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L. Marchisio, Dennis Vigil, O. Fox - 2003 - Implementation of the quadrature method of moments in CFD codes for aggregation–breakage pro|Views: 11|Likes: 0

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**

Implementation of the quadrature method of moments in CFD

codes for aggregation–breakage problems

Daniele L. Marchisio

∗

, R. Dennis Vigil, Rodney O. Fox

Department of Chemical Engineering, Iowa State University, 2114 Sweeney Hall, Ames, IA 50011-2230, USA

Received 10 January 2003; received in revised form 7 April 2003; accepted 11 April 2003

Abstract

In this work the quadrature method of moments (QMOM) is implemented in a commercial computational uid dynamics (CFD)

code (FLUENT) for modeling simultaneous aggregation and breakage. Turbulent and Brownian aggregation kernels are considered in

combination with dierent breakage kernels (power law and exponential) and various daughter distribution functions (symmetric, erosion,

uniform). CFD predictions are compared with experimental data taken from other work in the literature and conclusions about CPU time

required for the simulations and the advantages of this approach are drawn.

? 2003 Elsevier Ltd. All rights reserved.

Keywords: Population balance; Computational uid dynamics; Quadrature method of moments; Aggregation; Breakage; Particulate systems

1. Introduction

Aggregation and breakage play an important role in a

number of important chemical processes such as precipita-

tion, crystallization, separation processes, and reaction in

multiphase systems. Modeling and simulation of these pro-

cesses is complicated due to the diculties inherent in de-

scribing the evolution of a distribution of particle sizes and

because of the incomplete understanding of the mechanisms

by which aggregation and breakage occur, including the role

of hydrodynamics. This latter problem is often neglected,

despite considerable evidence that aggregation is strongly

inuenced by mixing. For example, Brown and Glatz

(1987) investigated the eect of the operating conditions on

particle size established during breakage of protein particles

prepared under isoelectric precipitation in an agitated ves-

sel. They found that the aggregation rate increases with both

particle concentration and shear rate. In another study, the

inuence of the type of ow on the aggregation rate was in-

vestigated using a Taylor–Couette reactor, a pipe-ow reac-

tor, and a at-bottomed tank reactor (Krutzer, van Diemen,

& Stein, 1995). These experiments showed that at equal

∗

Corresponding author. Tel.: 515-294-3186; fax: 515-294-2689.

E-mail address: marchis@iastate.edu (D. L. Marchisio).

energy dissipation rates, the aggregation rate is higher for

isotropic turbulent ows than for non-isotropic ows.

Raphael and Rohani (1996) investigated the eect of ag-

gregation on the particle size distribution (PSD) during sun-

ower protein precipitation and found that the maximumsize

of the aggregates is determined by the hydrodynamics of the

reactor and the mean residence time of the particles in the re-

actor. Serra, Colomer, and Casamitjana (1997) investigated

aggregation and breakup of particles in a Taylor–Couette

reactor. In their experimental work they analyzed the eect

of particle concentration, shear rate, and particle initial di-

ameter. Their results showed the existence of three regions

determined by particle concentration and type of ow es-

tablished (laminar or turbulent). Moreover, they found that

the ÿnal aggregate diameter in the turbulent regime is inde-

pendent of monomer size and is instead controlled by the

Kolmogorov micro-scale, whereas in laminar ow the ÿnal

mean particle size decreases as the diameter of the primary

particles is increased.

One means for characterizing the morphology of clus-

ters of particles formed by aggregation–breakage processes

is the fractal dimension, which provides an indication of

the compactness of aggregates. The relationship between

fractal dimension and physical properties has been studied

from both the experimental (Serra & Casamitjana, 1998a),

and theoretical viewpoints (Filippov, Zurita, & Rosner,

2000; Jlang & Logan, 1991). Hansen and co-workers used

0009-2509/03/$ - see front matter ? 2003 Elsevier Ltd. All rights reserved.

doi:10.1016/S0009-2509(03)00211-2

3338 D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351

a Taylor–Couette reactor to study orthokinetic aggregation

for monodisperse and bidisperse colloidal systems (Hansen,

Malmsten, Bergenstahl, & Bergstrom, 1999). Particle ag-

gregation was investigated by direct observation using a

CCD camera, and the observed aggregates were character-

ized by a high fractal dimension, suggesting that clusters

are rearranged and densiÿed by the shear.

Aggregation and breakage are often the last steps of a

complex sequence of phenomena, such as nucleation, fast

reactions, combustion, and molecular growth (Marchisio,

Barresi, & Garbero, 2002; Rosner & Pyykonen, 2002;

Baldyga & Orciuch, 2001). Such systems inevitably lead

to non-negligible spatial heterogeneities, and therefore a

method of modeling these processes that accounts for hy-

drodynamics is crucial for predicting reactor performance.

One approach to account for non-ideal mixing is to use

CFD methods. In such an approach the reactor is represented

by a computational grid and the continuity and Navier–

Stokes equations are solved over the computational domain.

When dealing with turbulent ows, the set of equations is

unclosed and turbulence models are used to solve the clo-

sure problem. In addition to these equations, the population

balance equation for the solid phase has to be solved.

The population balance is a continuity statement writ-

ten in terms of the PSD and has consistently received

attention since Smoluchowski (1917) introduced the math-

ematical formalism nearly a century ago. A compre-

hensive overview of the mathematical issues involved,

the numerical methods available, and possible develop-

ments for the future have been given by Ramkrishna

(1985, 2000) and Ramkrishna and Mahoney (2002).

A general form of the mean-ÿeld population balance for a

spatially extended systemcan be written as follows (repeated

indices implies summation):

cn(; x, t)

ct

+u

i

cn(; x, t)

cx

i

−

c

cx

i

_

(I

t

+ I)

cn(; x, t)

cx

i

_

= −

c

c¸

)

[n(; t)¸

)

] + h(; t), (1)

where ≡ (¸

1

, . . . , ¸

n

) is the property vector that speciÿes

the state of the particle, n(; x, t) is the number density func-

tion, u

i

is the Reynolds-average velocity in the ith direc-

tion, x

i

is the spatial coordinate in the ith direction, I is the

molecular diusivity and I

t

is the turbulent diusivity. For

turbulent ows I

t

I and thus it is commonly assumed

that I

t

+ I ≈ I

t

. The “ux in -space” is denoted by

¸

)

≡

d¸

)

dt

, ) ∈1, . . . , N, (2)

and h(; t) represents the net rate of introduction of new

particles into the system (Hulburt & Katz, 1964).

The main problem in solving the above equation is the

presence of the extra variables ¸

i

, which deÿne the particle

size, shape, etc. In most CFD codes it is possible to intro-

duce user-deÿned scalars by using user-deÿned subroutines,

but these scalars must only be functions of time and space.

Hence, in order to reduce the dimension of the problem,

several methods have been developed.

The discretized population balance (DPB) approach is

based on the discretization of the internal coordinates (i.e.,

the components of the property vector). A detailed compar-

ison of the performance of the most popular DPB methods

has been carried out by Vanni (2000a). The principle ad-

vantage of the DPB method is that the PSD is calculated di-

rectly. However, in order to maintain reasonable accuracy,

a large number of scalars (i.e., particle classes) are required.

As a consequence, the DPB approach is computationally in-

tractable for spatially heterogeneous systems and therefore

not suitable for CFD applications.

An alternative to PBE approaches is to implement a

stochastic analog via a Monte Carlo algorithm (Smith &

Matsoukas, 1998; Lee & Matsoukas, 2000; Rosner & Yu,

2001). These methods have the advantage of satisfying

mass conservation as well as correctly accounting for uc-

tuations that arise as the system mass accumulates in a small

number of large aggregates. However, incorporation of

these methods into CFD codes is also not computationally

tractable because of the large number of scalars required.

In contrast to the DPB or stochastic approaches, the mo-

ment method (MM) is suitable for use with CFD codes be-

cause the internal coordinates are integrated out such that

solution only requires a small number of scalars (i.e., 4–

6 moments of the PSD) at each grid point. Of course the

vast reduction in the number of scalars, which makes im-

plementation in CFD codes feasible, comes at the cost of a

less-detailed description of the PSD. However, provided that

the PSD function is suciently simple (e.g., monomodal or

bimodal), a low-order moment description may be sucient.

The method was ÿrst proposed many years ago by Hulburt

and Katz (1964), but it has not found wide applicability due

to the diculty of expressing the transport equations for the

moments of the PSD in terms of the moments themselves.

More recently, several approaches for contending with this

“closure” problem have been developed, and a discussion

of these can be found in Diemer and Olson (2002).

When the population balance is written in terms of one

internal coordinate (e.g., particle length or particle volume)

the closure problem has been successfully solved with the

use of a quadrature approximation (McGraw, 1997), where

weights and abscissas of the quadrature approximation can

be found by using the product-dierence (PD) algorithm de-

scribed by Gordon (1968). The so-called quadrature method

of moments (QMOM) has been validated for several prob-

lems (e.g., molecular growth, aggregation, breakage) and

by using dierent internal coordinates (Marchisio, Pikturna,

Fox, Vigil, & Barresi, 2003a; Barret & Webb, 1998). More-

over, the method has been extended to the study of aerosol

D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351 3339

dynamics by using population balances with two internal

coordinates: particle volume and surface area (Wright, Mc-

Graw, & Rosner, 2002).

The main purpose of this work is to implement the

QMOM approach to solving the population balance equa-

tion in a commercial CFD code and to verify the feasibility

of these calculations for practical applications. The spe-

ciÿc problem considered is aggregation and breakage in

turbulent Taylor–Couette ow.

The CFD-based predictions for the particle size distribu-

tions are generated by using several dierent combinations

of conventional expressions for the aggregation and breakup

kernels and are compared with experimental data from Serra

et al. (1997) and Serra and Casamitjana (1998a, b). The

paper is organized as follows: governing equations are dis-

cussed, aggregation and breakage models are presented, and

the results of the case study considered, particularly with re-

spect to the number of scalars involved in the calculations,

the quality of the predictions, and the CPU time in compar-

ison with alternative approaches.

2. Governing equations

In this section the QMOM is presented and explained.

Particular attention will be devoted to its implementation in

FLUENT.

2.1. Quadrature method of moments

In this work, we consider a number density function de-

ÿned in terms of particle length (¸

1

≡ L). The resulting

population balance is (Randolph & Larson, 1988)

cn(L; x, t)

ct

+u

i

cn(L; x, t)

cx

i

−

c

cx

i

_

I

t

cn(L; x, t)

cx

i

_

= −

c

cL

[G(L)n(L; x, t)] + B(L; x, t) −D(L; x, t), (3)

where G(L) is the growth rate, and B(L; x, t) and D(L; x, t)

are, respectively, the birth and death rates due to aggrega-

tion and breakage. The moments of the PSD are deÿned as

follows:

m

k

(x, t) =

_

∞

0

n(L; x, t)L

k

dL, (4)

and thus the transport equation for the kth moment is

cm

k

(x, t)

ct

+u

i

cm

k

(x, t)

cx

i

−

c

cx

i

_

I

t

cm

k

(x, t)

cx

i

_

=(0)

k

J(x, t) +

_

∞

0

kL

k−1

G(L)n(L; x, t) dL

+B

a

k

(x, t) −D

a

k

(x, t) + B

b

k

(x, t) −D

b

k

(x, t), (5)

where J(x, t) is the nucleation rate and where

B

a

k

(x, t) =

1

2

_

+∞

0

n(z; x, t)

_

+∞

0

[(u, z)

×(u

3

+ z

3

)

k}3

n(u; x, t) du dz, (6)

D

a

k

(x, t) =

_

+∞

0

L

k

n(L; x, t)

_

+∞

0

[(L, z)

×n(z; x, t) dz dL, (7)

B

b

k

(x, t) =

_

+∞

0

L

k

_

+∞

0

a(z)b(L|z)n(z; x, t) dz dL, (8)

D

b

k

(x, t) =

_

+∞

0

L

k

a(L)n(L; x, t) dL (9)

are the moments of the birth and death rates, respectively,

due to aggregation and breakage. The aggregation kernel

[(L, z) represents the rate coecient for aggregation of two

particles with lengths L and z whereas the breakage kernel

a(L) deÿnes the rate coecient for breakage of a particle of

length L. The fragment distribution function for the break-

age of a particle of size L is given by b(L|z). A detailed

derivation of these equations can be found elsewhere (see

Marchisio, Vigil, & Fox, 2003b); discussion of the choice

of aggregation and breakage kernels can be found in

the following sections.

The QMOM is based on the following quadrature approx-

imation

m

k

=

_

+∞

0

n(L)L

k

dL ≈

N

d

i=1

w

i

L

k

i

, (10)

where weights (w

i

) and abscissas (L

i

) are determined

through the product-dierence (PD) algorithm from the

low-order moments (Gordon, 1968); a detailed explanation

of the method can be found in Appendix A. By using the

PD algorithm, a quadrature approximation with N

d

weights

and N

d

abscissas can be constructed using the ÿrst 2N

d

moments of the PSD. For example, if N

d

= 3 only the ÿrst

six moments (m

0

, . . . , m

5

) are tracked, and the quadrature

approximation is given by

m

k

=

N

d

=3

i=1

w

i

L

k

i

= w

1

L

k

1

+ w

2

L

k

2

+ w

3

L

k

3

. (11)

Knowledge of w

i

and L

i

suces to close the transport equa-

tions for the moments, and in the speciÿc case of aggrega-

tion and breakage without nucleation and molecular growth,

the moment equations become

cm

k

(x, t)

ct

+u

i

cm

k

(x, t)

cx

i

−

c

cx

i

_

I

t

cm

k

(x, t)

cx

i

_

=

1

2

i

w

i

)

w

)

(L

3

i

+ L

3

)

)

k}3

[

i)

3340 D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351

−

i

L

k

i

w

i

)

[

i)

w

)

+

i

a

i

b

(k)

i

w

i

−

i

L

k

i

a

i

w

i

, (12)

where [

i)

= [(L

i

, L

)

), a

i

= a(L

i

), and

b

(k)

i

=

_

+∞

0

L

k

b(L|L

i

) dL. (13)

It has been shown (Marchisio et al., 2003a, b; McGraw,

1997; Barret & Webb, 1998) that by using this quadrature

approximation it is possible to track the moments of the PSD

with very high accuracy.

2.2. Aggregation kernel

Aggregation of solids suspended in a uid is a complex

phenomena that in general depends upon particle–particle

and particle–uid interactions, particle morphology, as well

as uid mixing. However, regardless of the speciÿc mech-

anism by which aggregation occurs, the process can be di-

vided up into two steps: (1) particle–particle collision and

(2) “sticking” or fusion of colliding particles. The aggre-

gation kernel can then be expressed as the product of the

“sticking coecient” and a collision frequency function.

In certain simpliÿed cases, the aggregation kernel can

be computed exactly, provided that certain assumptions are

satisÿed. For example, if long-range particle–particle forces

are absent, if particles are Euclidean (as opposed to fractal),

and if the particles are suciently small so that they neither

inuence the uid phase nor are disturbed by uid shear, then

the collision frequency may be described by the Brownian

kernel:

[(L, z) =

2k

B

1

3j

(L + z)

2

Lz

, (14)

where k

B

is Boltzmann’s constant, 1 is the absolute temper-

ature, j is the uid viscosity, and L and z are particle sizes,

as ÿrst proposed by Smoluchowski (1917).

When particles are suciently large compared to shear

gradients, particle–particle collision frequencies are inu-

enced by uid motion. In the case of turbulent ow, the ra-

tio between particle size and the Kolmogorov micro-scale is

of primary importance. When particles are smaller than the

Kolmogorov micro-scale the aggregation kernel can be com-

puted as follows (Adachi, Cohen Stuart, & Fokkink, 1994):

[(L, z) =

4

3

_

3¬

10

_

1}2 _

c

v

_

1}2

(L + z)

3

, (15)

where c is the turbulent dissipation rate and v is the kinematic

viscosity. In fact, by using Taylor’s statistical analysis of

isotropic turbulence and assuming a normal distribution of

the velocity gradient, it can be shown that the shear rate

produced by uctuating turbulent velocities is proportional

to

_

c}v. Saman and Turner (1956) used this result to ex-

plain the formation of drops in clouds, and Tontrup, Gruy,

and Cournil (2000) used it for modeling turbulent aggrega-

tion of titania particles in water.

For chemically inert systems, aggregation eciency

is primarily determined by the balance between attrac-

tive (e.g. Van der Waals) and repulsive (e.g. electrical

double layer) forces. This balance is strongly inuenced by

the ionic strength of the solution. When the ionic strength

increases, the double layer repulsion is reduced, and at very

high values it is practically negligible. In these conditions

the aggregation eciency is usually considered to be equal

to one. Aggregation eciency can also be related to the

probability of fragmentation of newly formed aggregates.

In fact, the fragmentation kernels presented in the next

section are suitable for breakage of particles that have had

sucient time to restructure after collision (Gruy, 2001). If

a new aggregate does not have sucient time for restructur-

ing and is fragmented into its original two components, it

can be referred to as null aggregation eciency (Brakalov,

1987). Another important factor in determining the aggre-

gation eciency in precipitating particle system is the rate

of formation of “bridges” in zones of high supersaturation

(Baldyga, Jasinska, & Orciuch, 2002; Hounslow, Mumtaz,

Collier, Barrick, & Bramley, 2001). In the present work,

we consider only aggregation and breakage of particles in

chemically inert systems.

2.3. Breakage

Particle breakage functions can be factored into two parts.

The breakage kernel, a(L), is the rate coecient for breakage

of a particle of size L, and b(z|L) deÿnes the probability

that a fragment of size z is formed from the breakage of an

L-sized particle. Several expressions for the breakage kernel

relevant to hydrodynamic breakage mechanisms have been

derived by dierent authors and they are summarized in

Table 1.

Breakage kernel (1) in Table 1 was derived for disruption

of disperse liquid droplets in turbulent ow under the hy-

pothesis of local isotropy and assuming that the droplet size

is within the inertial subrange. Abreakage event occurs if the

kinetic energy transmitted by an eddy to a droplet is greater

than the droplet surface energy. The breakup frequency is

derived by considering the fraction of eddies present in the

system with sucient kinetic energy to cause breakage. This

can be done by estimating the fraction of drops breaking and

by estimating the characteristic time required for breakage

(t

b

) through the second-order structure function of the uid

velocity D

LL

(r). This function represents the covariance of

the dierence in velocity dierences between two points at

a given distance r and according to turbulent theory (Frisch,

1995) it can be written as

D

LL

(r) = c

2

(cr)

2}3

, (16)

D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351 3341

Table 1

Breakage kernels proposed in literature

System a(L) Reference

(1) Liquid–liquid a(L) = k

1

L

−2}3

c

1}3

exp

_

−

k

2

o

j

d

c

2}3

L

5}3

_

Coulaloglou and Tavlarides (1977)

(2) Liquid–liquid a(L) = [

z

erfc

_

3.5(

L

L

s

)

−5}6

_

Narsimhan, Gupta, and Ramkrishna (1979)

(3) Liquid–liquid a(L) = c

4

_

c

L

2

_

1}3 _

1

¸

min

(1+¸)

2

¸

11}3

exp

_

−

12c

[

o

[j

d

c

2}3

L

5}3

¸

11}3

_

d¸ Luo and Svendsen (1996)

(4) Solid–liquid a(L) =

1

√

15

(

c

v

)

1}2

exp

_

−

t

[

j(c}v)

1}2

_

Ayazi Shamlou, Stravrinides, Titchener-Hooker, and Hoare (1994)

(5) Solid–liquid a(L) = c

1

v

:

c

[

L

¸

Luo and Svendsen (1996)

Kramer and Clark (1999)

Wojcik and Jones (1998)

where c

2

is a numerical constant and c is the turbulent dis-

sipation rate. Assuming that the motion of the daughter

droplets is similar to the relative motion of two lumps of

uid in a turbulent ow and that the distance r is the droplet

diameter, we can write that

_

L

t

b

_

2

≈ D

LL

(L) = c

2

(cL)

2}3

, (17)

which can be solved for t

b

. The ÿnal expression for a(L) is

a function of the surface tension o and the droplet density

j

d

and is reported in Table 1 [see breakage kernel (1)].

Breakage kernel (2) in Table 1 was derived by consid-

ering the frequency that eddies arrive at the surface of a

disperse phase droplet, whose maximum stable diameter is

indicated by L

s

. Under the same phenomenological simpliÿ-

cations of the above mentioned models, and considering the

dierent contributions of the population of eddies in the in-

ertial subrange, it is possible to derive an expression for the

breakage rate without unknown constants [see kernel (3) in

Table 1], where ¸ = p}L, p is the eddy length-scale, c

4

is a

constant of order unity (c

4

=0.92), [=3}2, c

[

is the increase

coecient in the surface area [c

[

= [

2}3

+ (1 −[)

2}3

−1],

and [ is the volume fraction of one of the two fragments

(the function is symmetric about [ = 0.5).

As with breakage of liquid droplets, breakage of solid ag-

gregates depends strongly on the ratio between the particle

size and the smallest turbulent eddy. When the size of a par-

ticle is greater than the size of the smallest eddies, break-

age is likely to occur by instantaneous normal stresses due

to pressure uctuations acting on the surface of the parti-

cle. For particle sizes smaller than the turbulent micro-scale,

breakage is likely to be caused by shear stresses originat-

ing from the turbulent dynamic velocity dierences acting

on the opposite sides of the particle. Under these conditions

the breakage kernel can be written as a function of the ag-

gregate strength (t

[

), which can be estimated as follows:

t

[

=

9

8

k

c

[F

1

¬L

2

o

, (18)

where L

o

is the diameter of a primary particle, k

c

is the co-

ordination number, and F is the inter-particle force between

two primary particles (Ayazi Shamlou et al., 1994). The re-

sulting breakage kernel is reported in Table 1 [see kernel

(4)]. The inter-particle force F can be computed as follows:

F =

AL

o

12H

2

o

, (19)

where A is the Hamaker constant for the liquid-particle sys-

tem and H

o

is the distance between two primary particles.

The coordination number is based on experimental observa-

tion and can be calculated as

k

c

≈ 15[

1.2

, (20)

where [is the volume fraction of solid within the aggregates.

This quantity can be determined once the fractal dimension

d

[

of the aggregates in known

[(L) = C

_

L

L

o

_

d

[

−3

, (21)

where C = 0.414d

[

−0.211 (Vanni, 2000b).

Starting from the same basic considerations, but using a

simpliÿed approach, Kramer and Clark (1999) developed

another hydrodynamic breakage model for solid aggregates.

They classiÿed failure modes by deÿning manifestation, in-

duction and location of the failure, and stated that aggregates

break when the maximum eigenvalue of the stress tensor is

greater than the aggregate strength (t

[

). Using the assump-

tion that the number of aggregate bonds with a strength at or

below the failure strength t

[

is not a linear function of the

strain rate and that size-dependency should also be consid-

ered in a breakup model, the resulting form of the breakage

kernel is the one given as expression 5 in Table 1.

By invoking semi-theoretical considerations and ÿtting to

experimental data, several values of the exponent ¸ have

been proposed ¸ = 0, 1}3, 2}3, 1 (Luo & Svendsen, 1996).

Pandya and Spielman (1982) found that ¸=1, whereas Peng

and Williams (1994), by ÿtting the model to experimental

3342 D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351

Table 2

Fragment distribution functions: L

o

is the size of the primary particles

Mechanism b(L|z)

b

(k)

i

Symmetric

fragmentation

_

_

_

2 if L =

z

2

1}3

0 otherwise

2

(3−k)}3

L

k

i

Erosion

_

¸

¸

_

¸

¸

_

1 if L = L

o

1 if L = (z

3

−L

3

o

)

1}3

0 otherwise

L

k

o

+ (L

3

i

−L

3

o

)

k}3

Uniform

_

_

_

6L

2

z

3

if 0 ·L ·z

0 otherwise

L

k

i

6

k+3

data, found that ¸ can assume values ranging between 1 and

3 and that [ = 1}2.

Serra and Casamitjana (1998b) ÿt experimental data and

found that the relationship between the breakage kernel and

the turbulent dissipation rate c depends on the solid frac-

tion. When the solid fraction is low [ = 0.9, whereas for

higher values of the solid fraction [ is much higher. This

can be explained by the fact that particle–particle collisions

are more eective if the solid fraction is higher. Their results

conÿrm ÿndings by Spicer and Pratsinis (1996), who used

data from Oles (1991) and found [ = 0.8 for low values of

solid concentration.

In their investigation of nucleation, growth, agglomera-

tion and disruption kinetics for calcium oxalate, Zauner and

Jones (2000) found a linear dependency between the break-

age rate and the turbulent dissipation rate c (i.e., [ =1) and

the breakage kernel was size-independent (¸=0). In another

work (Wojcik & Jones, 1998) using a size-dependent break-

age kernel, a linear relationship between the kernel and the

turbulent dissipation rate ([ = 1) was also found.

The form of the fragment distribution function, b(L|z),

depends upon many factors including the particle properties,

such as strength and morphology, as well as the breakup

mechanism. Because the fragment distribution function is

likely to be highly system-speciÿc, we consider a variety of

possibilities suggested by experiments on disruption kinetics

of animal cell aggregates undergoing hydrodynamic break-

age (Moreira, Cruz, Santana, Aunins, & Carrondo, 1995).

Some of these distribution functions include erosion of pri-

mary particles, formation of two equal fragments, formation

of two fragments with ÿxed mass ratio (e.g., one to four),

and uniformdistribution of fragments. The distribution func-

tions corresponding to these cases are reported in Table 2.

3. Computational details and case study

The experimental data used in this study are taken from

Serra et al. (1997) and Serra and Casamitjana (1998a, b).

The reactor used in their work is a Taylor–Couette device,

which consists of a uid conÿned to the annular region be-

tween two concentric cylinders (outer cylinder stationary,

inner cylinder rotating). The wetted diameters of the inner

and outer cylinders are d

1

=193 mm and d

2

=160 mm, re-

spectively, thereby giving an annular gap D=(d

1

−d

2

)}2=

16.5 mm. The reactor length is H =360 mm, resulting in an

aspect ratio I

A

= H}D ≈ 22. Latex particles were used in

the experiments, and in order to avoid sedimentation eects,

the density of the solution was set at the same value as that

of the latex particles (j

s

=1.055 g}cm

3

) by adding an inor-

ganic salt to the solution (KCl). Samples were continuously

taken from the bottom of the reactor and passed through the

optical cell of a particle analyzer, and then pumped back

to the top of the reactor. The ux in the tubes was laminar

so that disruption of aggregates formed in the reactor could

be minimized. The residence time of the aggregates in the

tubes was also kept short in comparison with the time spent

in the reactor (about 300 times shorter).

Although aggregation–breakage experiments were car-

ried out with inner cylinder rotational speeds in the range

40–200 rpm, we compare simulation results only with data

in the turbulent owregime (N=80–200 rpm). An overview

of the various hydrodynamic regimes in the reactor can be

found in the review by Kataoka (1986), whereas validation

of ow ÿeld predictions in turbulent regimes has been car-

ried out in our previous work (Marchisio, 2002).

In the absence of an applied axial ow, the hydrodynam-

ics in a Taylor–Couette reactor depend upon the azimuthal

Reynolds number

Re =

r

1

c

1

D

v

, (22)

where r

1

= d

1

}2 is the radius of the inner cylinder, c

1

is

the angular velocity of the inner cylinder, D is the annular

gap, and v is the kinematic viscosity of the uid. When the

rotational speed of the inner cylinder is very small, circular

Couette ow is established. If the rotational speed of the in-

ner cylinder is increased past a critical value, this circular

ow becomes unstable and laminar toroidal vortices (Tay-

lor vortices) are formed. The critical azimuthal Reynolds

number for Taylor instability Re

c

, also depends upon the

speciÿc reactor geometry and can be calculated by using

well known correlations (Kataoka, 1986). Other instabilities

occur at higher values of Re, and the azimuthal Reynolds

number ratio Re}Re

c

, can be used to determine which hy-

drodynamic resides in the reactor.

In this work, the ow ÿeld in the reactor was modeled

by using the commercial CFD software FLUENT 6.0. Since

the solid particles are smaller than 20–30 m, and the solid

concentration is smaller than 0.1%, the inuence of the solid

phase on the ow ÿeld can be neglected and single-phase

turbulence models can be used. Thus, the Reynolds Stress

Model with standard wall function was used to model the

ow ÿeld. In our previous work (Marchisio, 2002) this com-

bination of turbulence model and near-wall treatment was

D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351 3343

Fig. 1. Sketch of the Taylor–Couette reactor and of the computational

domain used in the simulation (grey section).

found to give the best agreement with experimental data.

Simulations were carried out in two dimensions under the

hypothesis of axial-symmetry. Moreover, since the ow was

found to be symmetrical about the center of the reactor, only

one half of this section has been modeled.

A sketch of the reactor and of the computational do-

main used in the simulations is shown in Fig. 1. Several

grids were tested in order to verify that the solution was

grid-independent, and it was found that a grid with 18 nodes

in the radial direction and 181 in the axial direction for a to-

tal of 3060 computational cells was sucient. In our previ-

ous work (Marchisio, 2002) a comparison between 2D and

3D simulations was also carried out. It was found that with-

out axial ow and in a range of operating conditions similar

to this work no appreciable dierence was detected between

2D and 3D predictions.

The QMOM was implemented with three nodes, and as a

consequence the ÿrst six moments were tracked. This choice

is justiÿed by previous ÿndings (Marchisio et al., 2003b)

where N

d

= 3 was found to be the best conÿguration in

terms of accuracy and computational costs. The transport

equations for the ÿrst six moments were implemented by

using compiled user-deÿned functions, and details can be

found in Fluent Inc. (2002).

The quadrature approximation can be determined by

ÿnding the roots of the polynomial of order N

d

belonging

to the sequence of orthogonal polynomials with respect

to the ‘measure’ n(L) (see for details Dette & Studden,

1997). Since root ÿnding of a polynomial is a notori-

ously ill-conditioned problem, weights and abscissas of the

quadrature approximation can be calculated by using the

PD algorithm. Following this procedure a tridiagonal matrix

of rank N

d

is calculated from the ÿrst 2N

d

moments, and

the eigenvalues and the square of the ÿrst component of

the eigenvectors of this matrix are respectively the abscis-

sas (L

i

) and weights (w

i

) of the quadrature approximation.

The eigen-value/eigen-vector problem was implemented in

FLUENT via user-deÿned-subroutine by using the C sub-

routine TQLI (Press, Teukolsky, Vetterling, & Flannery,

1992).

The computational procedure was as follows. First, the

ow ÿeld was solved until a steady-state solution was

reached. The convergence criteria required that all normal-

ized residuals be smaller than 10

−6

. Next, the moments were

determined (m

0

, . . . , m

5

). Their initial values were deÿned to

be uniform throughout the computational domain and then

a time-dependent simulation was initiated with a ÿxed

time step of 10 s. The convergence criteria for all scalars

required that the normalized residuals be smaller than 10

−6

.

Several cases were investigated using dierent combina-

tions of breakage kernels and fragment distribution func-

tions. In all the cases investigated, aggregation was modeled

using an aggregation kernel consisting of the summation of

the Brownian and hydrodynamic kernels reported in Eqs.

(14) and (15). As already mentioned, experiments were con-

ducted in saline solutions in order to match the uid density

with that of the latex particles. Since the double-layer re-

pulsion is very sensitive to the value of ionic strength [and

at high salt concentration is practically negligible (Serra

et al., 1997)], the aggregation eciency can be consid-

ered to be unity. Knowledge of the solid volume fraction

[

t

=2.5×10

−5

and of the diameter of the latex primary par-

ticles L

o

=2×10

−6

m is sucient for determining the initial

conditions of the six moments (m

0

=3.125×10

12

m

−3

; m

1

=

6.25 × 10

6

m

−2

; m

2

= 12.5 m

−1

; m

3

= 2.5 × 10

−5

; m

4

=

5.0 × 10

−11

m; m

5

= 1.0 × 10

−16

m

2

). A summary of the

aggregation and breakage functions used in each of the dif-

ferent cases is reported in Table 3.

The exponents of the power-law breakage kernel [see

cases (1, 2, 3) in Table 3 or kernel (5) in Table 1] were found

through a dimensional analysis, forcing a linear dependence

for the particle size (i.e., ¸ =1). The resulting exponent for

the turbulent dissipation rate ([ = 3}4) is in good agree-

ment with the value found by ÿtting with experimental data

([ =0.5–1). Moreover, direct experimental evidence seems

to conÿrm the linear dependence with respect to the particle

size (¸ = 1). As concerns the exponential breakage kernel

we ÿrst need to identify some quantities such as the size of

3344 D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351

Table 3

Cases tested for the comparison with experimental data

Case a(L) b(L|z)

(1) c

1

c

3}4

v

−5}4

L Symmetric fragmentation

(2) c

1

c

3}4

v

−5}4

L Erosion

(3) c

1

c

3}4

v

−5}4

L Uniform

(4) c

A

c

1}2

exp

_

−c

B

[(L)

2.2

c

1}2

_

Symmetric fragmentation

(5) c

A

c

1}2

exp

_

−c

B

[(L)

2.2

c

1}2

_

Erosion

(6) c

A

c

1}2

exp

_

−c

B

[(L)

2.2

c

1}2

_

Uniform

For all cases investigated, L

o

= 2 × 10

−6

m and the solid volume

fraction [

t

= 2.5 ×10

−5

.

the primary particles (L

o

=2 ×10

−6

m), the fractal dimen-

sion of the particles d

[

=2.6 (Serra & Casamitjana, 1998a;

Sonntag & Russel, 1986), the value of the Hamaker constant

(A=10

−21

J, for details see Fitch, 1997), and the interparti-

cle distance that can be approximated as H

o

=2−4×10

−9

m.

Hence, the breakage constants [compare kernel (4) in Table

1 and cases (4, 5, 6) is Table 3] are given by c

A

=1}

√

12v ≈

258.2 and c

B

= (t

[

v

1}2

)}(j[

2.2

) ≈ 17.9. However, since A

and H

o

are properties of the system that are dicult to esti-

mate accurately, the constant c

B

will be expressed in terms

of the parameter group A}H

2

o

as follows

c

B

= 2.24 ×10

5

A

H

2

o

. (23)

As already mentioned, although the numerical value of the

group A}H

2

o

can be calculated by using values of A and H

o

found in the literature (Ayazi Shamlou et al., 1994; Fitch,

1997), the eect of changes in A}H

2

o

on the ÿnal mean aggre-

gate size will be investigated. It should be highlighted here

that this approach presents an inconsistency due to the fact

that the QMOM in the form presented in this work, assumes

non-fractal aggregates. However, since these aggregates are

compact (i.e., d

[

is very close to 3), the application of the

QMOM (assuming d

[

=3) and the calculation of the break-

age kernel (assuming d

[

= 2.6) seems acceptable. Indeed,

the introduction of the fractal dimension as an independent

parameter in the QMOM formulation represents one of the

next steps of our work, but it requires the formulation of the

population balance using at least two internal coordinates.

In Fig. 2 breakage frequency rates as a function of particle

size for the exponential and power-law kernels are shown

for two rotational speeds, N=125 and 165 rpm (Re}Re

c

=96

and 127), which correspond to volume-averaged turbulent

dissipation rates c = 0.035 and 0.070 m

2

s

−3

, respectively.

It is evident that the exponential kernel exhibits a much

stronger dependency on particle size. In fact, it scales with

the sixth power for low c and with the third power for high c.

L/L

o

0 10 20 30 40

N = 165 rpm

N = 125 rpm

L/L

o

a

(

L

/

L

o

)

0 10 20 30 40

10

-3

10

-2

10

-1

10

0

10

1

10

a

(

L

/

L

o

)

10

-5

10

-3

10

-1

10

1

Fig. 2. Comparison between breakage kernels for c = 0.035 m

2

s

−3

(N = 125 rpm; Re}Re

c

= 96) and for c = 0.070 m

2

s

−3

(N = 165 rpm;

Re}Re

c

= 127); open squares: exponential kernel with c

1

= 6.0 × 10

−4

,

open circles: power-law breakage kernel with d

[

= 2.6.

a

x

i

a

l

c

o

o

r

d

i

n

a

t

e

,

m

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

radial coordinate, m

Fig. 3. Velocity vectors in a meridian section of the Taylor–Couette

reactor at several rotational speeds of the inner cylinder. From left to

right: 75, 125, 165 and 211 rpm (Re}Re

c

= 58, 96, 127, 162).

4. Results and discussion

In Fig. 3, the mean velocity vectors in a meridian section

of the Taylor–Couette reactor are shown for 75, 125, 165,

and 211 rpm. For the four rotational speeds reported above

we ÿnd that Re}Re

c

falls in the range between 50 and 160,

which corresponds to the Turbulent Vortex Flow regime

(see Marchisio, 2002).

In all cases, the contour plots show the expected counter-

rotating vortical structure. Although no experimental

D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351 3345

t, s

0 2500 5000

t, s

0 2500 5000

t, s

d

0 2500 5000

0

5

10

15

20

N = 211 rpm

t, s

0 2500 5000

0

5

10

15

20

25

t, s

0 2500 5000

0

5

10

15

20

25

t, s

0 2500 5000

0

5

10

15

20

25

t, s

0 2000 4000 6000 8000

0

5

10

15

20

25

30

t, s

0 2000 4000 6000 8000

0

5

10

15

20

25

30

t, s

0 2000 4000 6000 8000

0

5

10

15

20

25

30

t, s

0 5000 10000 15000

0

10

20

30

40

t, s

d

0 5000 10000 15000

0

10

20

30

40

t, s

0 5000 10000 15000

0

10

20

30

40

t, s

0 5000 10000 15000

0

10

20

30

40

N = 75 rpm

t, s

d

0 2000 4000 6000 8000

0

5

10

15

20

25

30

N = 125 rpm

t, s

d

0 2500 5000

0

5

10

15

20

25

N = 165 rpm

t, s

0 2500 5000

Fig. 4. Time-evolution of the normalized mean particle size for case 1 (circle: experimental data; dot–dashed line: c

1

= 0.3 × 10

−3

; dashed line:

c

1

= 0.6 ×10

−3

; continuous line: c

1

= 1.0 ×10

−3

).

velocity data are available for these speciÿc cases, the re-

sults are consistent with our previous ÿndings (Marchisio,

2002). Because the grid used in the CFD simulation only

represents half of the axial length of the actual reactor,

the predicted number of vortex pairs in the reactor must

be multiplied by a factor of two. At the lowest rotational

speed shown in Fig. 3, the CFD simulation predicts eight

vortex pairs, whereas at higher rotation rates, seven vortex

pairs are predicted. It is well-known that the axial wave

number in the turbulent Taylor vortex regime depends upon

the azimuthal Reynolds number history, but in general the

number of vortices decreases to a minimum value as Re

is increased beyond the critical value for the onset of tur-

bulent Taylor vortex ow (Lewis & Swinney, 1999). The

change in the number of vortices in mainly caused by the

increase in size of the top and bottom vortices, which is

caused by a well-known end eect, whereas the axial length

of the central vortices seems to be quite constant. The CFD

simulations are consistent with this trend.

Comparison of the aggregation–breakage simulations

with experimental data is made through the normalized

mean particle size d, which is the ratio between the mean

particle size L

43

and the size of primary particles L

o

. The

mean size of the aggregate L

43

is calculated as the ratio be-

tween m

4

and m

3

and corresponds to the volume-averaged

particle size. Notice that the particle size evolution reported

in the comparison is the spatial average over the entire

reactor volume.

4.1. Power-law breakage kernel

Case 1. In this case the aggregation–breakage pro-

cess was modeled by using a power law breakage ker-

nel and assuming that particles break into two equal

fragments.

The comparison between experimental data at four rota-

tional speeds of the inner cylinder with model predictions

for case 1 (see Table 3) for dierent values of the con-

stant c

1

is reported in Fig. 4.The model predictions and

experimental data both show that the steady-state mean

particle size decreases with increasing rotational speed.

However, the simulations predict a faster approach to

steady state, especially at the lower rotational speeds in-

vestigated. The best agreement between simulations and

experiments is found when c

1

=0.6×10

−3

. The constant c

1

is a dimensionless quantity that accounts for physical prop-

erties of the particles and attractive forces that maintain the

aggregate.

Case 2. In this case the aggregation–breakage process was

modeled by using a power-law breakage kernel and assum-

ing that particles undergo erosive breakage. The comparison

with experimental data is shown in Fig. 5. The combina-

tion of the strong hydrodynamic aggregation kernel with the

relatively weak erosion fragment distribution function leads

to simulation predictions of a rapid accumulation of most

of the system mass into a few very large particles. This is

not surprising, since erosion of large aggregates results in

two particles, one of which is a monomer and the other of

which is still a large aggregate. Changes in the value of c

1

are unable to reconcile the simulation predictions and ex-

perimental data, which suggests that erosion cannot be the

only breakage mechanism at play in the experiments. This

does not imply that erosion is not playing any role in the

fragmentation process. It may be possible to explain this

experimental behaviour in terms of a mixture of breakage

mechanisms.

3346 D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351

1 10 100 1000 10000

t, s

1

10

100

d

Fig. 5. Time-evolution of the normalized mean particle size for case

2 (experimental data: circles N = 75 rpm; squares N = 125 rpm;

diamonds N = 165 rpm; triangles N = 211 rpm; CFD predictions

with c

1

= 0.3 × 10

−3

: dot–dot–dashed line N = 75 rpm; dot–dashed

line N = 125 rpm; dashed–dashed line N = 165 rpm; continuous line

N = 211 rpm).

Case 3. In this case the breakage process was modeled

by using a power-law breakage kernel and assuming that

aggregates break into fragments with a uniform probability

distribution of sizes. In this case agreement between experi-

ment and simulation is quite good for a value of the constant

c

1

in the range between 0.6×10

−3

and 1.0×10

−3

(see Fig.

6). The results are also qualitatively and quantitatively com-

parable with case 1 (symmetric fragmentation), but in this

case it seems that the limiting particle size is reached after

a longer period of time, thereby improving the agreement

with the experimental data.

t, s

d

0 5000 10000 15000

0

10

20

30

40

50

N = 75 rpm

t, s

d

0 5000 10000 15000

0

10

20

30

40

50

t, s

d

0 2500 5000

0

5

10

15

20

25

30

N = 211 rpm

t, s

d

0 2000 4000 6000 8000

0

10

20

30

40

N = 125 rpm

t, s

d

0 2000 4000 6000 8000

0

10

20

30

40

t, s

d

0 2500 5000

0

5

10

15

20

25

30

N = 165 rpm

t, s

d

0 2500 5000

0

5

10

15

20

25

30

t, s

d

0 2500 5000

0

5

10

15

20

25

30

t, s

d

0 2500 5000

0

5

10

15

20

25

30

t, s

0 2500 5000

t, s

d

0 2500 5000

0

5

10

15

20

25

30

t, s

0 2500 5000

t, s

d

0 2000 4000 6000 8000

0

10

20

30

40

t, s

0 2000 4000 6000 8000

t, s

d

0 5000 10000 15000

0

10

20

30

40

50

t, s

0 5000 10000 15000

Fig. 6. Time-evolution of the normalized mean particle size for case 3 (circle: experimental data; dot–dashed line: c

1

= 0.3 × 10

−3

; dashed line:

c

1

= 0.6 ×10

−3

; continuous line: c

1

= 1.0 ×10

−3

).

4.2. Exponential breakage kernel

Case 4. This case corresponds to the exponential breakage

kernel coupled with a fragment distribution function that re-

quires the formation of two equal-sized fragments. In Fig. 7

the comparison between experimental data and exponential

breakage model predictions for the four rotational speeds

of the inner cylinder are reported. As was already men-

tioned, model predictions were calculated using dierent

values of the group of constants A}H

2

o

, due to the uncertainty

in determining the Hamaker constant A and the interparticle

distance H

o

. Neither the approach to steady state nor the

steady-state mean particle size are well predicted by the

exponential breakage kernel. This could be due to the fact

that in the beginning of the simulation the aggregates are

not fractal (i.e., d

[

is practically equal to three) and thus the

exponential breakage kernel does not give good predictions.

Case 5. In this case the exponential breakage rate function

was used with the erosive fragment distribution function.

Fig. 8 shows that A}H

2

o

= 0.8 × 10

−4

J}m

2

does not give

good agreement with experimental data. In fact, by using

this value a gelling transition is detected. Gelation occurs

when mass is no longer being conserved, and in a ÿnite time,

inÿnite-sized particles are detected. In terms of the moments

this is signaled by negative values of the zeroth moment.

By decreasing A}H

2

o

to 0.4 × 10

−4

J}m

2

, the gelling

transition is only delayed, and A}H

2

o

has to be decreased to

0.2×10

−4

J}m

2

in order not to have gelation within the ÿrst

5000 s of the simulation. The existence of a steady-state

solution for this case is very dicult to be proved, in fact, it

might be possible that the transition is again only delayed.

However, even if the solution for A}H

2

o

= 0.2 ×10

−4

J}m

2

was the actual steady-state solution, the predicted limiting

D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351 3347

t, s

d

0 2500 5000

0

5

10

15

t, s

d

0 2500 5000

0

5

10

15

t, s

d

0 2500 5000

0

5

10

15

t, s

d

0 2000 4000 6000 8000

0

5

10

15

20

t, s

d

0 2000 4000 6000 8000

0

5

10

15

20

t, s

d

0 2000 4000 6000 8000

0

5

10

15

20

t, s

0 5000 10000 15000

0

5

10

15

20

25

t, s

0 5000 10000 15000

0

5

10

15

20

25

t, s

0 5000 10000 15000

0

5

10

15

20

25

N = 75 rpm

t, s

d

0 2000 4000 6000 8000

0

5

10

15

20

N = 125 rpm

t, s

d

0 2500 5000

0

5

10

15

N = 165 rpm

t, s

d

0 2500 5000

0

2

4

6

8

10

N = 211 rpm

t, s

d

0 2500 5000

0

2

4

6

8

10

t, s

d

0 2500 5000

0

2

4

6

8

10

t, s

d

0 2500 5000

0

2

4

6

8

10

t, s

d

0 5000 10000 15000

0

5

10

15

20

25

Fig. 7. Time-evolution of the normalized mean particle size for case 4 and for d

[

= 2.6 (circle: experimental data; continuous line: A}H

2

o

= 0.7 ×10

−4

;

dashed line A}H

2

o

= 0.8 ×10

−4

; dot–dashed line A}H

2

o

= 0.9 ×10

−4

).

Fig. 8. Time-evolution of the normalized mean particle size for case 5 and

for d

[

=2.6 (circle: experimental data; continuous line: A}H

2

o

=0.8×10

−4

;

dashed line: A}H

2

o

= 0.4 ×10

−4

; dot–dashed line: A}H

2

o

= 0.2 ×10

−4

).

particle size established is much smaller than what is exper-

imentally observed.

Case 6. The last case considered pairs the exponential

breakage rate with the uniform fragment distribution func-

tion. Results in this case are very similar to case 4, but the

predictions are more sensitive to the value of the parameter

A}H

2

o

(see Fig. 9).

4.2.1. Comparison with the homogeneous model

It is interesting to compare the predictions of the CFD

model with the predictions of a spatially homogeneous

model. Fig. 10 shows the CFD predictions of the distribu-

tion of turbulent dissipation rate over the reactor volume for

two rotational speeds. Note that there is little spread in the

distribution, which is one of the most important and attrac-

tive aspects of turbulent Taylor–Couette ow. Nevertheless,

if simulations are performed neglecting spatial inhomo-

geneities and using volume-averaged values of turbulent

properties, signiÿcant dierences arise in the predictions of

the homogeneous and spatially heterogenous models. For

example if spatial inhomogeneities are neglected, then the

mean particle size can be overestimated by 30–50%, de-

pending on the choice of kernels. If the reactor is modeled

by using a small number of perfectly mixed reactors with

dierent turbulent properties, according to the hystogram

reported in Fig. 10, the agreement may improve without

resorting to the direct solution of the population balance

equation in the CFD code. However, if for example the

solid particles are produced by a fast chemical reaction, or

if the solid concentration is higher and the ow ÿeld has to

be described by using a multiphase model, this “full-CFD”

approach seems to be necessary (Baldyga et al., 2002;

Marchisio et al., 2002).

5. Conclusions

Simultaneous aggregation and breakage of particles in a

Taylor–Couette reactor was simulated by implementing the

QMOM in a commercial CFD code (FLUENT). Experi-

mental data taken from the literature was compared with the

CFD predictions for a range of operating conditions and for

several combinations of aggregation and breakage kernels.

The implementation of the QMOM in FLUENT was

found to be very convenient. In fact, by tracking only six

scalars and using the quadrature approximation the mo-

ments of the PSD were tracked with very small errors. It is

important to emphasize that achieving the same accuracy

with a DPB method requires use of at least 20–40 classes

3348 D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351

t, s

0 5000 10000 15000

0

5

10

15

20

25

30

t, s

0 5000 10000 15000

0

5

10

15

20

25

30

t, s

0 5000 10000 15000

0

5

10

15

20

25

30

t, s

d

0 5000 10000 15000

0

5

10

15

20

25

30

N = 75 rpm

t, s

d

0 2000 4000 6000 8000

0

5

10

15

20

N = 125 rpm

t, s

d

0 2000 4000 6000 8000

0

5

10

15

20

t, s

d

0 2000 4000 6000 8000

0

5

10

15

20

t, s

d

0 2000 4000 6000 8000

0

5

10

15

20

t, s

d

0 2500 5000

0

5

10

15

N = 165 rpm

t, s

d

0 2500 5000

0

5

10

15

N = 165 rpm

t, s

d

0 2500 5000

0

5

10

15

N = 165 rpm

t, s

d

0 2500 5000

0

5

10

15

N = 165 rpm

t, s

d

0 2500 5000

0

2

4

6

8

10

N = 211 rpm

t, s

d

0 2500 5000

0

2

4

6

8

10

N = 211 rpm

t, s

d

0 2500 5000

0

2

4

6

8

10

N = 211 rpm

t, s

d

0 2500 5000

0

2

4

6

8

10

N = 211 rpm

Fig. 9. Time-evolution of the normalized mean particle size for case 6 and for d

[

= 2.6 (circle: experimental data; continuous line: A}H

2

o

= 0.7 ×10

−4

;

dashed line: A}H

2

o

= 0.8 ×10

−4

; dot–dashed line: A}H

2

o

= 0.9 ×10

−4

).

turbulent dissipation rate, m

2

s

-3

v

o

l

u

m

e

%

0 0.25 0.5 0.75 1

0

20

40

60

80

N = 165 rpm

turbulent dissipation rate, m

2

s

-3

v

o

l

u

m

e

%

0 0.1 0.2 0.3 0.4 0.5

0

20

40

60

80

N = 125 rpm

Fig. 10. Histogram of the distribution of the turbulent dissipation rate

over the reactor volume at 125 and 165 rpm (Re}Re

c

= 96 and 127).

(Marchisio et al., 2003b). For this kind of calculation the

controlling step is the solution of the convection and turbu-

lent diusion terms and thus the global CPU time is mainly

inuenced by the number of scalars to be tracked. Although

a general rule for ÿnite-volume codes does not exist, it is

reasonable to expect that the increase in the CPU time with

the number of scalars is stronger than a linear function. For

this reason we can infer that an increase in the number of

scalars from six to 20–40 would cause a drastic increase

in the CPU time, thereby rendering the CFD approach im-

practical, especially for complex geometries and if coupled

with multiphase models. A detailed comparison between

the QMOM and a DPB approach with a multiphase model

for bubble columns is under investigation, and ÿrst results

appear to conÿrm this statement. Moreover, previous results

showed that by using the QMOM the speciÿc CPU time per

scalar solved is constant for dierent kernels (Marchisio

et al., 2003a). Further conÿrmation is provided by the fact

that with all the tested combinations of kernels used in this

work, the global CPU time was approximately constant (i.e,

about 3–4 h of wall time for simulating two hours of real

experiment). This is not true for most DPB approaches,

where the discretization of the internal coordinate can

generate mathematical stiness.

Although the QMOM like all moment methods, does

not provide a detailed description of the PSD, recent work

by Diemer and Olson (2002) shows that knowledge of

the lower-order moments is sucient to infer the shape of

the PSD. Moreover, in many applications knowledge of the

PSD is not required. It is important to point out that since

the information needed during the simulation is directly

obtained from the moments, the PSD reconstruction repre-

sents a post-processing step at the end of the simulation,

and thus does not increment the global CPU time.

Concerning the choice of breakage kernels, the exponen-

tial kernel is attractive since its formulation does not require

the invocation of unknown constants. The exponential ker-

nel can in fact be expressed in terms of physical properties of

the aggregate and of the suspending solution. The power law

kernel has no physical basis and proportionality constants

and exponents can be found only through semi-theoretical

D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351 3349

analysis and comparison with experimental data. However,

use of the power-law kernel improved the agreement with

the transient behavior. As already mentioned, this can be

caused by the fact that for short times the aggregates are

very compact and small and therefore the fractal description

underpredicts the breakage rates. Concerning the daughter

distribution function, it appears that the experimental behav-

ior might be explained in terms of a mixture of breakage

mechanisms, for example erosion for small aggregates and

symmetric breakage for large ones.

It is very dicult to assess the suitability of dierent ker-

nels since the comparison with experiments is made in terms

of the volume-averaged mean particle size. For this reason,

the experimental investigation should be carried out using a

continuous reactor and an in-situ image analysis system to

gather local information for comparison with CFD predic-

tions. Such an investigation is under way (Marchisio et al.,

2002). Moreover the approach has been also applied in a di-

rect formulation (direct quadrature method of moments) for

the investigation of multiphase systems (Marchisio & Fox,

2003). Results from these studies will be reported in greater

detail in future communications.

Notation

a(L) breakage kernel

A Hamaker constant

b(L|z) daughter distribution function

b

(k)

i

kth moment of the daughter distribution function

for L = L

i

B(L; x, t) birth term due to aggregation and breakage

B

a

k

(x, t) kth moment transform of the birth term due to

aggregation

B

b

k

(x, t) kth moment transform of the birth term due to

breakage

d dimensionless mean particle size

d

1

diameter of the inner cylinder of the Taylor–

Couette reactor

d

2

diameter of the outer cylinder of the Taylor–

Couette reactor

d

[

fractal dimension

D annular gap between the inner and outer cylinder

of the Taylor–Couette reactor

D(L; x, t) death term due to aggregation and breakage

D

a

k

(x, t) kth moment transform of the death term due to

aggregation

D

b

k

(x, t) kth moment transform of the death term due to

breakage

F inter-particle force of the fractal aggregate

G molecular growth rate

H length of the Taylor–Couette reactor

H

o

primary particle distance in the aggregate

J(x, t) nucleation rate

k

B

Boltzmann constant

k

c

co-ordination number of the fractal aggregate

L particle size

L

i

abscissa (or node) of the quadrature approxima-

tion

L

o

primary particle size

L

43

mean particle size

m

k

(x, t) kth moment of the PSD

n(L; x, t) particle size distribution function

N rotational speed of the inner cylinder of the

Taylor–Couette reactor

r

1

inner cylinder radius of the Taylor–Couette re-

actor

Re Reynolds number

Re

c

critical Reynolds number for the transition to the

laminar Taylor Vortex Flow

t time

u

i

Reynolds-averaged velocity in the ith direction

w

i

weight of the quadrature approximation

x position vector

x

i

ith component of the position vector

Greek letters

: exponent for the kinematic viscosity in the

power-law breakage kernel

[ exponent for the turbulent dissipation rate in the

power-law breakage kernel

[(L, z) aggregation kernel

¸ exponent for the particle size in the power-law

breakage kernel

I molecular diusivity

I

A

aspect ratio of the Taylor–Couette reactor

I

t

turbulent diusivity

c turbulent dissipation rate

z particle size

j viscosity of the suspending uid

v kinematic viscosity of the suspending uid

j

s

solid particle density

t

[

aggregate strength

[(L) volume fraction of solid within the aggregate

c

1

angular velocity of the inner cylinder of the

Taylor–Couette reactor

Acknowledgements

This work has been ÿnancially supported the US

Department of Energy (Project award number DE-FC07-

01ID14087).

Appendix A.

The procedure used to ÿnd weights (w

i

) and abscissas

(L

i

) from the moments is based on the PD algorithm. The

ÿrst step is the construction of a matrix P with components

3350 D. L. Marchisio et al. / Chemical Engineering Science 58 (2003) 3337–3351

P

i, )

starting from the moments. The components in the ÿrst

column of P are

P

i, 1

= o

i1

, i ∈1, . . . , 2N + 1, (A.1)

where o

i1

is the Kronecker delta. The components in the

second column of P are

P

i, 2

= (−1)

i−1

m

i−1

, i ∈1, . . . , 2N + 1. (A.2)

Since the ÿnal weights can be corrected by multiplying by

the true m

0

, the calculations can be done assuming a nor-

malized distribution (i.e., m

0

=1). Then the remaining com-

ponents are found from the PD algorithm:

P

i, )

= P

1, )−1

P

i+1, )−2

−P

i, )−2

P

i+1, )−1

,

) ∈3, . . . , 2N + 1 and i ∈1, . . . , 2N + 2 −). (A.3)

If, for example, N = 2 then P becomes

P =

_

¸

¸

¸

¸

¸

¸

¸

¸

_

1 1 m

1

m

2

−m

2

1

m

3

m

1

−m

2

2

0 −m

1

−m

2

−m

3

+ m

2

m

1

0

0 m

2

m

3

0 0

0 −m

3

0 0 0

0 0 0 0 0

_

¸

¸

¸

¸

¸

¸

¸

¸

_

.

(A.4)

The coecients of the continued fraction (:

i

) are gener-

ated by setting the ÿrst element equal to zero (:

1

= 0), and

computing the others according to the following recursive

relationship:

:

i

=

P

1, i+1

P

1, i

P

1, i−1

, i ∈2, . . . , 2N. (A.5)

A symmetric tridiagonal matrix is obtained from sums and

products of :

i

:

a

i

= :

2i

+ :

2i−1

, i ∈1, . . . , 2N −1 (A.6)

and

b

i

=−

√

:

2i+1

:

2i−1

, i ∈1, . . . , 2N −2, (A.7)

where a

i

and b

i

are, respectively, the diagonal and the

co-diagonal of the Jacobi matrix. Once the tridiagonal ma-

trix is determined, generation of the weights and abscissas

is done by ÿnding its eigenvalues and eigenvectors. In fact,

the eigenvalues are the abscissas and the weights can be

found as follows:

w

)

= m

0

t

2

)1

, (A.8)

where t

)1

is the ÿrst component of the )th eigenvector v

)

.

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