Prediction of bulk solids behaviour using the multi-scale design concept

T. Sheikhzeinoddin, 1P. N. Sharratt, School of Chemical Engineering and Analytical Science, The University of Manchester, PO Box 88, Sackville St, Manchester, M60 1QD, UK, tel. +44 161 200 3975, fax: +44 161 306 9321, e-mail: Tinoush.Shz@postgrad.manchester.ac.uk; 1tel. +44 161 306 4367, fax: +44 161 306 4399 e-mail: Paul.Sharratt@manchester.ac.uk

Abstract

Much research has been carried out to measure various behaviours and properties of bulk solids. Nevertheless, no quantitative or semi quantitative approach is proposed to model and predict bulk solids behaviours in the context of equipment selection and while process design. This paper discusses various methods of measuring different bulk solids properties at various scales. The IMPULSE multiscale philosophy is applied to enhance understanding of bulk solids behaviours. A semi-quantitative approach is proposed to link particle properties at micro-scale to bulk solids properties at meso-scale and solids behaviours.

Keywords: Multi-scale design, bulk solids behaviours, particle properties.

Introduction

This research is a part of EU FP6 IMPULSE project (Integrated Multi-scale Process Units with Locally Structured Elements) (www.IMPULSE-project.net) which aims at effective, targeted integration of innovative process equipment such as microreactors, compact heat exchangers, thinfilm devices and other micro and/or meso-structured components, to attain radical performance enhancement for whole process, thereby contributing to significant improvement in supplychain sustainability for the chemical industry.

The IMPULSE approach represents a paradigm shift in chemical engineering. It offers new opportunities by encouraging the use of flexible, integrated equipment and process units with appropriately targeted multi-scale structuring. The multi-scale design approach of IMPULSE 1

aims to deliver the desirable operating conditions for a given physicochemical transformation through precise engineering rather than conventional approach of adapting operating conditions to equipment limitations. Therefore, understanding the underlying physics, processing needs and equipment are necessary for design and selection of processing equipment.

This paper demonstrates the application of the IMPULSE multi-scale philosophy to bulk solids behaviours to promote the application of the multi-scale concept in solids handling field.

Multi-Scale Processing

Many physical and chemical phenomena are usually involved in a typical processing plant. Their complexity and the pressure for optimising and designing processes with higher efficiency and low waste production oblige process engineers and researchers to continuously develop new concepts and methods. This necessitates an integrated system approach for simultaneous and coupled phenomena and processes that take place at different length (10-8106 metres) and time (10-6 - 108 seconds) scales (Figure 1). New concepts are now required to design, analyse, operate and optimise such processes.

Figure 1: Multi-scale and multi-time approach, after Lerou and Ng (1996)

Ng (2004) draw attention to the fact that different scales may overlap. For instance, there is an overlap between reactor scale and plant scale. The more overlap, the more interactions arise between them. There is considerable overlap between equipment, transport, reaction and 2

particle formation which suggests a substantial interaction of these factors in determining the operability and performance of equipment.

Sharratt et al. (2007) asserts that the concept of multi-scale process design, [i.e. matching the length and time scales delivered by processing equipment to intrinsic needs of the process, with the aid of micro technologies and structured devices such as microreactors, rotating packed bed reactors, compact reactor-exchangers, spinning disc reactors, static mixers and even structured catalysts] can bring remarkable possibilities to chemical production industries some of which are: on-site, on-demand manufacture, distributed, delocalized production, variable, modular throughput, and mass customization of product properties.

It should be kept in mind that the multi-scale approach needs a workflow and systematic procedures to focus on the right scale, while the overall objective is development of an optimal process in terms of delivering desirable operating conditions with the right cost, environmental impact, operational performance, etc. within constrains effort and time. Also, defined subtasks at each scale should support the overall objective.

Tools and methodologies are being developed by a part of IMPULSE consortium to support structured multi-scale process design and development. Rational approaches are taken to select appropriate piece of processing equipment to match the needs of the process, instead of just using standard equipment and adapting process conditions to the capabilities of this device.

Solids properties and behaviours

Design procedures for solids and solids-containing processes are considerably different from liquid-liquid and liquid-gas systems and are strongly based on pilot plant studies and laboratory data. Solids processing plants face many operational problems. This is partially due to complexity of solids processing and the large number of parameters involved in the process. Bulk solids do not form a continuum phase like liquid and gas and their behaviour may vary significantly when either single particle properties or ambient conditions change. For instance, the flowability of bulk solids changes when the moisture contents changes. Thus, it is essential to establish a link between particle properties at micro-scale and bulk solids behaviour at meso-scale. The understanding of basic properties of particles and bulk 3

solids as well as interactions between particles and equipment is the basis to find a proper multi-scale approach to solids processing.

4.1

Particle Properties

Particles or powders are in the sizes of less than 1 mm by definition (BSI, 1993). Particle properties can be divided into mechanical, thermal, electrical and chemical. Mechanical properties are associated with internal structure and characteristics of atomic bonding e.g. Young modulus, strength and hardness. Thermal properties such as thermal expansion, heat capacity and thermal conductivity arise from internal energies that introduce atomic and electronic movements. However, thermal properties can influence mechanical behaviour and properties. Electrical properties such as Hamaker constant and electrical resistance are mainly originated from electron movements and charge displacements. Other fundamental properties of individual particles can be listed as size, shape (particle shape and size are often referred as crystal habit in pharmaceutical industries), porosity and particle density, surface properties and chemical composition and structure. Chemical composition and atomic structure of a particle influences the density, mechanical properties such as deformation and strength (Youngs Modulus) as well as electrical properties. Details of materials properties are discussed by Bean et al. (1967) and Van Vlack (1970).

The underlying science associated with the application should be identified and taken into account in design or equipment selection of solids processing equipment. A source of uncertainty is selection of right definition for some of the basic particle properties. For instance, particle size can be expressed in various terms such as equivalent-volume sphere diameter, equivalent surface sphere diameter, equivalent projected area circle diameter, Stokes diameter and aerodynamic diameter as mentioned by Seville et al. (1997). The difference between various diameters increases when the particle is more anisometric. However, the appropriate method should be selected to measure the parameter that is functionally important for the physical system being studied. For example, if the health hazard of a dust is studied, then the movement of the particle suspended in the air into and out of the mouth and nose of an operator is governed by the aerodynamic diameter of the particle. On the other hand, if sedimentation of particles is to be studied, the Stokes diameter of particles should be studied. 4

Another source of uncertainty and complexity may arise in determination of particle shape. Shape characterisation is complex due to irregularities of particles. It can be defined in various terms such as sphericity, Heywoods method, elongation ratio, and aspect ratio (Fayed and Otten, 1997; Seville et al., 1997). Irregularities become important when one studies the motion of a particle or transfer phenomena, as the surface area of the particle is a critical parameter, and a relevant method should be selected again based on the physical characteristics of the system. 4.2 Bulk Solids properties

When discussing particle and bulk solid properties and behaviours, one should consider the fact that some bulk properties and behaviours are meaningful where they apply to a set of particles; some of those properties are particle size distribution (PSD), bulk density, segregation, etc. But, attrition, adhesion and, breakage are those behaviours which can be analysed for both single particle and bulk solid.

It is necessary to account for the PSD in synthesis of solids processes, as it is an important parameter in design of most of the processes such as crystalliser as well as quality control of pharmaceuticals. Selection of relevant sampling and measurement methods is vital and physics of the process should be taken into account.

Particles are normally packed together in random orientation regardless of their crystal habit and leave certain amount of free space between them. Therefore, a bulk solid is a combination of particles and space. The knowledge of bulk density of particulate systems is necessary to design silos, transport equipment, storage vessels, etc. 4.3 Bulk Solids Behaviours

A particulate system may demonstrate various behaviours such as segregation, agglomeration, etc. which can be generally described by cohesion, adhesion forces, etc. or in one word as its flowability. Two approaches can be considered to develop a model for predicting the behaviour and flow of bulk solids which are based on either continuum or particulate approach. There are various methods to evaluate flowability, some of which are suggested by Carr (1965b), Jenike (1966), Geldart (1973) and Johanson (1995). Emerging advanced techniques have also been developed in recent years among which Freeman (2007) can be mentioned. Nevertheless, none of the above methods 5 are online and a series of

experiments should be carried out offline on a specific amount of sample. However, the link between the values obtained by the latter method to flowability of particles in the process is yet to be explored.

Linking particle physical properties and powder behaviours

While each methodology mentioned before gives an insight into bulk solids behaviour through experimental procedures, the link between properties at micro and meso scales is still missing. A multi-scale systematic approach is required to predict material flow by establishment of strong link between particle properties and bulk solids, taking into account equipment parameters and behaviour of bulk solid in each process.

The proposed methodology is a three dimensional matrix, in which properties at mesoscale are linked to behaviours through basic particles properties at microscale. The matrix presents a semi-quantitative approach in linking various properties and parameters of solids at various scales, and is formed and treated without having any specific process and equipment in mind, as the behaviours and bulk solids parameters varies from one to another.

Basic properties of a particle are shape, size, density, moisture content, Youngs modulus, strength (hardness), electric charge (Hamaker and dielectric constants), porosity, surface tension of liquid (to include capillary force between particles when moisture presents) and ratio between the dimension of asperities and particle diameter. PSD can also be considered a microscale property of a particulate system.

At mesoscale, bulk solids behaviour as well as the interaction between particles and equipment geometry should be considered. The parameters at mesoscale are history (cracks, geometrical position in the equipment or bulk solids, orientation, etc.), bulk density (representative of voidage), equipment geometry, angle of repose, compressibility, angle of spatula, uniformity coefficient/cohesion and shear strength. On the other hand, the behaviours of bulk solids or interaction between micro and meso scales are flowability, breakage, agglomeration, attrition, segregation, adhesion to the wall, compaction and abrasion (effect on the equipment).

Particle and bulk solids properties manifest themselves as behaviours once the materials are 6

being handled. The magnitude and direction of the behaviours depend on the process as well as properties of the materials. The third dimension of the matrix links the material properties (at particle and bulk levels) to a set of bulk solids behaviours such as flowability, blockage, agglomeration, attrition, etc. The equipment geometry is also included which plays a significant role in behaviour of bulk solids. This should be specified case by case for equipment to which the matrix is applied.

The parameters and behaviours at various length scales are listed in Table 1 and a point-based system are used to link them together based on the carried out literature survey. In this table, value +/-1 means strong link, +/-0.5 weak link, 0 no link and ? unknown link. Positive sign is used when two parameters are directly proportional and negative when reversely proportional.

Under each physical property there are two columns. In the right column, the link between particle properties and meso properties (e.g. history, PSD, etc.) and in the right column (in grey) the link between particles properties and behaviours (e.g. flowability, blockage, etc.) are established. The procedure is as follows:

Evaluate basic property (at micro-scale) against meso-scale parameters (establishing the link by marking) in the white column under each property;

Evaluate basic property against behaviours (establishing the link by scoring) in the grey column under each property,

Having done that, the table now shows the connection of one meso parameter to behaviours through particle properties. If a meso-scale property is marked 0.5 or 1, it is linked through the basic property to all behaviours which are not marked 0 under that property.

For instance, the history of a particle is strongly linked to the shape (marked 1), and flowability is also a function of shape. Thus, flowability can be linked back to the history by the particle shape, i.e. the flowability in equipment depends on previous positions of particle which is strongly dependent on particle shape. Same approach was taken towards each micro scale property. The goal is finding the functionality of bulk solids behaviours with measurable values at meso- and micro- scales. 7

Table 1: Linking parameters and properties at micro and meso scales

Mesoscale properties

Shape 1 1 1 ? 1

Size 1 1 1 -1 1 1 1 -1 1 -1 1 1 1 1

PSD 2 1 1 1 1 1 1 1 -1 1 -1 0 1

0 0 0 ? 1 0 0 ?

MC 1 1 1 1 1 1 1 -1 1 1 ? -1 1 1 ?

YM 1 0 1 0 0 0 0 0 0 0 -1 0 0 0 1 1 0 1 0 0 0 0

H 0 0 0 1 0 0 0 1 1 0 1 1

EC -1 1 1 ? -1 1 0.5 ? 1 1 ? ? 1 ? ?

? ? ? ? ? ? ? 0 ? 0 1 1 ? ? ?

ST -1 ? 1 0 -1 1 ? 0 1 1 1 1 1 1 1

? 1 1 1 0 ? 1 ?

Behaviours Flowability Blockage Agglomeration Attrition Segregation Adhesion to the wall Compaction Abrasion

History- cracks, 1 position, orientation, etc. Bulk density Equipment geometry Angle of repose Compressibility Angle of spatula Uniformity coefficient or cohesion -1 1

-1 0.5 -1 ? -1 ? 0 0 0 0

-1 0.5 1 -1 1 -1 ? 1

0.5 1 1

: Particle density; MC: moisture content; YM: Youngs Modulus; H: Hardness; EC: electric charge; : porosity; ST: surface tension of liquid; : ratio between the dimension of asperities and particle diameter
1 2

Shape measured by sphericity. + means approaching the sphericity of 1 PSD: the width of distribution, N = (d90-d10)/d50; the smaller the N value, the narrower the width of PSD

Also, equipment geometry can be influenced by particle shape and vice versa; besides, particle shape influences some behaviours of the particulates such as flowability, blockage, agglomeration, attrition, to some extent segregation (score 0.5), compaction and abrasion; however, its influence on adhesion to the wall is unknown (marked ?). Therefore, one can deduce that equipment geometry is affecting all behaviours marked 1 or 0.5 in the right column (in grey) under the particle shape, i.e. flowability, blockage, attrition, to some extent segregation, compaction and abrasion of the equipment.

Furthermore, one can also establish the following equation based on the table:
flowability = fn (shape, size ), (MC , EC , , ST , PSD )

(1)

The merit of using such a table is twofold. First, it gives more understanding towards design, operation or selection of equipment with regard to underlying physics, and secondly it illustrates the gaps in establishment of a clear link between micro and meso-scales. Such a table can capture the linkages between phenomena and properties that are in essence the process understanding. It can be used to support design of experimentation, testing of hypotheses and assessment of the risk that exists as a result of incomplete understanding.

The table has to be employed intelligently by identifying key particle properties for each process; for instance, in size reduction process the key parameters can be PSD, shape, size, YM and H. A sensitivity analysis should be considered to identify key parameters in the design. Examples are given here to demonstrate the ability of the table to propose pathways for flowability improvements.

Titanium Dioxide (TiO2) is used in many industries and is a poorly flowing material. Commercial grades of TiO2 are coated with hydrous oxides which improves the durability and gloss of pigment. Treatment of TiO2 with Naphthenic acid is shown to improve flowability of the pigments (US Patent 4,303,702). Based on equation (1), decreasing the electrical charge in the material will result in better flowability character, as documented in the patent.

The influence of moisture content on flowability of powders is widely discussed in the literature. For instance, the flowability of four different food powders (flour, skim-milk, tea and whey-permeate) decreases with increase in moisture content as demonstrated by Teunou

et al. (1999), which is in accordance with the equation (1). Therefore, manipulation of moisture content will change flowability of materials as desired.

Another example is the link between angle of repose and flowability of the materials. Angle of repose is a function of particle shape, size, width of PSD, moisture content, electrical charge, and surface tension of the liquid content based on Table 1. A clear link between angle of repose and flowability can be established through micro-scale properties of materials. Table 1 demonstrates that flowability is a function of shape and the width of PSD. Thus, if the width of PSD increases the table predicts an increase in angle of repose and a decrease in flowability. On the other hand, a +1 link exists between the width of PSD (N) and blockage in Table 1. This means that an increase in N and angle of repose raise the probability of blockage in solids handling systems such as hoppers. This is in accordance with findings of Carr (1965b; 1965a).

Finally, it should be noted that if one is applying the laboratory methods explained before for engineering purposes, sampling is a serious issue in all the methods, and it is of significant importance to take a representative sample in order to make the outcome of the experiment reproducible.

Conclusion

Various methods have been proposed to assess the behaviours of bulk solids most of which based on the experimental data and discard the basic physical properties of the particles. Thus, no strong link has been established between properties at micro and meso scales.

This new systematic approach provides more insight into solids handling by identifying the effect of particle and bulk solids properties; hence, a process engineer should be able to predict the direction and magnitude (order of magnitude analysis) of the change in the material behaviours once one or some of the properties at micro- and meso-scales have changed. Furthermore, it reveals the gaps which are required to be tackled in order to achieve the better understanding of phenomena happening at various length scales which is key in delivering the right conditions to the materials. This can be carried out by further targeted experiments when the matrix displays the existing gaps.

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A more analytical approach is yet required to consider the change of the behaviours and other properties of bulk solids, when the materials are being processed in each unit.

Acknowledgement

The authors would like to express their gratitude to European Union for funding of the IMPULSE project and Universities UK for ORSAS award.

References

Bean, H. S., Beckett, A. H. and Carless, J. E. (1967). Advances in pharmaceutical sciences, volume 2. First edition. London: Academic press Inc. 329pp. BSI (1993). BS 2955:1993, Glossary of terms relating to particle technology. BSI - British Standards Institution. http://www.bsonline.bsi-global.com. 30pp. Carr, J. R. L. (1965a). Classifying flow properties of solids. Chemical Engineering, 72(3), 6972. Carr, J. R. L. (1965b). Evaluating flow properties of solids. Chemical Engineering, 72(2), 163-168. Fayed, M. E. and Otten, L. (1997). Handbook of powder science & technology. Second edition. New York: Chapman & Hall. 898pp. Freeman, R. (2007). Measuring the flow properties of consolidated, conditioned and aerated powders -- A comparative study using a powder rheometer and a rotational shear cell. Powder Technology, 174(1-2), 25-33. Geldart, D. (1973). Types of gas fluidization. Powder Technology, 7(5), 285-292. Jenike, A. W. (1966). Storage and flow of solids. First edition. Salt Lake City: Bulletin of the University of Utah - v.53, no.26. 198pp. Johanson, J. (1995). Flow Indices in the prediction of powder behavior. Pharmaceutical Manufacturing International, 159-164. Lerou, J. J. and Ng, K. M. (1996). Chemical reaction engineering: A multiscale approach to a multiobjective task. Chemical Engineering Science, 51(10), 1595-1614. Ng, K. M. (2004). MOPSD: A framework linking business decision-making to product and process design. Computers and Chemical Engineering, 29(1), 51-56. Seville, J. P. K., Tuzun, U. and Clift, R. (1997). Processing of particulate solids. First edition. UK: Blackie Academic & Professional. 372pp. Sharratt, P. N., Matlosz, M., Bayer, T. and Bazzanella, A. (2007). IMPULSE - adopting a new processing paradigm in chemical and pharmaceutical industry. MST News, (1), 33-35. Teunou, E., Fitzpatrick, J. J. and Synnott, E. C. (1999). Characterisation of food powder flowability. Journal of Food Engineering, 39(1), 31-37. Van Vlack, L. H. (1970). Materials science for engineering. First edition. Japan: AddisonWesley publishing company. 545pp.

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