Chemical Engineering Science 56 (2001) 2445}2457

A PDF modelling of precipitation reactors

L. Falk *, E. Schaer

Laboratoire des Sciences du Ge& nie Chimique, Ecole Nationale Supe& rieure des Industries Chimiques-CNRS, 1 rue Grandville, B.P. 451, 54001
Nancy cedex, France

Centre de Ge& nie Chimique des Milieux Complexes, Ecole Nationale Supe& rieure des Industries Chimiques-CNRS, 1 rue Grandville, B.P. 451, 54001
Nancy cedex, France

Abstract

E!orts to model precipitation processes in chemical reactors need to combine #uid mechanics with precipitation processes
description. The main di$culty is to consider together micromixing phenomena, which are known to play an important role, with
complex reactions kinetics and particles size distribution in the #ow. In the present study, a probability density function (PDF)
method is presented to calculate the evolution of the particles size distribution. The main advantage of the method is to include
a micromixing model based on a Lagrangian frame where chemical reactions are treated without modelling and which requires
minimal computational resources. The micromixing model considered is the interaction and exchange with the mean (IEM).
Precipitation reactions are nucleation, growth and aggregation. Because of the nature of the powerful numerical technique used, based
on Monte-Carlo simulations, the method is able to produce, at any point in the #ow, reactants concentration and supersaturation
"elds, and the particles size distribution "eld, by simple moments method. The main advantage of the method over traditional
population balance solvers is its capability to treat multi-dimensional (e.g. size, crystal morphology, chemical properties, etc.)
population balances just as e$ciently as it treats high-dimensional PDF. The PDF code is coupled with the commercial CFD
package FLUENT which is used for the turbulent calculation of the #ow (classical k}
turbulence model), where the presence of the
solid phase is assumed not to a!ect the #ow "eld. An example is presented in the case of silica particles aggregation. The in#uence of
initial reactants concentration and hydrodynamics parameter are investigated.  2001 Elsevier Science Ltd. All rights reserved.

Keywords: Probability density functions; Precipitation; Mixing; Aggregation; Silica

1. Introduction precipitation processes are often controlled by hydrodyn-

Precipitation typically consists in mixing of two liquid
streams to create supersaturation, which then induces
nucleation, particle growth and (very often) agglomer-
ation. The precipitation processes are frequently followed
by solid}liquid separation processes, to obtain a dry
product. Most of the time, the "nal product has to ful"l
speci"c requirements such as crystal size, morphology,
composition or purity. When the time scale of the pre-
cipitation kinetics is much longer than the time scale of
mixing, the mixing processes of the two liquid streams are
terminated prior to the reaction. In this case, the "nal
product characteristics mainly depend on physico-chem-
ical parameters, but not on mixing conditions. However,
* Corresponding author.
E-mail address: falk@ensic.u-nancy.fr (L. Falk).
amics and mixing processes: indeed, when precipitation
kinetics are faster or of the same order of the mixing
process, nucleation, growth and agglomeration begin be-
fore a homogeneous supersaturation level is achieved in
the reactor. The inhomogeneous "eld of supersaturation
then causes di!erent driving forces, which in turn drasti-
cally a!ects the "nal product properties.
Therefore, e!orts to model precipitation processes in
chemical reactors need to combine #uid mechanics with
precipitation processes description. The main di$culty is
to consider together macromixing and micromixing phe-
nomena, with complex reactions kinetics, and particle
size distribution in the #ow.
The in#uence of macro- and micromixing on nuclea-
tion and particle growth has been identi"ed by several
researchers. Various mixing models (Garside & Tavare,
1985; Marcant & David, 1991; David & Marcant, 1994)
have been proposed and computed for continuous and
semi-batch stirred tank precipitators. Design factors,

0009-2509/01/$ - see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 4 4 7 - 4
2446 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457

such as feed addition mode, feed rate, feed location, feed species at point X and time t, between C and C#dC.
concentration, stirring speed, and stirrer type have been The transport equation of f can be derived from the
A
shown to a!ect the resulting average particle size conservation equations for passive scalars and can be
(Mersmann & Kind, 1988; Aslund & Rasmuson, 1992; written as (Pope, 1985)
Franke & Mersmann, 1995). However, majority of these
previous works have considered simple phenomenologi- !  0  
cal models of the #ow, based on residence time distribu- CDE CFDFE
tion (RTD). They describe the #ow pattern by perfect f f 
A #;  A # (S (C)f )
reactors associations, as plug #ow or perfect stirred tank t G x C H A
reactors, coupled with micromixing models. This ap- G H
proach is simple to develop and may give tendency re- 2
    +    
sults but does not, in general, re#ect details of the real CFFDFFE CFFFDFFFE

 
#ow patterns in a complex 3D apparatus. With the devel-   1
"! (u  Cf ) ! D C C f . (1)
opment of computational #uid dynamics (CFD) codes, it x G A C  A H A
G H
is now possible to calculate satisfactorily the #ow struc-
ture and mixing in complex precipitators. However, the The left-hand side terms of this expression include the
description of turbulent reacting #ows is still di$cult accumulation of probability, the probability transport in
because of the randomness of the #ow "eld and the real space by the mean velocity "eld ;  and the prob-
complex chemical processes involved. Studies have been G
ability transport in composition space of species j by
carried out in this "eld (Van Leeuwen, Bruinsma, & Van chemical reactions S . These terms are calculated exactly
Rosmalen, 1996; Wei & Garside, 1997) but perfect mi- H
without any assumptions. On the right-hand side are the
cromixing was assumed to exist in each computational unclosed terms which include probability transport in
cell. As nucleation has been shown to be very sensitive to real space by the velocity #uctuations u and the prob-
micromixing, such a strong assumption may lead to G
ability transport in composition space by molecular dif-
considerable errors in particle size distribution predic- fusion (micromixing). These terms must be modelled.
tion. Therefore, for such mixing-sensitive reactions, all
scales must be considered.
Traditionally, reacting #ows equations are solved us- 2.1. Turbulent diwusivity model
ing the Reynolds decomposition, introducing the concen-
tration moment which deals with averaged quantities of Classically, the Boussinesq assumption, i.e. the gradi-
the #ow and concentration "elds. The mean scalar "eld ent di!usion model, is used to close the turbulent trans-
equation contains unclosed terms as the mean reaction port term:
rate which is the most di$cult term to close and, unfortu-
f
nately, it is of great importance in reactive #ow model- u  Cf "!D A , (2)
ling. When several reactants are involved with complex G A R x
G
"nite rate chemistry as in precipitation processes, the
where D is the turbulent di!usion coe$cient. Typically,
di$culties associated with moment closures are insur- R
D can be estimated by using the turbulence k}
model
mountable and other methods must be employed. R
D "(C /0.7)k/
where C "0.09, k is the turbulent
Full probability density functions (PDF) methods are R I I
tractable methods for industrial complex reactive #ows. kinetic energy and
the turbulent energy dissipation.
They combine an exact treatment of chemical reactions
with a closure of turbulence "eld and are an e$cient tool 2.2. Micromixing model
for complex reaction processes. The aim of this paper is
to present PDF methods for precipitation processes In this study, we closed the micromixing phenomena
simulation, including nucleation, growth and agglomer- by the classical Lagrangian interaction by exchange with
ation kinetics together with micromixing phenomena. An the mean (IEM) model proposed by Villermaux and
application example will be presented in the case of Devillon (1972), also known in turbulent combustion as
agglomeration of silica particles. the LMSE model proposed by Dopazo (1975):

   
1 (C !C )
D C C f " H H f, (3)
2. PDF methods  A H A t A
I
In the composition PDF approach, adopted here, the where C is the concentration of species j in a #uid
H
vector of species concentrations C is described by aggregate and where C " C f dC is the local
H  H A H
a multi-dimensional probability density function f , so mean concentration of species j. The micromixing time
A
that f dC is the probability to have the concentration of t is estimated using the k}
model by t "k/
.
A I I
 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457 2447

3. Precipitation reactions example by a crystal bridge between two or more crys-

The left-hand side terms of the PDF transport equa-
tion include a probability transport term in composition
space by chemical reactions. The considered precipita-
tion reactions may be nucleation, growth and agglomer-
ation. The kinetics implemented in the PDF code are
presented hereafter.
3.1. Kinetics
3.1.1. Supersaturation
The thermodynamic driving force for crystallization is
given by the di!erence in chemical potential of the crys-
tals. The formation of this bridge requires crystal growth,
for which supersaturation is an essential prerequisite. It
has to be distinguished from aggregation that occurs in
the absence of supersaturation. During precipitation pro-
cesses, both aggregates and agglomerates are essentially
observed. From a global point of view, dealing with
supersaturated solutions, we will consider agglomeration
as the generic term.
The agglomeration of two particles of volumes u and
v!u into a particle of volume v can be represented,
according to the classical work of Smoluchowski (1917),
by the birth and death functions:


1 T
tallizing compound in a supersaturated solution and in B(v)" (v!u, u) n (v!u)n(u) du,
the crystal. The chemical potential of the dissolved com- 2

pound can be de"ned by way of activity while the super-


saturation ratio is de"ned as D(v)"n(v) (v, u)n(u) du. (9)




a CJ>CJ\
J J CJ>CJ\ J
S" ! " > \ !A " > \
. The aggregation kernel , expressed as a function of
a CJ> CJ\
J K !A
! > \ ! A particle volume, is a measure of the frequency of collision
(4)
between particles of volumes u and v!u that are suc-
Thus it is necessary to know the stoichiometric mean cessful in producing a particle of volume v.
activity coe$cient
in order to calculate the super-
!A
saturation ratio. In the case of relatively dilute solutions, 3.2. Moment transformation
it is approximated to one.
3.2.1. Kinetic expression
3.1.2. Nucleation The size distribution of the particles that are trans-
The nucleation rate of particles of volume <H can be ported by the #ow is characterised by the moment equa-
represented, according to the classical primary nuclea- tions. The moments of the distribution represent the
tion theory, by average or total properties of the solid phase and can be
used to calculate properties such as mean particle size or


A
B"B exp ! , (5) distribution variance. Following the treatment proposed
ln S by Hulburt and Katz (1964) (i.e. multiplying by vH and
where integrating each term with respect to v over the entire
4

N< particle volume range), the moment transformation of
A" ? K (6) the population balance yields for the moment's kinetic
27
(R¹)
T expression
and the critical volume <H of the nucleated particles is
S H "B<HH#jG
deduced from the Gibbs}Thomson relation I H\



  1


4

<  (v#u)H!vH (v, u)n(u)n(v) du dv. (10)
<H"
(¸H)"
? K . (7) #
T T 3
R¹ ln S  
2
T
Moments equations for the "rst three moments are then:
3.1.3. Growth


The overall growth rate relating the particle volume 1  
S  "B! (v, u)n(u)n(v) du dv,
variation against time is frequently expressed by the I 2
 
relation
S  "B<H#G ,
G"k (S!1)E. (8) I 
E

 
The growth rate is here taken to be independent of the S  "B<H#2G # uv(v, u)n(u)n(v) du dv. (11)
I 
particle volume.  
3.1.4. Agglomeration
Agglomeration is here taken as the uni"cation of par-
ticles which are cemented later by chemical forces, for
The "rst moment  (which represents the total volume

of the particles per volume of solution) is conserved
during agglomeration. For analytically convenient ker-
nels (i.e. kernels that yield analytical solutions of the
2448 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457

Table 1
Solutions of the agglomeration term for analytically convenient kernels

Form of kernel (u, v)" (u, v)" (uv) (u, v)" (u#v)
  
(constant kernel) (product kernel) (sum kernel)

Moment's order
1 1 !  
0 !   !     
2   2  
1 0 0 0
2  
 
agglomeration term, see Table 1) analytical solutions for
the "rst three moments can be found.
3.2.2. Concentration variation
The variation of the solution-phase precipitating com-
pound may be described by the variation of the solid
mass produced:
  2  
    
model is used. The results are the mean velocity compo-
nents "eld, the turbulent kinetic energy k and the turbu-
lent energy dissipation
"elds.
In the second step, the PDF simulation is performed
by a home-made code. It is based on a set of notional
particles moving in the computational domain, where the
Monte-Carlo code mesh is the same as the CFD mesh.
Each of the notional particles follows a set of stochastic
dC dC  d

> > "
\ \ "! N . (12) di!erential equations which mimic the PDF transport in
dt dt M dt physical and phase spaces, where each particle transports
N
species concentration and particles distribution mo-
Finally, the resolution of the coupled concentration and
ments.
moments transport equations, including micromixing, at
Two types of Monte-Carlo codes can be used, a Lag-
any point of the #ow, yields the reactants concentration,
rangian or an Eulerian frame. Our code has an Eulerian
supersaturation and distribution moments "elds.
form and in that case, the PDF transport equation is very
The average and total properties of the distribution
similar to the classical population balance of notional
can directly be obtained from these position-dependent
particles over each computational cell. We can consider
moments. For example, the average particle volume and
inter-cell or macromixing processes * such as spatial
distribution variance are here characterised by
transport by mean convection and by turbulent di!usion


   exchange notional particles between cells * and intra-
< "  , "   !1 . (13)
  T  cell processes * such as chemical reaction and microm-
  ixing. The intra-cell processes are commonly subdivided
The resolution has been here described for the number into two di!erent steps. For each notional particle, the
population density expressed as a function of particle chemical reaction step is "rst considered where the time
volume. As it will be seen in the next part, the method can evolution of the composition vector C (concentration
H
also be applied for the moments expressed as a function and particles distribution moments) is calculated by in-
of particle diameter. tegration of the balance equation over a small time inter-
val t:
dC
4. Stochastic solution method H "S . (14)
dt H
The composition PDF is a multidimensional distribu- The micromixing step is then considered where the time
tion of (n #dim) independent variables, with n being evolution of the composition vector C is calculated by
G G H
the number of composition variables (generally more integration of the IEM balance equation over a small
than 5, 2 for chemical species and 3 for the particle size time interval t:
distribution moments) and dim, the spatial dimension. As

 
dC (C !C )
the computational e!ort to solve the equation using H" H H , (15)
a "nite-di!erence grid grows exponentially with the num- dt t
I
ber of variables, more e$cient techniques have to be used where the micromixing time t is calculated using the
to solve the problem. For multi-species PDF a Monte- I
local values of k and
. The mean value of the composi-
Carlo technique is used as the solving method (Pope, tion vector C is computed by averaging the composition
1985; Fox, 1996). The procedure is split in two steps: H
values over the N notional particles:
The turbulent #ow "eld, without any reaction, is "rst
solved using the CFD commercial code FLUENT, based 1 ,
C " C . (16)
on a "nite-volume method. The standard k}
turbulent H N HI
I
 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457 2449

Fig. 1. Coaxial mixing jet reactor.

Table 2
Flow con"guration parameters

Con"guration 1 Con"guration 2

Velocity inlet: u 4 m s\ 2 m s\


In#ow A (interior) [Na>] concentration 0 mol m\ 0 mol m\
[SiO ] concentration 6000 mol m\ 12 000 mol m\

Velocity inlet: u 0.25 m s\ 0.5 m s\

In#ow B (annular) [Na>] concentration 6000 mol m\ 3000 mol m\
[SiO ] concentration 0 mol m\ 0 mol m\


Compared to classical methods which do not solve
microscales processes, PDF methods are considerably
more computationally expensive. To keep an acceptable
statistical noise level, it is necessary to consider not less
than 100 notional particles per computational cell. For
coarse 2D meshes * 2000 cells, for instance * and
a composition vector of 5 species (2 chemical species and
3 particles size distribution moments), 10 di!erential
equations have to be solved. For stationary reactive
#ows, the PDF transport equation is integrated over time
until the calculated composition "elds reach stationary
values. Typically, in an open system, integration time is
of the order of several residence times. On a Pentium
300 MHz PC, stable results are reached after several
CPU hours of calculation.
5. Application
5.1. Fluid yow and passive tracer validations
5.1.1. Flow conxguration
The aggregation is carried out in a coaxial mixing jet
reactor as illustrated in Fig. 1. The tubular reactor has an
internal diameter of 5;10\ m and the central injection
tube 1;10\ m in diameter. The central in#ow (A) feeds
the reactor within a silica solution, i.e. one of the react-
ants that contains particles, whereas the annular in#ow
(B) is composed of sodium ions, that will increase the
ionic strength of the solution, promoting aggregation of
the particles. Mixing between the two streams is realised
by the shear created by the high-velocity di!erence.
From dimensional analysis, it can be shown that the
#ow in such a coaxial mixing jet can be described by
a dimensionless number, named the Craya-Curtet num-
ber (Becker, Hottel, & Williams, 1963):
(u /u )((D/d)!1
C"   . (17)
R (1!(u /u )
 
A critical value of the number C "0.976 (Barchilon
R  
& Curtet, 1964) has been experimentally determined for
which a recirculation loop appears when C (C ,
R R  
inducing a back-mixing e!ect in the reactor.
In order to illustrate the in#uence of mixing on the
aggregation reaction, two di!erent #ow con"gurations
characterised by a di!erent value of the Craya-Curtet
number (cf. Table 2) are compared:
Con"guration 1: C "0.296,
R
Con"guration 2: C "1.414.
R
The reactor is designed for a speci"c production of ag-
gregated silica particles. As our objective is to reach the
same silica production for both #ow con"gurations, the
inlet concentrations of silica and sodium are adjusted to
the inlet #ow rates.
The characteristics of both #ows are given in Table 2.
5.1.2. Passive tracer validation
In order to validate the CFD and the Monte-Carlo
calculations, simulation results for #ow con"guration
1 are compared with experimental data. These data are
provided from Guiraud, Bertrand, and Costes (1991),
who characterised turbulent #uid #ow by laser Doppler
2450 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457

Fig. 2. (a) Mean axial velocity on the axis. (b) Kinetic turbulent energy. Points: experiments (Guiraud et al., 1991). Lines: CFD.

Fig. 3. (a) Mean concentration on the axis. (b) R.m.s. concentration. Points: experiments (Guiraud et al., 1991).

velocimetry and turbulent mixing of a passive tracer by

laser-induced #uorescence. Fig. 2a and b, present the
CFD simulations and measurements for the mean velo-
city and the turbulent kinetic energy on the tube axis.
Fig. 3a and b compare the mean concentration pro"le
and the root mean square (r.m.s.) concentration on the
axis. Fig. 4. Stream velocity function in the coaxial mixing jet reactor. Upper
The agreement for the mean velocity and concentra- part: #ow con"guration 1. Lower part: #ow con"guration 2.
tion pro"les is good, but there are some discrepancies for
the turbulent velocity. This may be explained by the fact
that the k}
model used for this simulation is not well value of the Craya-Curtet number, a recirculation loop
adapted to describe non-isotropic #ow occurring in the appears in #ow con"guration 1 which does not exist in
tubular jet mixer. However, the agreement for the turbu- #ow con"guration 2. The in#uence of the loop (backmix-
lent concentration pro"les is quite acceptable. ing) on mixing performance can be shown by calculating
the radial mixture fraction f of a passive tracer:
5.1.3. Mixing performance
The obtained stream function "elds for both #ow con- "Cr dr
f"  . (18)
"gurations are illustrated in Fig. 4. In agreement with the "r dr

 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457 2451

1997). A silica sol (Ludox HS30 manufactured by Du

Pont, containing monodisperse, stable, 12 nm in dia-
meter, silica particles) was destabilised by adding a given
quantity of sodium ions. The evolution of the particle size
distribution against time showed that the silica particles
aggregation proceeds, for mean number sizes smaller
than 250 nm, in a perikinetic aggregation stage, whose
rate depends on physico-chemical parameters only. For
larger sizes, the aggregation proceeds in an orthokinetic
aggregation stage, whose conditions depend then on the
local turbulence level also. The evolution of the "rst
seven moments (expressed in the length coordinate sys-
tem) during the perikinetic aggregation stage can be
Fig. 5. Dimensionless mixture fraction > as a function of axial position.
described by the general relation


dm j!3
H"  m m for 0)j)6,
dt 3   H
By choosing the following inlet concentration (C "1

and C "0) for both con"gurations, the calculated and

values of the mixture fraction are:
m
E at z"0 (inlet): f "f "0.04, ¸ "  )250 nm (20)
   m
E at in"nite length f (complete mixing): f " 
  with  depending only on physico-chemical parameters:
0.4, f "0.14, 



in order to compare both con"gurations, a dimensionless 9387
 "1.88;10 exp 8.466;10\[Na>]! , (21)
mixture fraction is used:  ¹
where  is in s\, [Na>] in mol m\ and ¹ in Kelvin.
( f!f )
 . 
>" (19)
( f !f )
  5.2.2. PDF modelling of silica aggregation
The longitudinal evolution of the dimensionless mixture From the above relations, the moment's kinetics ex-
fraction for the two con"gurations is drawn in Fig. 5. The pression becomes, in length coordinates:
mixing performances are very similar in both cases from


j!3
the inlet to about 3 cm. For greater axial positions, the S H"  m m (22)
K 3   H
macromixing performance is signi"cantly higher for con-
"guration 1. More precisely, complete mixing is reached with  depending on temperature and on sodium con-

when the axial position exceeds about 10 cm while for centration.
con"guration 2 the maximal value of > is about 0.9 at the Since no chemical reaction occurs, the silica and
outlet of the reactor. In conclusion, the back-mixing sodium concentration pro"les depend only on mixing.
occurring in con"guration 1 strongly enhances the mac- Silica aggregation is calculated in the same geometry as
romixing performance. presented in Section 5.1. For both #ow con"gurations,
silica particles are fed into the inner tube, and sodium
5.2. Application to silica aggregation ions introduced into the annular space. The sodium and
silica inlet concentrations are identical (6 M) for #ow
The in#uence of macro- and micromixing on nuclea- con"guration 1, and the molar #ow rates have been
tion and particle growth has been identi"ed by several conserved for both con"gurations ; the sodium and silica
researchers. Because of complexity, the study of the com- concentrations for #ow con"guration 2 are then (accord-
plete precipitation process undergoing nucleation, ing to the velocity values, see Table 2) respectively, 3 and
growth and agglomeration cannot be presented here. 12 M. The inlet length coordinate moments are those of
Therefore, for illustration of the PDF method, we choose a monodisperse, 12 nm in diameter (¸ "12 nm), par-

to focus on aggregation (i.e. in the absence of super- ticles solution:
saturation) alone. The studied aggregating system is sil-
[SiO ]
ica. m"  (¸ )H\, (23)
H
 
T N
5.2.1. Kinetic modeling of silica particles aggregation where [SiO ] is the silica weight concentration.

The aggregation kinetics of precipitated silica particles If the local concentration of sodium is null, almost no
have been studied in a batch laboratory vessel (Schaer, aggregation takes place (for [Na>]"0 and
2452 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457

Fig. 6. (a) [Na>] "eld for #ow con"guration 1 ([Na>] values in mol m\). (b) m "eld for #ow con"guration 1 (m values in m m\). (c) [Na>] "eld
 
for #ow con"guration 2 ([Na>] values in mol m\). (d) m "eld for #ow con"guration 2 (m values in m m\).
 

¹"298.15 K,  "4;10\ s\). Similarly, in the ab- 5.3. Results


sence of particle (m &0) no aggregate can be formed,

irrespective of the value of  . The aggregation kernel 5.3.1. Mixing process

and the particle size distribution depend then upon mix- Fig. 6a and b present the [Na>] and m "elds for #ow

ing of the two #uids. con"guration 1 (same inlet concentrations of 6 M). The
The average number particle size and the distribution vertical axis corresponds to the [Na>] or m concentra-

variance are respectively given by tions, the x-axis to the radial distance (from !0.05 to
0.05 m) which has been expanded for visual convenience,


m m m and the y-axis corresponds to the longitudinal coordi-
¸ " ,  "   !1 . (24)
 m * m nate (from 0 to 0.2 m).
 
The "elds of these two non-reacting quantities (since
From Eq. (24), it can be noticed that the particle's size the third moment is conserved during aggregation) trans-
distribution characteristics are de"ned by the "rst four late the mixing conditions of the two inlet #uids. For
moments, and that the calculation of the fourth to sixth z"0 (initial axial position), [Na>] is null in the inner
distribution moments is useless. Therefore, the illustra- tube and of course maximum in the annular space. It
ting results concern the "rst four moment's "elds at any decreases slowly as it mixes with the inner #ow. On the
point of the #ow. contrary, m is maximum in the central injection tube

 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457 2453

and reaches, after complete mixing, a "nal value of about

m /2 (since the feed #ow rates are quasi-identical for this

con"guration). One can remark that mixing of the two
#uids is almost complete for z (or axial position) between
0.05 and 0.1, which con"rms previous observations from
Fig. 5.
The [Na>] and m "elds for #ow con"guration 2 are

presented in Fig. 6c and d. As for #ow con"guration 1,
[Na>] is maximum at the annular space outlet, whereas
m is maximum at the inner tube outlet. The concentra-

tion values decrease as the two #uids are mixed together.
The "nal values are not the same as for #ow con"gura-
tion 1, since the concentrations and the volumetric #ow
rates have been changed. After complete mixing, the "nal
value of [Na>] is 2.57 M (it is 3 M at the annular space
entrance) and the "nal value of m is 0.087 (it is 0.61 at

the inner tube entrance). According to previous investiga-
tions on mixing performances (see Fig. 5), we observe
that mixing is not completed until the end of the reactor.
Comparing the two #ow con"gurations, the macro-
mixing performance is higher for #ow con"guration 1.
The back-mixing occurring in con"guration 1 (and which
does not exist in #ow con"guration 2) enhances here the
macromixing performance. Full PDF method coupled
with CFD simulation allows to give a complete descrip-
tion of concentration "elds. It is a tractable tool for the
investigation of complex reactive #ows.

5.3.2. Aggregation rate

Owing to the PDF method, it is possible to visualise
the aggregation rate "eld and to better understand where
the formation of aggregates takes place. The S   "elds
K
(where S  "! m m is proportional to aggregation
K   
rate) for both con"gurations are presented in Fig. 7a and
b. One can "rst notice a sharp di!erence between the two
#ow con"gurations. It seems that for #ow con"guration
1, aggregation proceeds in a very localised area near the
#ows inlet, where the #uids are mixed together, whereas
for #ow con"guration 2, aggregation proceeds all along
the axial axis.
More precisely, the S   term depends on both the
K
sodium and silica concentrations: it is maximum where
the two #uids meet and decreases when dilution or ag-
gregation occurs. As the reactants concentrations are
di!erent in both con"gurations, we do not compare the
absolute values of S   but their relative axial evolutions.
K
In #ow con"guration 1, the aggregation rate is radially
rather homogeneous for axial position larger than
0.04 m, and decreases along the axial axis. For axial
position smaller than 0.1 m, aggregation remains near
the maximum value (5;10 no m\ s\), irrespective of
the radial position. At the end of the reactor, the values
have fallen down to less than 1;10 no m\ s\ which
may then have little in#uence on the particle size distri-
bution. On the contrary, for #ow con"guration 2, for
axial positions smaller than 0.05 m, the aggregation rate
Fig. 7. S   "eld for (a) #ow con"guration 1; (b) #ow con"guration
K
2 (S   values in no m\ s\).
K
is radially not homogeneous. The values are almost
axially constant, near the maximum, up to the end of the
reactor. As the values of the zeroth-order moment are
still relatively high, aggregation processes may then con-
tinue after the reactor outlet.
Once again, the recirculation loop characteristic of
#ow con"guration 1 enhances the macromixing perfor-
mance, which leads to a more homogeneous aggregation
rate in the device. Aggregation conditions are here better
controlled, more particularly at the beginning of the
process, where the contact of the two #uids takes place.
In practice, this should lead to highly reproducible "nal
product properties.
5.3.3. Number of particles
As the variations of the number of particles in the
reactor are rather large (more than several decades), the
m "elds for both con"gurations (since m is the total
 
number of particles per unit of volume) are presented in
logarithmic scale in Fig. 8a and b.
2454 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457
Fig. 8. m "eld for (a) #ow con"guration 1; (b) #ow con"guration 2 (m
 
values in no m\).
For #ow con"guration 1, the m "eld is homogeneous

along the radial axis and decreases for axial positions
greater than 0.1 m, when aggregation proceeds. The total
number of particles varies from about 1;10 no m\
near the inlet to less than 1;10 no m\ at the outlet of
the reactor. The "nal particle concentration is then about
1000 times smaller than at the inlet.
The longitudinal evolution of the number of particles
illustrates two characteristic behaviours of the process.
From 0 to 0.15 m, m is almost constant since aggrega-
 
tion e!ects are very low because they are delayed by the
mixing step. Beyond this macromixing length, corre-
sponding to the length necessary for complete Na> con-
centration homogenisation (see Fig. 6a), the aggregate
sizes increase drastically. However, because of the mi-
cromixing limiting step, the global aggregation process
does not proceed as fast as in perfect mixing conditions.
The small #uctuations in the m values which can be

detected are due to the stochastic calculation method.
These variations may be avoided by using more notional
particles which would drastically increase the calculation
time.
For #ow con"guration 2, there are almost no particles
near the annular tube inlet. As there is no recirculation
loop, the particles coming from the inner tube cannot
reach this part of the device, which then is not used for
aggregation. For axial position smaller than 0.05 m,
the m "eld is not homogeneous in the radial direction.

The number of particles then slightly decreases along
the axial axis (the "nal m value is around

2.5;10 no m\), but remains near its initial value
(3.5;10 no m\). The total number of particles is here
divided by a factor of 14 which is twice the value of the
dilution factor by mixing of the inlet #ows (see Section
5.3). Compared to the high reduction values obtained in
con"guration 1, almost no aggregation proceeds in this
con"guration.
The "rst and second moments "elds for both con"g-
urations, not presented here, evolve like the zeroth mo-
ment.
5.3.4. Particle size and distribution variance
The mean number size ¸ and the variance  of the
 *
particle size distribution can be calculated for both the
#ow con"gurations according to relations 24. We have
seen, in the previous section, that stochastic Monte-Carlo
methods lead to some #uctuations in the moment "elds.
In the simulation presented in this study, the mean num-
ber size and the variance of the PSD "elds, calculated
from the moments ratio, present then higher #uctuations
which may have no physical sense. To increase the accu-
racy of the method, calculations with larger notional
particles number should be carried out. For this example,
we have plotted longitudinal evolution of ¸ or  ,
 *
calculated as the average radial values, instead of
3D maps.
Figs. 9 and 10 present the mean radial values of mean
number size ¸ and of variance  along the axis for
 *
both #ow con"gurations.
For #ow con"guration 2, there is almost no aggrega-
tion along the reactor: the mean number particle size
does not vary against the axial position. As aggregation
is not e!ective, the particle size distribution remains
monodispersed all along the device.
For #ow con"guration 1, the large variations of
¸ and  between 0.12 and 0.2 m illustrate the numer-
*
ical dispersion of the moments values. Nevertheless,
evolution of the particle size and variance against axial
position illustrates once again the two characteristic be-
haviours of the process. From 0 to almost 0.15 m, the
particle sizes remain near their initial value (12;10\ m)
and the distribution is almost monodispersed since ag-
gregation is not e!ective (aggregation e!ects are very low
because they are delayed by the mixing step, see Fig. 6a).
Beyond this length (for axial position '0.15 m), the
particle sizes increase linearly as the particles aggregate.
 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457
Fig. 9. Average radial values of the mean number size ¸ against axial position: (a) #ow con"guration 1; (b) #ow con"guration 2.

Fig. 10. Average radial values of the variance  against axial position: (a) #ow con"guration 1; (b) #ow con"guration 2.
*
The formation of larger particles induces a distribution
broadening. However, because of the micromixing limit-
ing step, the size variation does not proceed as fast as in
perfect mixing conditions.
6. Conclusion
The PDF method coupled with CFD description of
the #ow is an e!ective tool for studying turbulent reactive
#ows, involving complex kinetics as in precipitation pro-
cesses. All scales of mixing, including macro- and mi-
cromixing may be included, which are of primary
importance for mixing sensitive reactions. Furthermore,
the complex kinetics may be treated exactly without any
assumption. The method is well adapted to localise speci-
"c rate processes, such as nucleation, growth and ag-
gregation in complex #ows and to handle the calculation
of the particle size distribution expressed in moments.
The illustration of silica aggregation showed that mixing
may drastically a!ect the aggregation process and that
all coupled phenomena must be considered to describe
properly fast reaction processes. The stochastic calcu-
lation procedure used for the PDF method may, how-
ever, lead to some #uctuations in PSD moments, which
can be a di$culty for accurate estimation of mean num-
2455
ber size ¸ and of the variance  . To reduce the
 *
statistical noise level, more notional particles per com-
putational cell could be employed, at the cost of higher
computational time. As the power of computers is con-
tinuously increasing, complex and "ne-scale calculations
now possible on large supercomputer, will be e!ective in
a few years on PC.
The presented method based on the uncoupling of
#ow "eld and reaction calculation, is only supportable
for dilute systems. However, for more concentrated
systems, PDF methods remain applicable, but back-
action of the particle dynamics/reaction chemistry on the
parameters describing the continuous phase #ow has to
be done.
Notation
A model constant in nucleation kinetic
a mean ionic activity, mol m\
!
B nucleation rate, no m\ s\
B model constant in nucleation kinetic,
no m\ s\
B(v) birth rate function, expressed as a function
of particle volume, no m\ s\
C vector of species concentrations
2456 L. Falk, E. Schaer / Chemical Engineering Science 56 (2001) 2445}2457

C ,C concentration of cation, anion, mol m\ Greek letters

> \
C concentration of species j, mol m\
H
C Craya-Curtet number, dimensionless  size-independent factor, s\
R 
D, d diameters, m (u, v) aggregation kernel, expressed as a function
D molecular di!usion, m s\ of particle volume, m s\
A
D turbulent di!usion coe$cient
surface tension of the particles, J m\
R
(" /Sc ), m s\
stoichiometric mean activity coe$cient ex-
R  !
D(v) death rate function, expressed as a function pressed in molarities
of particle volume, no m\ s\
turbulent energy dissipation, W kg\
f mixture fraction, mol m\
surface shape factor
?
f multidimensional probability density func-
volumetric shape factor
A T
tion  jth moment of the number volume distri-
H
G volumetric growth rate, m s\ bution, no mH\
k turbulent kinetic energy, kg m\ s\  turbulent viscosity ("0.09k/
),
R
k growth rate constant, m s\ kg m\ s\
E
K thermodynamic solubility product,
"
#
number of ions into which a molecule dis-
QN > \
mol m\ sociates
¸H critical size of the nucleated particles, m  density of continuous phase, kg m\
¸ average number particle size, m  density of the particles, kg m\
J N
m jth moment of the number length distribu-  variance of the number size distribution
H *
tion, no mH\  variance of the number volume distribu-
T
M molecular weight of the particles, tion
N
kg mol\
n(v) number population density function, ex- Superscripts
pressed as a function of particle volume,
no m\ 0 initial
N Avogadro number ("6.02;10
no mol\)
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