CRYSTALLIZATION AND

PRECIPITATION ENGINEERING
Alan Jones, Rudi Zauner and Stelios Rigopoulos
Department of Chemical Engineering
University College London, UK
www.chemeng.ucl.ac.uk
Acknowledgements to: Mohsen Al-Rashed, Andreas
Schreiner and Terry Kougoulos; EPSRC, EU and GSK
Outline of talk
! Introduction to crystals and crystallization
! The ideal well-mixed crystallizer
! Prediction of Crystal Size Distribution
! Mixing effects in real crystallizers
! Precipitation processes
! Crystallization processes
! Scale up
! Scale out
! Conclusions
Crystallization Processes
! Crystallization is a core technology of
many sectors in the chemical process
and allied industries
! Involves a variety of business sectors, e.g.
Agrochemicals, catalysts, dyes/pigments,
electronics, food/confectionery, health products, nano-materials,
nuclear fuel, personal products & pharmaceuticals
! Processes can involve complex process chemistry together with
non-ideal reactor hydrodynamics
Hence can be difficult to understand and scale-up from laboratory
to production scale operation
! Crystallization also forms part of a wider process system
Crystallization Process Systems
Convey

Feed
Recycle
Liquor
to recycle
Liquor to recycle
Hot air
Water
Clean air
Liquor to recycle
PRODUCT CRYSTALS
Mix, convey, etc.
Slurry
Mill
oversize
Screen
Jones, A.G. Crystallization Process Systems, Butterworth-Heinemann, 2002
CRYSTAL CHARACTERISTICS
Crystals appear in many:
!sizes,
!shapes and
!forms,
Which affect both:
!performance during processing, and
!quality in application
Phase Equilibria
Understanding phase equilibria is
crucial to crystallizer operation
! Undersaturated - crystals will
dissolve
! Metastable - crystals will grow
! Labile - solution will nucleate
spontaneously
Solubility-supersolubility diagram
Supersaturation
!Thermodynamically, solute in excess of solubility
RT
ation Supersatur
! "
#
where ! = chemical potential
!For practical use
* c c c $ # "
* / c c S #
or
where c = concentration of solution
c* = saturation concentration
Supersaturation, "c, is sometimes called the concentration driving force
Crystallization Kinetics
!Nucleation rate - rate of formation of new crystals
where b = 'order of nucleation
B = nucleation rate rate of increase of crystal number
!Crystal growth rate of increase of crystal dimension
where g = 'order of growth
G = growth rate rate rate of increase in crystal size
nuclei/s m
3
m/s
b
n
c k B
dt
dN
" # #
g
g
c k G
dt
dL
" # #
Corresponding expressions exist for crystal agglomeration and breakage.
Thus particle formation processes all depend upon supersaturation
The Well-mixed Crystallizer


















IN
OUT
Precipitation reactions
! Reactants flow into vessel
and form a reaction zone
! Particles form from reacting
species via crystallisation
! Process kinetics can be
dominated by mixing process
! Can get undesired
product forms, e.g. solvates
from solvent drown out
Note: For batch operation:
Outflow of product is zero
Hydrodynamic ratio (W/D) varies as function of fill during reaction
Reactant mixing & hence precipitation kinetics require optimisation
Designing for Crystal Size Distribution
(CSD)
! Key goal: Characterise
inter-relationship between
reactor residence time
process kinetics
product CSD
! Understand relationship as
function of reactor scale size
! Design reactors and process
operating conditions to yield
desired CSD
Kinetics
Residence Time
CSD
The Crystallization Triangle
Conservation Equations
Mass balance
! "concentration (inlet - outlet) %Mass Yield
! Only gives crystal yield not how mass distributed
in crystal size the CSD
! Need crystal number balance population balance
Population balance
! Accounts for number of crystals formed & their size
! Hence CSD & mean particle size can be predicted
! Incorporates terms for crystal nucleation, growth,
agglomeration & breakage
Population Balance Model (PBM)
! PBM (Randolph & Larson 1962) provides population of crystals as
described by number density function n(L,t)
L - crystal size and t - time
Represents probability to have crystals with size L at moment t
! Numerical solution of PBE produces Crystal Size Distribution (CSD)
0 d d a a
o
B D B D B
n n
L
) nG (
t
n
& $ & $ #
$
& &
' (
(
(
(
! G - growth rate
! B & D - Birth & Death functions for agglomeration & breakage
! B
0
- nucleation rate
! ' - residence time (for continuous crystallisation)
! Indices a, d & 0 relate to agglomeration, breakage & nucleation
A partial integro-differential equation solved by numerical methods eg finite element. For non
well-mixed systems need to include velocity derivatives in addition to crystal growth rate.
Problems with Reactive Precipitation
! Spatial variation in reactant concentration & crystallizer
performance thus sensitive to
mixing conditions
processing scale size
! For fast supersaturation rises and large vessel sizes
this gives variability in particle formation rates
! Scale-dependant fluid mechanics also effect process
kinetics through its impact on secondary nucleation
! Mixing effects tends to be particularly pronounced
for fast precipitation systems (Danckwerts, 1958)
Danckwerts, P. V., 1958. The effect of incomplete mixing on homogeneous reactions. Chemical Engineering Science., 8, 93-99.
Computational Fluid Dynamics
Why use CFD?
! To investigate localised mixing effects and fluid
hydrodynamics
1. Local velocities
2. Local energy dissipation ()
loc
)
3. Solid volume fraction
*
4. Heat transfer and temperature profile
*
! For the development of crystallizer
compartmental modelling framework
! To facilitate modelling, scale-up and design
* Kougoulos et al., Scale-Up of Organic Crystallization Processes. In AIChE National Meeting, Recent Developments.
In Crystallization and Evaporation. San Francisco, CA, USA, 16-21 November 2003, (New York: AIChE), Paper 310B
Agitated Vessel Mixing

! Real agitated
vessels are not well-
mixed except at small
volumes and/or high
power inputs, which
may cause particle
disruption
! Uniformity of mixing
decreases as vessel
size increases
!Numerical solution
of the Navier-Stokes
Equations
Some CFD and Precipitation Studies
!Seckler et al. 1993 Precipitation of calcium phosphate
in a 2-D CFD jet mixer
!Van Leeuwen et al. 1996 Zonal CFD model of BaSO
4
precipitation
!Wei and Garside 1997 Precipitation of BaSO
4
in stirred
tanks
!Al-Rashed & Jones 1999 CFD modelling of gas-liquid
precipitation
!Bezzo et al. 2000 Integration of CFD and process
simulation
!Baldyga and Orciuch, 2001 PDF CFD methods
!Zauner and Jones 2002 CFD-Segregated Feed Model
!Rigopoulos & Jones 2003 CFD-Reaction engineering model
Mixing Effects in Gas-liquid Precipitation
0.0E+0
2.0E-9
4.0E-9
6.0E-9
8.0E-9
1.0E-8
1.2E-8
1.4E-8
0 1 2 3 4 5 6
Ti me / (s)
C
r
y
s
t
a
l

M
e
a
n

S
i
z
e

/

(
m
)
CFD
Penetrat ion
Film
CFD + PBM simulations in
qualitative agreement with
experiment but v. slow *
compartmentalisation
Al-Rashed, M.H. and A.G. Jones. "CFD modelling of gas-liquid reactive precipitation". Chem Engng Sci., 54 (1999), 4779-4784
Precipitated Calcium Carbonate Crystals
Note presence of agglomerates and fines attrition?
Mixing Effects: Segregated Feed Model
!Villermauxs (1989) Segregated Feed Model (SFM)
based on physically meaningful mixing parameters
involving
diffusive micro-mixing time
convective meso-mixing time
!SFM particularly suitable for modelling mixing
effects, as it combines advantages of both
compartmental model
physical model
Segregated Feed Model (SFM)
Q
f1
Q
f2

u
1,2

u
1,3
u
2,3

Q
b


reaction
plume f
1


reaction
plume f
2




bulk b
SFM divides reactor into three
zones:
two feed zones f
1
and f
2
bulk b
Feed zones exchange mass
with each other & with bulk
Process depicted by flow rates
u
1,2
, u
1,3
and u
2,3
respectively
According to time constants
characteristic for micro-mixing
& meso-mixing
Characteristic Mixing Times
Meso-mixing bulk blending
Micro-mixing molecular diffusion
Based on time constants (Baldega et al 1995)
Time constants t
micro
& t
meso
can be regarded as
inverse coefficients for mass transfer by diffusion &
convention, respectively
Energy dissipation rate (!) predictable from CFD
2 / 1
3 . 17
+
+
,
-
.
.
/
0
1 #
loc
micro
t
)
2
s
loc
avg
meso
d N
Q
A t
3
4
3
1
)
)
#
Precipitation Process: Scale-up Methodology
Hydrodynamic
model (CFD)
Population balance
Mixing model
(Segregated Feed
Model SFM)
Laboratory-scale
experiments

Large-scale
reactor
! Carry out laboratory scale
measurements (kinetics etc)
! Model hydrodynamics
via computational
fluid dynamics (CFD)
! Use population balance
model for particle
properties (number/CSD)
! Link two models via
segmented feed model (SFM)
! Predict precipitation
performance as
function of scale size
Process Scale-up: Semi-batch Precipitation
!In contrast at
high values of
energy input
breakage acts
as size-reducing
process
!This leads to
smaller particles
1E-3 0.01 0.1 1 10
5
10
15
20
25
30
1 l reactor, exp.
5 l reactor, exp.
25 l reactor, exp.
1 l reactor, model
5 l reactor, model
25 l reactor, model
L
4
3

[
!
m
]
Specific power input ) [W/kg]
! Note small
particle sizes at
low energy
inputs
! Results from
local zones with
high levels of
supersaturation
& nucleation
Calcium Oxalate Precipitation: Particle Size vs Power Input
Zauner, Rudolf and Alan G. Jones. "Scale-up of continuous and semi-batch precipitation processes." Ind Engng Chem Res, 39, (2000). 2392-2403.
Precipitation in Bubble Columns
!The formation of a solid product via a gas-liquid
reaction
!Common applications: inorganic salts (e.g. CaCO
3
,
CaSO
4
), fine chemicals
!Apart from yield, the Particle Size Distribution (PSD)
of the product is very important
Conventional Approaches to Bubble
Column Modelling and Scale-up
! Experimental approach - use of empirical
correlations
Limited validity of correlations, often lead to
contradictory conclusions
! Hydrodynamic approach - entirely based on CFD
Not yet possible to couple with the non-linear
dynamics of fast reactions and crystallisation
mechanisms that occur at the gas-liquid
interface
A Trade-off: Hybrid CFD - Dynamic
Reaction Engineering Model
Hydrodynamic
scale
(mesoscopic)
C
x
Interfacial
scale
(microscopic)
Bulk scale
(macroscopic)
Model Assumptions
! Isothermal operation
! Only primary processes of particle formation (i.e. no
secondary processes that involve particle-particle
interactions such as agglomeration)
! Dilute suspension, i.e. negligible influence of solids
presence on hydrodynamics
! Homogeneous bubbly flow, i.e. no bubble coalescence
CFD Modelling of Gas-liquid Flow in
a Bubble Column
! Captures the gross
hydrodynamic effects
that determine the
overall long-time-
average gas hold-up and
liquid circulation
! Eulerian-Eulerian two-
dimensional dynamic
model considered
adequate for that
purpose
! Use of CFX flow solver
0
2
4
6
8
10
0 2 4 6 8 10
gas flowrate, m
3
/s (x10
-4
)
g
a
s

h
o
l
d
-
u
p

i
n

r
i
s
e
r
,

%
riser, model
riser, experiment
downcomer, model
downcomer, experiment

CFD and experimental gas hold-up
Rigopoulos, Stelios and Alan G. Jones. "A hybrid CFD - reaction engineering framework for multiphase reactor
modelling: Basic concept and application to bubble column reactors". Chem. Eng. Sci., 58, (2003), 3077-3089.
Case Study: CaCO3 Precipitation via
CO2 Absorption in Ca(OH)2 Solution
Equilibrium concentrations
0
0.2
0.4
0.6
0.8
1
3 5 7 9 11 13
pH
m
o
l

f
r
a
c
t
i
o
nCO3
HCO3
CO2
CO
2 (g)
%CO
2(aq)
absorption
CO
2(aq)
+ OH
-
3HCO
3
-
sub-reaction i
HCO
3
-
+ OH
-
3CO
3
=
+ H
2
O sub-reaction ii
Ca
++
+ CO
3
=
%CaCO
3(s)
crystal formation
Time Course of Concentration Profiles
7
8
9
10
11
12
13
0 20 40 60
time (min)
p
H
0
5
10
15
20
25
30
0 20 40 60
time (min)
c
o
n
c
e
n
t
r
a
t
i
o
n

(
m
o
l
/
m
3
)
CO2
CO3
HCO3
Evolution of Supersaturation
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 2 4 6 8 10
time (min)
c
o
n
c
e
n
t
r
a
t
i
o
n

(
g
m
o
l
/
m
3
)
CO3= gmol/m3
Ca++ gmol/m3
Supersaturation
Evolution of Nucleation Rate
10
1000
100000
1E+07
1E+09
1E+11
1E+13
1E+15
0 2 4 6 8 10
time (min)
l
o
g

n
u
c
l
e
a
t
i
o
n

r
a
t
e

(
n
u
c
l
e
i
/
s
e
c
)
Experimental Results and Model Predictions
Agglomerate
6
7
8
9
10
11
12
13
0 2 4 6 8 10
time (min)
p
H
0.0E+00
2.0E-07
4.0E-07
6.0E-07
8.0E-07
1.0E-06
1.2E-06
1.4E-06
P
a
r
t
i
c
l
e

s
i
z
e

(
m
)
pH (model) pH (exper.)
Size (model) Size (exper.)
Reasonable agreement up to the onset of agglomeration
SEM Micrographs of Calcium
Carbonate Crystal Agglomerates:
Effect of Crystal Agglomeration
21 litres Ca(OH)
2
= 3 mol/m
3
; 0.00001 : 0.0001 m
3
/s CO
2
: N
2
Current Work
!Compartmental model of
batch cooling crystallization
at high solids
content
Batch Cooling Crystallization
Pre-processing
!CFX-Promixus
!Multiple Frames of Reference
Simulations
!Multi-Fluid Model (MFM)
!Modified Drag coefficient
(Brucato, 1998)
!Monodisperse particle sizes
!Standard k-) turbulence model
!Heat transfer (estimated liquid
side heat transfer coefficient)
Computational Fluid Dynamics at
High(er) Solids Content
CFD clips of [1] velocity profile development and [2] particle concentration
[1] Shows flow dampening [2] Shows solids segregation
Illustration based on 5L batch cooling crystallizer operating at 300 rpm 200 !m 5 v/v% (7 % w/w)
Compartmental Model Flow (Rushton turbine)
[2]
3
6
7
2
1
4
5
8
9
[1]
[1] Shows overall flow pattern on different horizontal planes
[2] Overall flow pattern on vertical scale 45
o
angle to baffles
Compartmental Model Heat (Rushton turbine)
1. Heat transfer coefficient
2. Simulate linear cooling profile
(353K to 293K at -1
o
C min
-1
)
3. Cooling zones evident
4. Cooling profile influences
temperature gradients
c b a
Pr Re C
k
hd
Nu ! # #
C
o
o
l
i
n
g

Z
o
n
e
C
o
o
l
i
n
g

Z
o
n
e
Uniform Bulk
Temperature
Temperature profile after 360s simulation
Compartmental Model Slurry (Rushton turbine)
1
2
3
4
5 6
7
8
9
Q
1,2
Q
2,3
Q
3,4
Q
3,7
Q
3,9
Q
7,8
Q
8,9
Q
9,1
Q
4,5
Q
5,6
Q
4,2
Q
6,1
Q
9,2
Q
5,1
Q
5,2
Network of Zones
Network of Zones
Green: Bulk Zone
Orange: Cooling Zone
Blue: Impeller Zone
Red: High Solids Content Zone
Based on CFD modelling at different crystallizer scales using a Rushton impeller
Process Modelling
!gPROMS (Process Systems Enterprise Limited)
1. Dynamic Simulations
2. Compartmental facility available
3. Batch crystallization process can be simulated
4. Optimisation can be carried out
5. Population balance with crystallization kinetics
!New technology
1. CFD (Fluent) and gPROMS interface
2. Simultaneous CFD simulation & modelling in gPROMS
Simulations
!Initial boundary conditions
1. Seed distribution
2. Supersaturation
3. Temperature
!Define time steps for batch process
!Define parameters, variables & algebraic expressions
!Population, mass and energy balances are ODEs
Experimental CSD
Theoretical CSD
Prediction
0
1
2
3
4
5
6
0 50 100 150 200 250 300
Crystal Size, (!m)
M
a
s
s

d
i
s
t
r
i
b
u
t
i
o
n
(
%

w
/
w
)
A better way..?
Scale out, rather than up
Segmented Flow Tubular Reactor
(SFTR). After Lematre et al.
Reagents are mixed and
formed into well-mixed
mini crystallizer droplets
within a segmenting
fluid, which are
subsequently separated
Donnet, M., P. Bowen, N.Jongen, J. Lematre, H. Hofmann, A. Schreiner, A.G. Jones, R. Schenk, C. Hofmann and S. De Carlo. Successful scale-up from
millilitre batch optimisation to a small scale continuous production using the Segmented Flow Tubular Reactor. Example of calcium carbonate precipitation.
In Industrial Crystallization, 15-18 September 2002, Sorrento, Italy. Chemical Engineering Transactions, 3, (2002), 1353-1358.
Interdigital Micro Mixer.
(After Schenck et al. )
Schenk, R., M. Donnet, V. Hessel, H. Hofmann, N. Jongen and H.Lwe, 2001. Suitability of various
types of micromixers for the forced precipitation of calcium carbonate, In 5th International Conference
on Microreaction Technology (IMRET 5), Strasbourg, France 27-30 May 2001.
Predicted Mean Particle Sizes of
Calcium Carbonate
0
1
2
3
4
5
6
7
0.001 0.01 0.1 1
initial concentration [mol/l]
m
e
a
n

s
i
z
e

d
1
,
0

[
!
m
]
m (seeds) = 0 mg / L
m (seeds) = 0.1 mg / L
m (seeds) = 7.5 mg / L
m (seeds) = 10 mg / L
Schreiner, A. and A. G. Jones. Precipitation in the Segmented Flow Tubular Reactor (SFTR). In Industrial
Crystallization, 15-18 September 2002, Sorrento, Italy. Chemical Engineering Transactions, 3, (2002), 1245-1250.
Crystals From the SFTR
a). Vaterite b). Y-Ba oxalate.
(Courtesy www.bubbletube.com)
Conclusions
! New computational techniques for the analysis and design of
systems for the manufacture of particulate crystals have become
available
! The more complex precipitation processes whereby
crystallization follows fast chemical reactions have also been
analysed more deeply
! This progress has been aided by the growing power of the
population balance and kinetic models, CFD and mixing theory,
respectively
! Further progress may reasonably be expected in the
development of computer models, software and hardware
! Alternative techniques are under development to avoid mixing
problems and obtain efficient processes and high quality
products