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Solids Processing/Analysis

Selecting In-Process
Particle-Size Analyzers
Paul Barrett,
Lasentec, Inc.,
A Mettler Toledo Company

In-process particle
analysis is key to optimizing
particulate processes and
improving product quality
and performance.

HE INTERNATIONAL ORGANIZATION for


Standardizations (ISO; Geneva; Switzerland;
www.iso.ch) defines particle size as the volume
spherical equivalent diameter (SED). In other
words, the size of a particle is defined as being the
diameter of an imaginary sphere that has the same volume as the real and often non-spherical particle actually being measured. However, from an in-process
particle-characterization perspective, particle size alone
may not reveal enough information about a process to
allow for process optimization or tracking of a critical
product parameter. To select the proper instrument for
process monitoring, one must define the problem that is
occurring. One has to determine what attribute of the
particle system impacts the process or product parameter
of concern. Once the size region that has the largest impact on these parameters is identified, it can be tracked
in-process, opening up the realm of realtime process
control and optimization.

Basics of particle science


As a first step in analyzing a particle system, gather
as much information as possible about the key process
variables affecting the system, including operating temperatures, pressures, flowrates in pipes, mixing conditions, etc. With this information, attempt to define the
issue. Is the particulate process plagued by a filtration
problem or a reaction rate problem? Or is the final product quality or process efficiency not up to par?
In addition to the unit operation in question determine
which upstream unit operations impact the particle system. For instance, as particles are transported between
pieces of equipment, is attrition or aggregation occurring

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due to differences in temperature or


flowrate? Next, identify how the particle systems impact process parameters
(e.g., filtration rate, reaction rate or particle flowability) or the product parameter of concern (e.g., stability or particle strength). What aspect of the particle system is key to controlling the
problem or optimizing the solution?
And, are the fine or large particles driving the process problem?
Filtration, for instance, is heavily influenced by particle shape, solids loading and the relative amounts of
fine material to coarse material (1). Filtration will also
be dictated by the compressibility of the cake and the
selection of the filtration equipment (i.e., pressure filter
or centrifuge).
If the filtration problem is a solids-loading issue, the
process would be producing the same-sized material
during each batch, but the solids loading would change,
resulting in varying filtration times. In this case, measuring the solids concentration may suffice. But what if the
solids concentration is relatively constant from batch to
batch and the size of the material changes? Actually, this
is how the majority of filtration problems occur. In general, long filtration times and inconsistent filtration rates
are largely driven by the number of fine particles relative
to the number of coarse particles. Thus, from a filtration
perspective, it is crucial to have a handle on the number
of fine particles.
To decipher what region of the particle system is impacting a process, consider a simple example of two spherical particles measuring 10 m and 100 m. The average
size of this two-particle system depends on the type of
device used to measure the particles sizes. When the
number of particles is used as the basis of measurement,
the average size is 55 m. On a volume basis, the mean
particle size is actually 99.9 m. This is because when
measuring particle size on a volume basis, the outcome
is dominated by the largest particles.
While it is possible in theory to convert from a volume-based to a number-based distribution, it is difficult
if not impossible to do this effectively in practice, as instruments that measure on a volume basis offer little
sensitivity to the fine particles, resulting in a poor evalu-

Increase in
number of fine particles
No change in
number of
coarse particles

Counts, #

ation of the number or volume of fines. It


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is also worth noting that the majority of
commercially available sizing techniques
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(e.g., sieving or laser diffraction) provide
data on a volume basis.
It is vital to know the principle of an
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instruments measurement volume or
number in order to assess the statistics
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it provides. The following example illustrates how the appropriate (or inappropriate) selection of statistics can aid or blur
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the detection of a change in typical particle-based processes: Twenty-seven 100100
m particles (assume these particles are
spheres) are in a reactor/pipeline. One of
these particles breaks apart, forming one
0
thousand particles measuring 10 m.
1
There is no change in particle mass, but
the tremendous increase in the number of
6
particles increases the surface area of this
particle system by 37%. If these particles
are part of a reaction in which the surface
5
area of the solids drives the reaction rate,
this breakage event could have a signifi4
cant impact on the overall reaction kinetics. Similarly, the increase in the number
of fines will dramatically impact the fil3
tration rate.
On the other hand, the volume-based
2
mean particle size has changed by slightly
more than 3%. This is because the volume-based mean is insensitive to changes
1
in the number of fines. It is not a suitable
way to track changes in the fines distribu0
tion when coarse material is present.
1
Changes in the fines distribution have
a large bearing on the surface area. For
this reason, reactions in which the particle size (and surface
area) drive the reaction rate, or processes in which solids are
subjected to a filtration step, will be acutely influenced by
changes in the number of fine particles. The point is to use a
number-based statistic to track changes on the fines side of
the distribution.
Particle count in specific size regions is another important
concept in the quantification of particle systems. The ability
to count particles and classify them according to size is a
significant advantage. Consider an example where fine material (with a size distribution of approximately 10 m) is
added to coarse material (with a size distribution of approximately 200 m). The count-based distribution shown in Figure 1a provides the true picture of what is occurring in this
particle system the number of small particles is increasing but the number of coarse particles remains unchanged.
However, if these data are normalized and all particle-count
information is removed, it appears that the amount of coarse

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10

1,000

Dimension, m

Counts, %

Increase in
number of fine particles

Apparent loss
in number of
coarse particles

10

100

1,000

Dimension, m

Figure 1. In the particle-count-based distribution, the number of fine


particles present in the system appears to increase (a). However, when the
data in Figure 1a are normalized, there appears to be a reduction in the
number of coarse particles (b).

material has decreased, while the amount of fines has increased (Figure 1b). This is purely a function of the normalization, but without the number-based data, one could easily
draw the wrong conclusion.

Particle-sizing tools
Today, there is an extensive base of commercially available sizing equipment. Perhaps the most common and simplistic of these tools are sieves. With the emergence of computers and ever-improving electronics, several laboratorybased sizing techniques have come to the forefront. Today,
the two most popular offline particle-sizing techniques are
laser diffraction and electrosensing-zone methodology.

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Laser diffraction instruments are designed for offline particle-size measurement of solids or liquids suspended in another phase (i.e., a solid particle suspended in a liquid, a liquid suspended in another liquid, or a solid particle suspended
in air). These instruments use a light-scattering phenomenon,
coupled with mathematical algorithms, to calculate the volume-based particle-size distribution. The sizes of the particles, regardless of their shape, are typically reported as a volume-based distribution of spherical particles. This reported
distribution has a diffraction pattern similar to that of the
measured sample and ranges from 0.05 m to 2,000 m.
Diffraction involves a change in direction of the light
waves as they pass around an obstacle, in this case, a particle
in their pathway. The angles at which particles diffract light
are related to their sizes. For instance, if the particles are
spherical, large particles will scatter light at narrow angles,
and small particles will scatter light at wide angles.
In contrast to diffraction, the electrosensing-zone technique provides a number-based distribution. In the instrument, the particles are suspended in a weak electrolyte and
drawn through a small aperture. The width of the aperture is
sized for the particle sample in question, but can range from
0.4 m to 1,200 m. Current flows between the two electrodes located on either side of this aperture, creating what is
termed an electrosensing zone. As particles pass through
this charged aperture, their presence produces a current that
is proportional to their size. In this manner, the electrosensing-zone technique counts each particle.
The popularity of these instruments for laboratory-based
sample analysis is countered by their less-useful role in particle systems where knowledge of the rate or particle-system
dynamics are desired. Many attempts have been made to utilize offline tools for the characterization of high-concentration, dynamic particle systems that occur in industry. However, offline tools can only do so much.
It is often difficult, and sometimes hazardous, to take a
sample from an elevated-solids-concentration process (either
laboratory or production scale). A primary concern is whether
that slurry sample is representative of the process as a whole.
There have been several studies highlighting the impact of
sampling on the reliability of particle-size measurement (2).
Particles can change after they have been taken from the process, but before they are actually measured offline.
For instance, changes in temperature or pressure could
alter the particle system, thereby impacting how particles interact; fine particles could dissolve or aggregate. A typical example of this would be a crystallization process where, after
taking a sample, a temperature change causes additional crystal growth. Furthermore, most offline sizing techniques require low solids concentrations (typically, less than 2% by
wt., depending on the size and shape of particles), often demanding that the sample be diluted. Dilution can again
change the particle sample, rendering it non-representative of
what is occurring in the process. Sometimes, the samples are
filtered and dried in order to prepare them for measurement.

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0
0

100

200

300
m

Figures 2a and 2b. These images are taken in-process using a particle
vision and measurement (PVM) analyzer equipped with an in-process
video microscope. Images taken during a flocculation process indicate that
a large number of fine particles agglomerate to form a large particle (a).
Well-formed single hexagonal platelets can crystallize in a variety of forms
forms, depending on the solvent, the nature of the solute and
crystallization conditions (b).
The result is a poor portrayal of what actually occurred in the
elevated-concentration conditions of the production process.

Importance of particle shape


Another characteristic that must be taken into account
when the term particle size is used is particle shape. As

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Figure 2c and 2d. This image of paper fibers was taken in-process.
Papermaking is a complex process where interaction between the fibers
and fillers is extremely important (c). This crystal exhibits dendritic growth
that would be difficult to characterize offline, as crystals would break
apart in sample handling (d).

shown in Figures 2a2d, particles often exist in-process as irregularly shaped entities. But how do particles that are not
spherical affect measurement results?
Consider the simple sieve. Sieving will size a particle
based on its second largest dimension (2). Envision a 100m-dia. sphere vs. a 100-m-dia. 400-m long cylinder.
Although the rod has the greater mass, they will both fall

through the same size sieve aperture. The sieve data will be
incorrect if one does not account for shape. This example can
be extended to the majority of sizing techniques.
Most sizing instruments, including the Coulter counter
used during electrosensing, report an SED. However, regardless of the shape of the material under investigation,
most instruments assume that the measured signal comes
from a spherical particle, and in turn derive an SED based
on this assumption. The spherical assumption works fine if
the particles have a spherical shape, but the further a shape
moves away from a sphere, the worse this assumption becomes and the further the reported diameter is from the true
SED (Figure 3).
In fact, the algorithms that drive laser diffraction and
electrosensing-zone techniques do not account for particle
shape. A recent publication from a laser-diffraction instrument manufacturer highlights the limitations of these instruments when non-spherical particles are being measured (3).
Cases are cited in which laser diffraction and the electrosensing-zone techniques both failed to report the true
SED for particles ranging from boulder-shaped particles to
needle-like particles.
At this point, there are no successful correction factors in
commercial software (excluding some image-analysis packages) that account for non-spherical shapes. Most will generally track growth or reduction of shaped particles, but not in
an absolute sense.
The suitability of the SED should be judged bearing in
mind this sensitivity to shape. In addition, for non-spherical
particles, even if a true SED could be measured, it is of little
use this sphere will not represent the surface area of the
non-spherical particle, and it will not have the same flow or
handling characteristics of the non-spherical particle.
Imaging offers the ability to quantify particle shape and to
plot distributions of shape and dimension. Many laboratorybased imaging systems are available, from the simple microscope to automated image-analysis systems. However, when
it comes to sample size, imaging is at a disadvantage. A significant number of particles have to be measured to generate
a robust sample, which can be time consuming. Other shortcomings of imaging include low-end resolution and sensitivity to slight changes in dimension.

In-process particle characterization


The limitations of utilizing offline tools for the characterization of particle dynamics paved the way for the development of in-process characterization techniques. Over the last
decade, a variety of technologies have come and gone in this
market. Meanwhile, applications have developed in the dryend (i.e., particles suspended in air) and wet-end (i.e., particles or droplets suspended in a liquid) areas. This article will
address wet-system characterization. Ultrasonics, focusedbeam reflectance measurement (FBRM), and particle vision
and measurement (PVM) are among the most popular in-process techniques. In fact, a recent survey conducted by market

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Solids Processing/Analysis

10 m

300

100 m

Calculate diameter of
sphere with same
volume as "needle"

SED = 25.6 m

Dimension, m

250

200

150

100
LD Volume-based mean
FBRM Volume-based mean
PVM Analysis

50

Figure 3. When non-spherical particles are measured, a diameter is


reported, but it is not the actual spherical equivalent diameter (SED), as the
instruments either oversize or undersize the true SED depending on the
particle shape (3). Here, the surface area of the needle is 60% greater than
that of the sphere, so even if the true SED could be measured, it will not
relate to the physical properties of non spherical particles.

0
0

400

800
Time, s

1,200

Figure 4. Data shown are volume-based-mean particle sizes using both


focused-beam reflectance measurement (FBRM) and laser diffraction (LD)
for the same particle system. PVM image analysis quantifies the absolute
dimension of the particles, indicating that LD is oversizing the crystals.

Dimension, m

research firm Frost and Sullivan (San Jose, CA; www.chemicals.frost.com) says that the in-process particle-characterization market is dominated by FBRM and PVM.
phase), viscosity (for the liquid phase) and intrinsic attenuUltrasonics Ultrasonic techniques are split into two
ation. In a dynamic particle system, it can be difficult to
areas: acoustic spectroscopy and electroacoustic speccollect this information. Furthermore, the information can
troscopy. Acoustic spectroscopy is based on the scatterchange over time, making the acoustical techniques diffiing theory, which uses the fundamental equations of mass,
cult to implement.
momentum and energy to describe the
interaction between an ultrasonic wave
80
and a suspended particle. The interaction
Little change in volume-based mean
of a particle and wave. also depends on
=> Little change in course materials
the frequency of the wave and the size of
the particle. Therefore, if the fundamen60
tal equations and frequency are known,
Number-based median
the size of the particle can be deterVolume-based mean
mined. On the other hand, electroacoustic techniques use electric impulses to
40
stimulate the particles, which then proDrop in number-based median
duce sound waves that are proportional
=> More fine material
to the particle size.
Characterized by a wide measurement
20
range, ultrasonic techniques can measure
submicron-sized particles, and in some
cases, be implemented non-invasively.
0
Limitations include the fact that the mea800
0
400
600
200
surement is volume-based, and the partiTime, s
cle is assumed to be spherical. In addition, ultrasonic techniques typically require intricate knowledge about physical Figure 5. In characterizing a particle system, it is important to select the appropriate statistic to
track a change. Here, attrition is tracked with FBRM, revealing an increase in fine particles, but little
properties of the medium being mea- change in the number of large particles. The number-based median drops over time, indicating that
sured, including thermal conductivity, the number of fines has increased. Meanwhile, the volume-based mean is relatively
thermal dilation/expansion, heat capaci- stationary, indicating that this attrition is not breaking the large particles, but rather taking small
ty, shear rigidity/modulus (for the solid chips off their surfaces.

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Counts, #/s

Counts, #/s

FBRM This is a probe-based


measurement tool that is installed in a
4,000
reaction vessel or a pipeline, thereby
eliminating the need for sampling or di0
lution (4). It uses a focused beam of
30 s
3,000
laser light that scans in a circular path
60 s
across a particle or particle structure
passing in front of the probe window.
Upon hitting the particle, light is scat2,000
tered in all directions. The light scattered back towards the probe is used to
measure a chord length (i.e., the length
between any two points on a particle).
1,000
Reduction
Thousands of chords are measured per
in number
Increase in
second, providing a robust measureof fine Particles
dimension
ment that is sensitive to the change in
the number, dimension or shape of par0
1,000
1
100
10
ticles under investigation. This in-proChord Length, m
cess sizing technology is used for a diverse range of unit operations, ranging
from pulp-and -paper processing (5), bi60
ological applications (6), flocculation
Increase in
(7), oil/water dispersions (8), and crysdimension
50
0
tallization/precipitation (913). Advan30 s
tages of the technique include ease of
60s
40
use and very little maintenance or calibration requirements. A limitation is
that no shape information is provided.
30
However, this is both an attribute and a
limitation, as not assuming a shape is
20
important, especially during the measurement of non-spherical particles, and
10
when changes in shape and dimension
occur over time.
In-process imaging of particles offers
0
1,000
distinct advantages, as one can charac1
100
10
terize the shape of the material as it exChord Length, m
ists in a process. For instance, a measurement of the aggregation of particles Figure 6. Shows FBRM-count-based data during the course of a flocculation process. As flocculacan be estimated from the images. This tion progresses, the number of fine particles decreases, and the number of coarse particles increases
may not be evident from offline samples. (a). The volume of coarse material also increases during flocculation (b).
In-process imaging has also been used to
track the shape of crystals during crystallization (14).
Inline vs. offline techniques
PVM This is a probe-based high-resolution in-proFigure 4 shows FBRM data taken when monitoring a
cess video microscope that provides images of crystals as
crystal growth process where the crystals are increasing in
they exist in a process. The probe uses six independent
dimension over time. FBRM tracks the growth process,
laser sources to illuminate a fixed area within the slurry.
but the measured values of dimensions are lower than
Light scattered back towards the probe is used in conjuncthose observed via laser-diffraction. PVM images reflect
tion with a charge-coupled detector (CCD) to produce an
the true particle shape a well-formed octahedron.
image. The image has a field of view of 860 645 m with
Through image analysis of the PVM images, the SED of
resolution down to approximately 35 m. Ancillary softthese particles is plotted, revealing that laser diffraction
ware allows storage of up to 10 images/s. These images
oversizes and FBRM undersizes the true SED. However,
help validate particle shape and indicate particle dimension
for tracking dynamic processes, a measurement of absoand structure.
lute particle dimension is typically not necessary. What is

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required is a measurement that is sensitive to the process


parameter of interest, whether that be the fine or coarse
end of the distribution.

In-process monitoring
Attrition A simple example of the FBRM is shown in
a particle system undergoing attrition (Figure 5). Large
particles are stirred for 10 min. Over time, the distribution

Literature Cited
1. Mota, M., et al., Interference of Coarse and Fine Particles of Different Shape in Mixed Porous Beds and Filter Cakes, Minerals Engineering, 16 (2), pp. 135144 (Feb. 2003).
2. Allen, T., Particle Size Measurement, 4th Ed., Chapman and Hall,
London (1990).
3. Xu, R. and O. A. D. Guida, Particle Size and Particle Count Using
Light Scattering, Coulter Principle, and Image Analysis, World
Congress on Particle Technology 4, Sydney, AU, pp. 2125 (July
2002).
4. Barrett, P. and B. Glennon, In-line FBRM Monitoring of Particle
Size in Dilute Agitated Suspensions, Particle and Particle System
Characterization, 16, pp. 207211 (1999).
5. Dunham, A. J., et al., Effects of Dissolved and Colloidal Substances on Flocculation of Mechanical Pulps, Journal of Pulp and
Paper Science, 26 (3), pp. 95101 (2000).
6. Glennon, B., et al., In-Line Monitoring of Biological Systems
Using FBRM, Lasentec Users Forum, Charleston, NC (Feb. 24
27, 2002).
7. Owen, T., et al., The Impact of Polyacrylamide Flocculant Solution
Age on Flocculation Performance, International Journal of Mineral Processing, 67 (14), pp. 123144 (Nov. 2002).
8. Dowding, P. J., et al., Factors Governing Emulsion Droplet and
Solid Particle Size Measurements Performed Using the Focused
Beam Reflectance Technique, Colloids and Surfaces A.: Physicochemical and Engineering Aspects, 192 (13), pp. 513 (Nov. 2001).
9. Barrett, P., and B. Glennon, Characterizing the Metastable Zone
Width and Solubility Curve Using Lasentec FBRM and PVM,
Trans. IChemE, 80 (A), pp. 799805 (Oct. 2002).
10. Ruf, A., et al., Modelling and Experimental Analysis of PSD Measurements Through FBRM, Particle and Particle System Characterization, 17, pp. 167179 (2000).
11. Saranteas, K., Micromixing and Mesomixing Effects on Nucleation,
Agglomeration and De-Agglomeration Kinetics in a Dye Precipitation, Lasentec Users Forum, Orlando, FL (Feb. 28 Mar. 1, 2000).
12. Johnson, B. K., et al., Optimization of Pharmaceutical Batch
Crystallization for Filtration and Scale-Up, American Institute of
Chemical Engineers Annual Meeting, Los Angeles, CA (Nov.
1621, 1997).
13. Fitzsimons, P., Use of Lasentec FBRM in the Regulatory Environment of Bulk API Production, Lasentec Users Forum, New York,
NY (Feb. 2426, 2003).
14. Scott, D. M., et al., In Line Particle Characterization, Particle and
Particle System Characterization, 15, pp. 4750 (1998).
15. Daymo, E. A., et al., Acceptance Testing of the Lasentec Focused
Beam Reflectance Measurement (FBRM) Monitor for Slurry Transfer Applications at Hanford and Oak Ridge, Proceedings of SPIE
The International Society for Optical Engineering, 3536, pp.
8292 (1999).

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of fine particles increases, but the number of coarse particles does not change dramatically. The number-based median decreases over time, but the volume-based statistic remains constant. In this case, using the number-based mean
or the particle count on the fine side of the distribution
would be the appropriate to track this attrition event.
Flocculation To track flocculation in-process, one
needs to examine both sides of the distribution. Initially,
one starts with a high number of small particles, which aggregate through the addition of a flocculation agent (Figure
6a). As a result, the number of fines decreases and the
number of coarse particles increases (Figure 6b). Tracking
a flocculation process in this manner enables one to optimize the amount of flocculent to add, while assessing the
impact of essential process variables, such as agitation, on
the flocculated particles.
Opaque solutions Perhaps one of the greatest challenges
of in-process particle characterization is measurement in challenging process conditions high temperature or pressure, radioactivity (15) or opaque slurries. The use of FBRM for the
characterization of asphaltenes indicates that the naphtha to bitumen ratio has a marked effect on the rate and degree of asphaltenes precipitation and subsequent aggregation. Changes
in temperature, pressure and chemical composition may cause
asphaltenes to precipitate out of crude oil. Consequently, significant difficulties may arise in the production, transportation
and processing of crude oil. For example, precipitation and deposition inside an oil well may partially or completely block
the reservoir, thus damaging the reservoir and thwarting crudeoil recovery; or foul production lines and poison refinery catalysts. The economic impacts of these problems are tremendous. Yet, some of the most fundamental properties and behaviors of asphaltenes remain unresolved. In-process characterization sheds light on the crystallization process and its essential
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process variables.

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PAUL BARRETT is the director of applications for Lasentec, Inc. (15224 NE 95th
St.; Redmond, WA 98052; Phone: (425) 881-7117; Fax: (425) 881-8964;
E-mail: paulb@lasentec.com). He is responsible for the implementation of
Lasentecs in-process particle characterization technologies in a variety of
particulate processes. Barrett joined Mettler Toldo Lasentec in 2000 as a
crystallization specialist. He has earned BE and PhD degrees in chemical
engineering from Univ. College in Dublin, Ireland.