation rate was shown to be affected by the gap height between the distributor and the draught tube, but was not affected by the draught tube length of height of bed above it. A model was developed to predict the circulation rate, assuming that the driving force for circulation was the density difference between draught tube and annulus and that energy was dissipated by particle shear at the walls. The theory is in reasonable agreement with the experimental results. A tentative model for predicting the shear stress at the wall of a flowing fluidised bed is presented.     

Particle growth mechanisms in fluidised bed granulation—II: Comparison of experimental data with growth models

Growth data from batch granulation experiments have been fitted to simple geometrical models. Layered granule growth approximates to concentric coating of core particles with binder, although the actual mechanism of growth is different. In the case of agglomeration, a relationship is established betwee mean granule size and binder content.     

Nucleation and growth in fluidised hot melt granulation

Fluidised hot melt granulation (FHMG) is a novel technology for granulation process in pharmaceutical industry, which has distinct advantages over other commercial techniques. The aim of this research was to investigate granulation and the effect of process parameters that may affect FHMG process. In this work, ballotini beads were used as the model particles and Lutrol® F 68 Poloxamer 188 was used as meltable solid binder. In order to determine the granulation and nucleation mechanism in this co-melt FHMG system, several parameters were investigated, such as binder content, particle size of binder and particle size and hydrophobicity of ballotini. These parameters were correlated to granule size distribution, mean granule size and granule shape. Furthermore, these experimental investigations were designed so that the coalescence model could be applied to the co-melt FHMG system. The analysis indicated that the non-inertial regime extends over a relatively short time period of < 60s, however this accounts for the majority of the particle size increase in the entire process. A decrease in the extent of granulation was induced by increasing the hydrophobicity of the ballotini, which was ascribed to a decrease in capillary pressure of the system.     

Agglomeration in fluidised bed gasification of biomass

Three promising biomass fuels for southern Mediterranean regions were tested for their agglomeration tendency in an atmospheric lab-scale fluidised bed (FB) gasifier using quartz and olivine as bed materials. The defluidisation temperatures of the energy crops Giant Reed (Arundo donax L.) and Sweet Sorghum bagasse were respectively approx. 790 °C and 810 °C, in both bed materials, while the agro industrial residue olive bagasse caused defluidisation of the quartz bed at 830 °C and olivine bed at > 850 °C. Agglomerates from these tests were analysed with SEM/EDS. Coatings and necks between bed particles were formed due to ash derived potassium silicate melt. For the first two fuels cluster-type agglomerates around remains of char particles were observed. Thermodynamic equilibrium simulations of each chemical system were performed to cross examine the predicted ash melting temperatures and chemistry with experimental findings. Predictions of potassium liquid compounds, like K₂O·SiO_2(l) were verified by EDS analyses on the particle coatings. FB gasification of olive bagasse resisted defluidisation up to higher temperatures because of its lower potassium and higher calcium content, especially in the case of olivine bed. The latter experimental finding coincided with thermodynamic predictions.     

Assessment of fluidised bed ion exchange equipment

Continuous countercurrent fluidised bed ion exchange equipment has certain advantages over moving packed bed or fixed bed equipment. The treatment of high flow rate dilute waste streams containing particulate matter and the processing of uranium ore unfiltered pulps are considered in the application of fluidised bed systems. Methods of obtaining design data are outlined and techniques for calculating the performance of continuous counterflow systems are proposed for various situations.     

Mass transfer in fluidised bed electrochemical reactors

Electrochemical mass transfer experiments involving the cathodic deposition of copper from aqueous solutions containing H₂SO₄ have been performed for two distinct cases. (a) Determination of mass transfer rates at a plane wall electrode in the presence of a fluidized bed of inert particles (glass beads). In this work bed height, bed size and fluidization conditions have been varied and a correlating equation:

is suggested as applying over the range

Comparison is made with mass transfer data of several other authors, revealing considerable variance. (b) Determination of mass transfer rates between electrolyte and particles within an active bed of fluidized conducting copper particles. Analysis of the data yields a correlating equation:

in the range

This compares very well with another source for electrolytic fluidized bed mass transfer, but is somewhat lower than other equations for particle to fluid non-electrolytic mass transfer.     

Copper deposition in a fluidised bed cell

A fluidised bed cell with rectangular geometry is used to deposit copper from acidified aqueous solutions containing 2 g 1^?1 of copper.Potential and current distributions through the fluidised bed are measured and shown to follow a logical pattern compatible with previous results for electrosynthesis.The current sustained by the bed is interpreted terms of empirical charge transfer coefficients calculated with the aid of the experimentally potential profiles.Current efficiences of 95% are obtained at current densities of 2500 A m^?2.     

Kinetic behaviour of packed and fluidised bed electrodes

For the reaction of electrochemical quinone reduction at packed and fluidised bed electrodes an experimental parameter analysis of macrokinetic bed cd was carried out showing the influence of electrode potential, flow velocity, bed depth parallel to current flow direction, and electrolyte conductivity. A macrokinetic model of three-dimensional electrodes is established by introducing overpotential distribution within the electrode into the microkinetic rate equation. Theoretical calculations of macrokinetic bed cds yield reliable values as is shown by comparison with the experimental results. Both for packed and for fluidised bed electrodes analytical expressions are derived for penetration depth of diffusion limiting cd into bed electrodes.     

Ethanol production by alginate immobilised yeast in a fluidised bed bioreactor

Yeast, immobilised in alginate beads of known standard size and mechanical strength, has been utilised in a novel design of fluidised bed bioreactor which avoids problems of particle flotation and gas logging. Circulating substrate simultaneously entered the top and bottom of the bed. The bioreactor operated reliably for periods of up to 20 days. Increasing alginate concentration in the range 1–5% (w/w) had little effect on the performance of the immobilised yeast in converting ethanol to glucose but reduced the tendency of beads to split. Increasing bead diameter in the range 1–5 mm increased the tendency to split and reduced overall conversion of glucose. A model was developed to describe the consumption of glucose within beads based on Michaelis–Menten kinetics and the diffusion of glucose into beads. Application of the model to experimental results showed maximum reaction velocity to be independent of bead diameter and alginate concentration. The model confirmed that the observed reduction in ethanol yield compared with free yeast cells was caused by the lower substrate concentration towards the centre of the bead as opposed to any change in the metabolic rate of the immobilised cells.