Chemical Engineering Sctence, Vol. 46, No. 4, pp. 1089-1099, 1991. CW-2509/91 $3.W + 0.

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Printed in Great Britain. 0 1991 Pergamon Press plc

MONTE CARLO SIMULATIONS OF STRUCTURAL

PROPERTIES OF PACKED BEDS

SEBASTIAN C. REYES and ENRIQUE IGLESIA

Corporate Research Laboratories, Exxon Research and Engineering Company, Clinton Township,
Route 22 East, Annandale, NJ 08801, U.S.A.

(Firsr receiued 8 January 1990; accepted in revisedform2 Jury 1990)

Abstract-Monte Carlo simulations are used to obtain void fraction (@) and particle-particle contacts
radial profiles for nondeformable spheres contained within cylinders with impenetrable walls. Simulated
packings of monosize and multisize spheres are created by their sequential random placement within a
prescribed enclosure using packing rules consistent with loading procedures in packed bed reactors. The
resulting random-loose packings (@ = 0.42) differ significantly in local and global properties and in the
extent of ordering from random-close packings (a = 0.36). Void fraction and particle-particle contact
radial profiles in monosize packings show a heavily damped decay behavior near the wall, extending only
about two sphere diameters away from it. The damped oscillatory behavior characteristic of random-close
packings is not observed. Similar trends are observed for multisize sphere distributions. Void fraction
profiles for multisize spheres prescribed by continuous distributions are accurately described by a simple
linear combination of the profiles of the individual size components. In bidisperse size distributions, similar
superimposition rules also describe the qualitative details of the void fraction profiles, but do not account
for compaction effects caused by penetration of small spheres into the interstices between larger spheres.
Void fraction and contacts in segregated packings, in which monosize spheres of different size are dropped
into annular and core regions in the cylindrical enclosure, are also described. These simulations provide the
basis for our current studies of heat transport properties in packed beds, and for the generation of realistic
pore structure models of overlapping randomly-arranged spheres.

INTRODUCTION and theoretical studies; these are defined as random-

Packed beds are widely used in the chemical process close, random-loose, and random-poured packings
industry. They range from simple mass transfer sep- (Haughey and Beveridge, 1969).
aration devices to more complex designs where chem- Random-close packings are simulated by optim-
ical reactions take place. The packing is created by izing the relative positions of a pre-arranged assem-
loading solid particles into containers that are usually blage of spheres until a maximum bed density (0.64) is
cylindrical in shape. In general, the particles are ir- obtained (Jodrey and Tory, 1981). They are obtained
regularly shaped, cylindrical, or spherical and dis- experimentally by dumping spheres in a container and
tributed in size. The length of the packing and the subsequently compacted by shaking the packing in
tube/particle diameter ratio, D/d, vary widely with order to achieve maximum bed density (Scott, 1960,
application. Whereas packing lengths can range from 1962; Scott and Kilgour, 1969). Random-loose
a few centimeters to several meters, values greater packings are simulated by loading individual spheres
than about 30 particles across the tube diameter are into local minima in the upper surface of an evolving
somewhat typical for the latter. packing without allowing them to bounce to more
The structural properties of the bed strongly influ- stable equilibrium points or rearrangements of
ence the rate and mechanism of heat, mass, and already positioned spheres. Experimentally, they are
momentum transfer within it. For example, bed obtained by slow settling or individual loading of
void fraction, number of particle contacts, and size of spheres and result in bed densities of about 0.58.
the particles are fundamental properties controlling Intermediate packing densities, ranging from about
heat conduction. The interfacial area determines mass 0.60 to 0.62, are generally classified as random-poured
transfer rates across the packing boundary. The packings. They are obtained experimentally by the
pressure drop of a fluid traversing the packing de- dropping of many spheres simultaneously into fixed-
pends strongly on the size of the interparticle voids. In bed reactors and consist of a combination of local
general, any rigorous analysis of reaction and trans- regions of random-loose and random-close packings.
port within the packing requires detailed descriptions The simulation procedure resembles that for random-
of both local and global values of structural loose packings but spheres are placed sequentially
properties. into global (lowest stable equilibrium point), rather
than local minima, over the surface of the developing
packing (Matheson, 1974).
(a) Types of packings Random-close packings tend to exhibit local
Three types of random packing configurations are ordering behavior extending several sphere diameters
discussed most frequently in previous experimental away from a wall and resulting in damped oscillatory

1089
1090 SEBASTJANC. REYES and ENRJQUE IGLE~IA

void fraction profiles. Random-loose packing lack distributions of particle contacts in random as-
local ordered structures; wall effects quickly decay semblages of spheres [e.g. Adams and Matheson
within one to two sphere diameters of a wall. (I972), Visscher and Bolsterli (1972), Jodrey and Tory
(1979) and Powell (198O)j. In all of these investiga-
tions, however, only bulk properties of the bed were
(b) Previous work reported; hard wall effects were eliminated by using
Several theoretical and experimental investigations periodic boundary conditions.
have been carried out to describe the structural prop- The presence of damped oscillations away from a
erties of packed beds. Early studies are summarized restraining wall results from local ordering in random
by Haughey and Beveridge (1969). More recently, close-packed structures. Experimental packing void
computer simulations have provided structural de- fractions range from those corresponding to random-
tails not easily predicted by theory or measured by loose (0.42) to those more typical of random-cIose
experiments. (0.36) packings. Therefore, real packings may consist
Benenati and Brosilow (1962) experimentally estab- of local ordered and disordered regions and thus show
lished that large void fraction variations occur near combinations of damped oscillations, decay behavior,
the wall of cylindrical tubes packed with monosize and random fluctuations near the wall.
spheres. At a given tube height, local radial void
fraction profiles exhibit a heavily-damped oscillatory
behavior extending about five sphere diameters away (c) Extensions to previous work
from both concave and convex walls (convex walls are In the present study, we use Monte Carlo simu-
found in heat transfer devices that are immersed in the lations to analyze void fraction and number of par-
packing). Asymptotic void fractions were about 0.39, ticle contacts in random-loose packed beds. This
a value intermediate between those for random-loose work extends the scope of simulation techniques re-
(0.42) and random-close (0.36) packings. ported in previous investigations by: (a) using cylin-
In related experiments, covering a wider range of drical containers with impenetrable walls, and (b)
D/d than those of Benenati and Brosilow (1962), allowing the packing of arbitrary size distributions of
GoodIing et al. (1983) confirmed that local oscillations spheres in both homogeneous and radially segregated
in void fraction are detected up to a distance of five configurations.
sphere diameters away from the wall. They also ana- This study exploits these extensions by systemati-
lyzed void fraction profiles for packings with spheres cally characterizing void fraction and partide contact
distributed in size in order to describe actual packing profiles in both local and global scales for packings
devices more accurately; they showed that the domain with monosize and multisize spheres. Our work con-
of influence of the wall is very sensitive to the details of firms previous findings but also reports new results.
the size distribution. For distributions containing For example, for monosize spheres, average (axially
equal volumes of spheres of two different sizes, they integrated) void fraction profiles show a heavily
measured regular oscillations only up to a distance of damped decay behavior that attain asymptotic values
about two to three diameters (of the small spheres) of about 0.42 within two sphere diameters of the
away from the wall. For combinations of three sphere restraining wall in contrast with the damped oscil-
sizes, the influence of the wall was observed only latory behavior previously observed in random-close
within a distance of one (small) sphere diameter. They packings of spheres (Scott, 1962) as well as in packings
made no attempt, however, to characterize the ob- with intermediate void fraction (Benenati and
served profiles in terms of the properties of the indi- Brosilow, 1962). For aspect ratios D/d greater than
vidual components of the size distribution. about 20 the radial profiles become independent of
Thadani and Peebles (1966) experimentally showed D/d when the abscissa is scaled in units of sphere
that loosely packed (void fraction of about 0.40) diameter away from the wall; for those aspect ratios
spheres exhibit a fast decay in void fraction away from the surface of the tube behaves effectively as a flat
the restraining walls rather than the damped oscil- wall. Based on this unique profile for large aspect
latory behavior observed on more closely packed ratios, u priori predictions of void fraction profiles for
configurations. Ordered behavior disappeared within spheres distributed in size are readily obtained by
two sphere diameters away from the wall. linear combination methods. The variation in number
For monosize spheres, Gotoh et al. (1978) com- of contacts per sphere in the vicinity of the wall
bined computer simulations and mofecular pair-cor- greatly impacts radial heat conduction by particle
relation functions of statistical mechanics to predict contacts. Global values of bed void fraction and of
void fractions near the wall. Simulated packings were average number ofcontacts per sphere as a function of
created by slow settling of rigid spheres into a con- D/d are also reported for the first time for packings
tainer consisting of two impenetrable vertical planes contained within cylindrical hard walls. They allow
and two periodic boundaries, i.e. an infinite slab with quantitative predictions of the influence of the wall on
two rigid walls. Simulations, theoretical predictions, global packing properties and heat transport rates.
and experiments were in qualitative agreement. Finally, an alternate segregated packing configura-
Several other investigators also used computer tion, consisting of an annular and core section packed
simulations to determine bed void fraction profiles or with spheres of different size, is also described in order
 Monte Carlo simulations of structural properties of packed beds 1091

to explore its potential use to improve radial heat having an aspect ratio D/d = 30. This local profile,
conduction in packed beds. corresponding to one (N = 1) arbitrary axial position
in the tube, is computed at each radial position r as
S/P; here P is the perimeter of a tube-centered ring
MONTE CARLO SIMULATIONS
passing through r and S is the sum of the ring
The simulation code for the random packing of segments that lie outside the spheres. This is schemati-
spheres is similar to that described by Visscher and cally shown in Fig. l(b); the local void fraction at
Bolsterli (1972) and Jodrey and Tory (1979). The radial position is computed as the ratio between the
packing is created by simulating the very slow settling magnitude of the broken and the solid line. Figure l(a)
of hard spheres, one at a time, into a randomly packed clearly shows the heavily damped decaying behavior
bed. Impenetrable cylindrical walls instead of flat that develops close to the impenetrable wall. The void
hard walls or periodic boundary conditions are used fraction decreases sharply from a value of unity at the
in our simulations in order to incorporate the wall wall to a local minimum at a distance slightly greater
effect present in packed beds. Simulations neglect than half a sphere diameter. It then returns to a local
bouncing of spheres located at local minimum points maximum at exactly one sphere diameter away from
or the bumping of such spheres by incoming ones into the wall; the void fraction at this point does not return
global minimum points; previously placed spheres are to unity because the second row of spheres rests in the
not in any way consolidated or spread apart by cusps formed by the spheres in the first row. Beyond
incoming ones. The resulting random-loose packings one to two sphere diameters, the void fraction con-
have an asymptotic void fraction of about 0.42. The tinues to fluctuate randomly with low amplitude
code is written in general form in order to allow for ( -C 5%) around a mean value of about 0.42. These
the random placement of spheres of size prescribed by random fluctuations persist throughout the tube
an arbitrary distribution and to permit the placement cross-section and only disappear when a large num-
of such spheres in specific radial positions withm the ber of these local profiles are integrated along the
cylindrical container. A final packing consists of a reactor length [Fig. l(c)]. An enlarged view of the
random assemblage of spheres whose coordinates void fraction profile near the wall is shown in
within the tube are known exactly. The packing is Fig. l(d). The results of Fig. l(aHc) are reproducible
then analyzed for void fraction and sphere contacts at and valid in general for any aspect ratio D/d greater
both local and global scales. In order to avoid axial than 20.
end effects, only the central portion contained be- The random nature of the fluctuations in Fig. l(a) is
tween five sphere diameters above the bottom and demonstrated by the white noise nature of the
about five sphere diameters below the top are used in deviations in void fraction from its true asymptotic
structural characterization; the tube bottom effect- value when averaging 1, 30 and 50 local void fraction
ively behaves as a restraining wall while the top profiles (Fig. 2). The true average void fraction at any
surface shows irregularities of the order of a few radial position in the bed is obtained by averaging
sphere diameters due to the randomness of the 2000 local void fraction profiles, randomly selected
packing process. In general, a packing length of about within a packing length of 60 sphere diameters. This
60 sphere diameters was sufficient to attain average void fraction profile also exhibits a rapid
statistically reproducible results in repeated Monte decay pattern up to a distance of about one sphere
Carlo simulations. The number of spheres required to diameter away from the wall, reflecting the high
meet the above conditions ranged from a few thou- degree of orientation for spheres near the wall.
sand to as many as a hundred thousand, depending Beyond one sphere diameter, however, the random-
on the aspect ratio D/d. ness of the packing becomes rapidly dominant and the
average void fraction approaches its asymptotic value
PROPERTIES OF HOMOGENEOUS PACKINGS within about two sphere diameters away from the
(a) ~oidfrnction wall. The profile of Fig. l(c) is valid in general for
Bed void fraction, defined as the fraction of the aspect ratios D/d greater than about 20. This is dem-
packing volume that consists of interparticle voids, is onstrated in Fig. 3(a),(b). Figure 3(a) shows radial
one of the most important and commonly measured void fraction profiles for ratios D/d up to 20. For low
structural properties of a packed bed. It is a useful aspect ratios the curvature of the wall has a marked
property because it measures the capacity 6f the bed effect that gradually disappears as D/d increases past
to accommodate solid material, and because it ulti- about 15. Figure 3(b) corroborates that the profiles for
mately affects pressure drop and heat and mass trans- D/d greater than about 20 become essentially the
fer properties of the packing. In this section, we use same; the curvature of the wall no longer affects the
the previously discussed computer simulations to observed profiles.
measure bed void fractions for the homogeneous Simulated local void fraction profiles [Fig. i(a)] are
packing, in which the spheres are randomly dropped very similar to experimental profiles by Thadani and
with equal probability throughout the tube cross- Peebles (1966) for loosely packed spheres with an
section. asymptotic void fraction of about 0.40. The average
For monosize spheres, Fig. l(a) shows a typical profiles in Fig. l(c), (d) also resemble those obtained
radial void fraction profile for a simulated packing by Benenati and Brosilow (1962) for slightly denser
1092 SEBASTIAN C. REYES and ENRIQUE IGLESIA

1 -d
-2 I-- L ;- i-~-~
6 8 10
Sphere Diameters Away From Watt

(4 (b)

0.0 I I 1 1 ,
Cl 1 2 3 4 5
Sphere Diameters Away From Wall Sphere Diameters Away From Waif
Cc) (4
Fig. I. (a) Local void fraction (N = 1) as a function of sphere diameters away from the wall for a packing
with D/d = 30. (b) Schematic representation for void fraction calculation at radial position r in a packed
tube. (c) Average void Fraction (N = 2ooO) as a function of sphere diameters away from the wall for a
packing with Djd = 30. (d) Enlarged version of(c) in the region near the wall.

packings (asymptotic void fraction = 0.39). However, up to a D/d ratio of 50. The influence of the wall is
our simulated local void fraction profiles [Fig. l(a)] strong for low aspect ratios but becomes less import-
differ markedlyfrom those reported by the latter ant as the aspect ratio increases past about 10, giving
authors. They report damped oscillations in thin slices asymptotic void fractions that are similar to those
of their experimental packing; these oscillations con- observed experimentally for large aspect ratios. The
tinued for up to five sphere diameters away from the results of Fig. 4 are accurate and reproducible with
wall and suggest a long-range ordering effect of the standard deviations for 10 Monte Carlo realizations
wall on the packing. The long-range ordering ob- at each aspect ratio of less than 0.0003. The asymp-
served by these authors is surprising in view of their totic bed void fraction, computed from the central
high void fraction compared with random-close core (50 sphere diameters) of a packing with D/d = 70,
packings (0.36); their results suggest that small regions was found to he 0.4185. This value effectively corres-
of local ordered structures in intermediate density ponds to an infinite packing with no wall effects. As
packings (such as random-poured) are sufficient to expected, it is the same value obtained by Jodrey and
create damped oscillatory behavior near the wall. Tory (1979) using periodic boundary conditions.
Average void fraction profiles [Fig. 3(a), (b)] de- Radial void fraction profiles for simulated packings
scribe the influence of the wall on the global bed void of spheres distributed in size were also analyzed. In
fraction for packings with any aspect ratio D/d. The order to contrast discrete and continuous distribu-
global bed void fraction is simply obtained by calcu- tions, a bidisperse distribution with equal volume of
lating the fraction of voids existing in a packing of spheres with diameters d, and d,, and a Gaussian
length 606 for a given aspect ratio D/d. Alternatively, distribution (truncated at three standard deviations)
for D/d greater than about 20, the global bed void having sphere sizes distributed between d, and d,, on
fraction can he readily obtained by radially integrat- an equal-volume basis, were chosen for illustration.
ing the average void fraction profile [Fig. l(c)] start- Figures 5 and 6 show average void fraction profiles for
ing from the wall up to a distance equal to D/d sphere bidisperse and Gaussian distributions, respectively. In
diameters. Figure 4 shows the result of this calculation these figures, as well as in all subsequent profiles
 Monte Carlo simulations of structural properties of packed beds 1093

10 I I I I
s.d. = 1.9% N=l

-5

I I
-10 1 I 1 I I 1
Sphere Diameters Away From Wall
IO I I I I
s-d. = 0.4% N=30

5-
(b)

10 I / I 1
s.d. = 0.3% N=50
I I
0.5 1.0 1.5 0
Sphere Diameters Away From Wall

Fig 3. (a) Average bed void fraction as a function of sphere

diameters away from the wall for packings with D/d of 3, 5,
10, 15 and 20. (b) Average bed void fraction as a function of
sphere diameters away from the wall for packings with D/d
of 20, 30 and 40.
-5 -

-10 I I 1 1
0 2 4 6 6 10
Sphere Diameters Away From Wall

Fig. 2. Percent deviation from the true void fraction profile

when 1, 30, and 50 1ocA void fractron profiles are integrated
(D/d = 30).

corresponding to spheres distributed in size, the units

of length in the abscissa are diameters of the smallest
spheres d,. For both distributions the spheres had
radii distributed between one (d,/Z) and five (d,/2),
0.40 L--e 10
0 20 30 40 50
and the tube radius was equal to 50 (D/2). For the Tube/Sphere Diameter Ratio

Gaussian distribution case, the mean sphere radius is

given by d,/2 + dJ2 and equal to three, and one
standard deviation equals (2/3)d,.
Figure 5 shows that the asymptotic void fraction in
the bidisperse case is as much as 10% lower than the
corresponding value for spheres of uniform size pre-
sented in Fig. l(c). This clearly indicates that some of
the small spheres reside within the interstices among
the large ones. As expected, this compaction effect is
more pronounced as the width of the distribution,
d,/d, , increases. This is illustrated in Fig. 7, where the
asymptotic void fraction is plotted as a function of the
width of the distribution d,/d,. This figure offers an
Fig. 4. Global bed void fraction as a function of the aspect
ratio Dfd.
explanation for the large pressure drop increase often
reported in actual processing equipment as particle
disintegration or attrition occurs. Indeed, pressure
drop is very sensitive to local void fraction variations.
The compaction effect described above for bidis-
perse distributions is, however, not present in con-
tinuous distributions (such as the Gaussian case of
Fig. 6) and the asymptotic value of void fraction is
identical to that of Fig. l(c). The probability of finding
 SEBASTIAN C. REYES and ENRKJUE IGLESIA

1.0

0.8
1
0.6

0.4

0.2

0.0 -e-i 6 I 6I I 10
I I 12
1 1 14
I 1
IC
Sphere Diameters Away From Wall d,ld, Diameter Ratlo

Fig. 5. Average bed void fraction as a function of sphere Fig. 7. Asymptotic bed void fraction as a function of the
diameters away from the wall calculated for a simulated sphere diameter ratio d,/d,
packing with D/d = 30. Bimodal distribution having equal
volumes of spheres with diameters d, = 1 and d, = 5.

spheres, suggesting that some of them touch the wall.

The strength of the peak is, however, not as pro-
i nounced as the first peak because of the compaction
effect previously discussed and of the dampening
effect of many randomly placed spheres of size one.
Beyond two sphere diameters away from the wall, the
spheres of size one no longer feel the ordering effect of
the wall, and the void fraction rapidly approaches its
asymptotic value.
5 - Void fractions profiles for Gaussian distributions
5 (Fig. 6) and monosize spheres [Fig. l(c)] are very
4 0.2 -
similar. In both cases, a minimum and maximum in
0.0 t._- void fraction are observed. However, as a result of the
0 2 4 6 8 10
continuous distribution of spheres in the multisize
Sphere Diameters Away From Wall
case, neither the minimum nor the maximum in void
Fig. 6. Average bed void fraction as a function of sphere fraction are as sharply defined as for monosize
diameters away from the wall calculated for a simulated spheres. In contrast with Fig. l(c), void fraction
packing with D/d = 30. Gaussian distribution of spheres
with diameters between d, = 1 and d, = 5.
minima are slightly higher for Gaussian distributions
because larger spheres create larger voids close to the
wall. The void fraction maxima, however, are lower
because small spheres dampen fluctuations beyond
relatively large interstices where small spheres can two sphere diameters away from the wall. The radial
reside is apparently very small for continuous size location of the minimum and maximum qualitatively
distributions. Thus, in the absence of wall effects, the match those in Fig. l(c) if the abscissa of Fig. 6 is re-
void fraction of the packing is the same irrespective of scaled by some average diameter of the distribution.
whether the spheres are distributed in size or not, The volumetric average, equal to three in this case,
provided that the distribution is continuous. We have gives reasonably good agreement.
verified this result for Gaussian as well as for uniform The absence of noticeable compaction in the
distributions having ratios d,/d, as high as 7. The continuous distribution case suggests that (randomly-
uniform distribution is another example of a contin- placed) spheres of different sizes compete for available
uous distribution where sphere sizes between d, and volume with equal probability. Therefore, average
d, occur with equal probability. void fraction profiles for packed beds loaded with
The void fraction behavior close to the wall de- spheres continuously distributed in size can be ob-
pends on whether spheres are monosize or distribu- tained by simply adding the contributions to void
ted. In addition to the relative maximum at one fraction from the single-size components of the dis-
sphere diameter in Fig. 5, that is also found in tribution. Thus, the contribution ofa given size sphere
Fig. l(c), another maximum appears at position five. to the average void fraction profile is given by the void
The first maximum indicates that spheres of size one fraction profile of Fig. l(c) (valid for spheres of any
strongly dominate the shape of the profile within one size), weighted by the fractional volume of this size
sphere diameter from the wall (there are 125 spheres component in the distribution. The result of this
of size one per every one of size five in this case). The calculation, which is referred to here as the linear
second maximum clearly corresponds to the larger combination (LC) procedure, is illustrated in Fig. 8.
 Monte Carlo simulations of structural properties of packed beds 1095

This figure compares the actual computer simulated subtracting the offset value from the LC profile, the
profile (broken line) corresponding to the Gaussian predicted and simulated curves can be brought into
distribution of spheres used in Fig. 6 and the LC close agreement. As in the continuous distribution
prediction (solid line). The predicted and simulated case, a small discrepancy remains close to the wall.
profile curves closely agree, demonstrating the accur- We conclude that average void fraction profiles
acy of the LC procedure. The small discrepancy close (and consequently the global bed void fraction), for a
to the wall is clearly the result of some compaction tube packed with multisize spheres obeying Gaussian
effect because the larger void fraction fluctuations or uniform continuous distributions, are accurately
near the wall increase the interpenetration predicted simply by linear combinations of their
probability. single size component profiles. In the bimodal case,
The linear combination procedure was also used to good approximate predictions can also be obtained
predict void fraction profiles for bidisperse distribu- with the LC procedure, provided that compaction
tions (Fig. 9). The location of distinct peaks are pro- effects are independently described.
perly predicted but the LC procedure overestimates
void fractions throughout the radius of the tube, and (b) Sphere contncts
most markedly near the wall. For any ratio d,/d, , the The average number of contacts per particle is not
difference equals the asymptotic value (0.42) for experimentally measurable. It is defined as the num-
monosize spheres minus its corresponding value for a ber of particles in contact with a given particle, aver-
bidisperse distribution (Fig. 7). This suggests a com- aged over all particles. This property becomes import-
paction effect that is almost radially uniform. After ant because heat (and electrical) conduction in packed
beds and porous solids occurs via particle-particle
contacts. High packing connectivity leads to high
effective thermal (and electrical) conductivity and
h higher transport rates.
For monosize spheres, a typical profile for the

1
jk____-__
____
average number of contacts per sphere as a function of
radial position in a simulated packing having an
aspect ratio D/d = 30 is shown in Fig. 10. This local
profile is obtained at each radial position by dividing
the number of sphere contacts existing in a thin
annular cylindrical element by the equivalent number
of spheres enclosed in the volume element; it gives the
average number of contacts per sphere as a function of
0.04
0 2 4 6 8 10
radial position. Contacts with the wall and between
spheres that are touching the wall are excluded. As
defined, the average number of contacts per sphere at
Fig. 8. Average bed void fraction as a function of sphere these two locations depends on the selected thickness
diameters away from the wall predicted from the linear of the annular element. If a sufficiently thin annular
combination procedure for a simulated packing with D/d element is chosen (so as to obtain a true local property
= 30. Gausaan distribution of spheres with diameters be- at each radius), discontinuities would appear both at
tween d, = 1 and d, = 5.
the wall and at half a diameter away from the wall.
This is simply because a significant number of highly

r?I,, , , , 1i,
0 I 2 3 4 5
Fig. 9. Average bed void fraction as a function of sphere Sphere Diameters Away From Wall
diameters away from the wall predicted by the linear combi-
nation procedure for a simulated packing with D/d = 30. Fig. 10. Average number of sphere contacts per sphere as a
Bimodal distribution having equal volumes of spheres with function of sphere diameters away from the wall for a
diameters d, = 1 and d, = 5. simulated packmg with U/d = 30.
1096 SEBASTIAN C. REYES and ENRIQUE I~~LESIA

localized contacts occurs exactly at zero and half a
diameter away from the wall. Thus, for these two
locations, we report the number of contacts
separately.
Wall contacts can be expressed in two alternate
manners: (a) the number of contacts per unit area of
wall 4(1 - F.+)/7r&, and (b) the number fraction
of spheres that are in contact with the wall
[8(1 - F,)/3(1 - F,)]/fD/d). In the preceding equa-
tions, F, is the global bed void fraction for a given
aspect ratio D/d, and 1 - F, is the fraction of the wall
area taken up by the projection onto the wall of the
spheres that touch the wall. The value of F, corres-
ponds to the packing void fraction at half a diameter
away from the wall when only those spheres that are
touching the wall are left in the packing.
The number of particle-particle contacts at half a
diameter away from the wall clearly depends on D/d;
as we lower D/d, we increase the probability that these
contacts occur. The results of this calculation
plotted in Fig. II, where these particle-particle con-
the number of contacts per sphere. The value of three
contacts per sphere is in agreement with similar calcu-
lations for random-loose packings and it simply indic-
ates that each sphere has an average of about six
nearest neighbors. In this asymptotic region, the dis-
tribution of neighbors has a Gaussian shape with the
peak of the distribution at six neighbors. No spheres
with less than four or more than eight contacts were
found.
As with void fraction profiles, the particle contacts
profile can be used to estimate the influence of the wall
on the global average number of contacts per sphere
for packings with various aspect ratios D/d. These
results are reported in Fig. 12; they exclude contacts
with the wall but include the contacts between spheres
that are touching the wall. As expected, the influence
of the wall is very marked for low aspect ratios, but
rapidly disappears as D/d increases past about 10.
are
PROPERTIES OF SEGREGATED PACKINGS

tacts at 0.5 diameters away from the wall have been In previous sections, we described void fractions
normalized by the wall contacts. In heat transfer and average number of contacts per sphere for
processes, these contacts do not contribute to the net radially homogeneous packings, in which the spheres
radial heat transport properties of the packing. are randomly dropped with equal probability
In radial profiles, we find that the average number throughout the tube cross-sectional area. Here, we
of contacts per sphere increases sharply from zero, at briefly discuss the radial void fraction profiles of an
a distance just beyond half a diameter away from the alternate packing configuration, consisting of an
wall (Fig. 10); it reaches a maximum at a distance of annular region of thickness D -DC loaded with
less than one sphere diameter away from the wall and spheres of uniform diameter d,, and of a correspond-
a minimum at a distance slightly greater than one ing core region of diameter D, loaded with spheres of
sphere diameter, and then increases again to level off uniform diameter d,. The two regions are separated
at its asymptotic value at approximately two sphere by an imaginary boundary in order to avoid addi-
diameters away from the wall. Its shape is not surpri- tional wall effects. In this configuration, we explore
sing; it is a direct consequence of the void fraction how particle contacts and void fraction near the wall
profile of Fig. l(c). Basically, regions of low and high depend on the radial segregation of a size distribution.
void fraction result in regions of high and low num- In actual non-isothermal fixed-bed reactors, the heat
bers of contacts, respectively. The average number of transfer resistance is frequently greatest near the wall.
contacts per sphere in the absence of watl effects is Although, in general, several mechanisms of heat
equal to 3.009 ( _t 0.003). As defined in our calcu- transfer could be acting simultaneously, the Monte
lations the total number of contacts was divided by Carlo technique presented here provides valuable
the number of spheres in the control volume and information for any such mechanisms that involve
therefore the number of neighbors is equal to twice particle contacts. The quantities D, D,, d,, and d, are

i0 t 1

illii , , , , , , , 1
0 10 20 30 40 50
Tube/Sphere Diameter Ratio
Tube/Sphere Diameter Ratio

Fig. 11. Ratio of sphere-sphere to sphere-wall contacts as a Fig. 12. Average number of contacts per sphere as a func-
function of D/d. tion of D/d.
 Monte Carlo simulations of structural properties of packed beds 1097
some of the important design parameters that control adversely affecting the pressure drop properties of the
the heat transfer rates in packed beds. core region, which remains virtually unperturbed by
An annular configuration is chosen for illustration the presence of small spheres in the annulus.
purposes. Our packing code is capable of generating
radially segregated packings with arbitrary size and
SPECIFIC APPLICATIONS
spatial distribution. Gradients of arbitrary form in
both the radial and the axial directions can be readily Ultimate applications of the simulation code de-
introduced into the simulation procedure. scribed here provide strong motivation for its devel-
Segregated packings are created by sequentially opment and for its detailed description. Microscopic
dropping spheres of size d, into the annular region analyses of heat transfer processes between spheres
and of size d, into the core region in a random fashion. within packed beds are the subject of ongoing re-
The sequence in which these spheres are dropped search in our laboratory. Specifically, these calcu-
is determined by a simple criterion that requires that lations permit the optimization of thermal conductiv-
the heights of the two regions increase simultan- ity and wall heat transfer coefficients using segregated
eously during the packing process. The number packings such as those described in the previous
of spheres of size d, per sphere of size d, is given by section and drawn schematically in a cross-sectional
(Wd,) [(D/D,) - 11. view in Fig. 14(a).
A typical average void fraction profile for a packing In addition, random assemblages of spherical
with D = Sod,, D, = 4Od,, and d, = 3d, is shown in packings provide a suitable framework for generating
Fig. 13. The small spheres behave as those in a uni- realistic and tractable models of porous structures,
form packing except that the void fraction in the such as those found within catalyst and adsorbent
annular region (extending up to five sphere diameters pellets and inorganic membranes. Their void fraction
in this example) is lower due to a compaction effect. and pore size distribution determine their transport
This results from the presence of a few large spheres properties and their suitability and optimum struc-
that migrate from the core to the annular region by ture in separation and catalytic processes. These con-
crossing the imaginary boundary that exists between trolling properties are being simulated in our laborat-
the annulus and the core. Similarly, the slight decrease ory by a combination of partial overlap of adjacent
in void fraction (compared with monosize spheres) in spheres, that determine porosity, and of an appropri-
a narrow region between three and six sphere dia- ate choice of sphere size distributions, that determine
meters away from the wall results from compaction the interstice (pore) size distribution. Typical simu-
caused by a similar migration of small spheres into lated porous structures are shown schematically in
interstices between the larger spheres in the core Fig. 14(b), (c).
region.
These data demonstrate the ability of the simu- CONCLUSIONS
lation code to create and characterize well-defined The structural properties of packed beds are de-
segregated packings; in this particular example, the scribed using simulated packings created by sequen-
absolute length over which large void fraction vari- tial random placement of spheres into a cylindrical
ations occur can be controlled by selecting the thick- tube. Homogeneous and segregated packings are de-
ness of the annulus and the size of the small spheres in scribed. In homogeneous packings, monosize or
that region. The use of such small spheres near the multisize spheres are randomly dropped throughout
wall also increases the number of particle contacts the cylinder cross-section. In segregated packings,
with the wall. Improved heat transfer rates are ob- spheres of different sizes are randomly dropped into
tained with these segregated configurations without both annular and core sections of the tube. Void
fraction and particle-particle contact profiles near the
restraining wall are obtained. Global averages of these
properties as a function of the tube/sphere diameter
ratio, D/d, are also evaluated in order to quantify wall
effects.
In homogeneous packings of monosize spheres with
Dfd > 20, local radial profiles of void fraction and
particle contacts show a heavily damped decaying
behavior extending for a length scale of about two
sphere diameters away from the wall, followed by
random void fraction fluctuations throughout the
packing cross-section. By averaging these profiles
over the packing length a unique radial pattern is
obtained when void fraction is plotted in terms of
Sphere Diameters Away From Wall sphere diameters away from the wall. Void fraction
Fig. 13. Average bed void fraction as a function of sphere
again decays to its asymptotic value within two sphere
diameters away from the wall for a segregated packing with diameters of the wall but local fluctuations are re-
D = Md,, D, = 4Od,, d, = 3d,. moved by the averaging process. This unique profile
1098 SEBASTIANC. REVES and ENRIQUE IGLESIA

readily demonstrates that global packing averages of For homogeneous packings with multisize spheres,
void fraction and particle contacts increase and de- local and average void fraction profiles also exhibit a
crease, respectively, with decreasing D/d because of rapid decay behavior near the wall. The decay length
increasing wall effect contributions. is, however, strongly dependent on the form of the

Fig. 14. (a) Cross-sectional view of simulated segregated packing (void fraction data and packing proper-
ties as in Fig. 13). (b) Cross-sectional view of simulated pore network constructed of partially overlapping
monosize spheres (void fraction = 0.20). (c) Three-dimensional view of simulated pore network constructed
of a Gaussian distribution of partially overlapping spheres (void fraction = 0.11).
 Monte Carlo simulations of structural properties of packed beds 1099

distribution. The void fraction profiles for packings FW void fraction at half a sphere diameter away
with multisize spheres, prescribed by any continuous from the wall of only those spheres that
distribution, behave as linear combinations of their touch the wall
single size components. For bidisperse distributions,
linear combinations also describe void fraction pro-
files except for a compaction effect caused by inter-
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