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Separation and Purification Technology 48 (2006) 159–166

Dynamic modelling optimisation and control of lactose crystallisations:


Comparison of process alternatives
T.T.L. Vu a,∗ , R.J. Durham a , J.A. Hourigan a , R.W. Sleigh b
a Food Research Group, CPAFS, University of Western Sydney, Locked Bag 1797, Penrith South DC, NSW 1797, Australia
b Food Science Australia, Sydney, NSW 2113, Australia

Abstract

A general technique is derived to formulate and solve the dynamic optimisation problems for crystallisation, in order to re-evaluate the
growth rate correlations and search for the optimal cooling and heating strategies (evaporative mode only). The dynamic model of a process
making ␣-lactose monohydrate is first revised for these operations using seed crystals: batch cooling, semi-batch cooling and heating, and
continuous cooling. Experiments are conducted in 2 and 20 L crystallisers under various seeding, cooling and heating strategies to evaluate
the constants in the power law function, which correlates the growth rate of the particles with supersaturation. Using a nonlinear least square
method, the best curve fitting of experimental data to the model yields G = 0.007T(100(x␣ /xw ) − sol␣ )2.7 . The value of n = 2.7, which is
applicable to all operations investigated in the study. The value of k however, must be estimated for selected seeding and cooling strategies,
and most importantly for the type of syrup fed to the crystalliser. Using k = 0.007 in simulations and experiments of jet-milled seeds at 1.5%
seeding ratio, the experimental results agreed well with predictions before the growth became slow. A semi-batch is slightly faster than a batch
process and evaporative semi-batch is much faster than cooling operation but is more difficult to control. The performance of a cooling and
seeding run in continuous mode is simulated. The system reached steady state after seven residence times but the predicted particle size could
only be stabilised after 100 h. The developed methodology can be applied to the crystallisation of many other substances but is not limited to
the food or dairy industries.
© 2005 Published by Elsevier B.V.

Keywords: Continuous performance; Cooling profile; Evaporative semi-batch; Growth rate; Cooling crystallisation; Seeding

1. Introduction ubility at the ambient temperature is low. Last but not least,
the difference between the metastable concentration and sol-
The possibility of growing pure crystals of a controlled ubility of lactose, referred to as the metastable zone, is quite
size distribution has made crystallisation one of the most large, which allows controlled cooling in seeded batch oper-
important purification and separation techniques in the food ation to minimise unwanted nucleation.
industries, particularly in the sugar and dairy industries. In 1998 the Centre for Advanced Food Research, in con-
While either evaporative vacuum batch or evaporation in con- junction with Food Science Australia developed new technol-
tinuous mode is the only technique applied to extract sugar ogy to generate pure lactose syrup from whey ultra-filtrate [1].
from cane juice, both cooling and heating can be employed This opens major new opportunities for crystallisation, since
to create supersaturation in crystallisation of lactose from for the first time crystallisation can be optimised for particle
whey permeate, a yellow waste material, which contains min- formation rather than purification as in the current indus-
eral salts and nitrogenous compounds, remaining after cheese trial practices of manufacturing ␣-lactose monohydrate. In
manufacturing. Lactose is mainly manufactured by cooling order to maximise the advantages of using high purity lactose
crystallisation of whey permeate in the dairy industry since feed for crystallisation, different operating conditions must
the lactose solubility–temperature curve is not flat and its sol- be compared, e.g., batch versus continuous modes, cooling
versus evaporation. The best seeding and cooling or heating
∗ Corresponding author. Tel.: +61 2 4570 1426; fax: +61 2 4570 1579. strategies must be selected to ensure the highest yield and
E-mail address: l.vu@uws.edu.au (T.T.L. Vu). quality of the product. To minimise the number of labora-

1383-5866/$ – see front matter © 2005 Published by Elsevier B.V.


doi:10.1016/j.seppur.2005.07.015
160 T.T.L. Vu et al. / Separation and Purification Technology 48 (2006) 159–166

[8]. A nonlinear least square method must be applied instead


Nomenclature of a single regression analysis in order to take into account
the effect of cooling temperatures.
C mass fraction (kg kg−1 ) In the following sections, the dynamic model of a cooling
F feed rate (kg h−1 ) crystalliser to produce ␣-lactose in a seeded batch is firstly
G growth rate (␮m h−1 ) defined and then modified for other operations: evaporative
M mutarotation rate (h−1 ) semi-batch and cooling in continuous mode. The method-
sol solubility (◦ Brix) ology of formulating and solving the dynamic optimisation
T temperature (◦ C) problems generated in the study is described. Cooling semi-
t time (h) batch operation is the focus of the work since it is a start-up
W total mass (kg) stage of both batch and continuous operations. Hence exper-
x mass (kg) iments are carried out in batch and semi-batch crystallisers
xd particle mean size (␮m) along with simulation results to validate the computer model,
ẋ rate change in mass (kg h−1 ) which can be used for industrial scale crystallisations. For
comparison, dynamic optimisations are also conducted for
Greek symbol an evaporative case study. Neither continuous nor evapo-
λ conversion ratio rative lactose crystallisation is commonly practiced in the
dairy industry or studied in the literature except some work
Subscripts
on continuous cooling done by Thurlby and Sitnai [9] and
c crystals of pure lactose
by Shi et al. [5]. Based on the results found for semi-batch
f feed
operation, experimental design and simulation in continuous
fin final
mode are also investigated here to compare with batch and
imp impurities
semi-batch.
lac lactose
The outcome anticipated from this study is a mathemati-
nv number of variables
cal model applicable to alternative processes, which produce
p product
uniform distribution of crystals in the highest yield.
w water
␣ dissolved ␣-lactose
␤ dissolved ␤-lactose
0 initial seed 2. Methodology

2.1. Process model

tory and pilot-plant experiments, preliminary results can be Fig. 1 shows a schematic of a batch cooling process
obtained from simulations if mathematical models describing implemented both in the laboratory and pilot plant, and a
the processes are well developed. bench-scale evaporative crystalliser. The dynamic model of
In the last quarter century many authors measured the a batch cooling process is fully described by the mass and
growth rate of ␣-lactose monohydrate in an isothermal seeded population balances. In the case of ␣-lactose monohydrate
batch or a continuous cooling crystalliser [2–5]. Recently additional differential equations are required to incorporate
Butler [6] and Lifran et al. [7] have resumed lactose kinetic the mutarotation rate (M), calculating the dynamic transfor-
studies. Based on experimental results at various tempera- mation between ␣- and ␤-lactose in water. If a batch is initially
tures, a power law function was proposed to correlate the fed with seed crystals closely sized between two adjacent
growth rate of the particles with supersaturation. Previous sieve sizes, the dynamic of the particle size distribution can be
authors have presented the growth rate in different units but ignored. The state equations become the rate change (kg h−1 )
used a similar form of power law function for lactose crystalli- in mass of water (xw ) dissolved ␣-lactose (x␣ ), ␤-lactose (x␤ ),
sation kinetics growth rate (G) = f(temperature) × (driving crystals of pure lactose (xc ) and average size of lactose par-
force)n . In this format a nonlinear function k exp(−Eg /RT) ticles (xd ).
or a linear relationship k × T can be used to incorporate the The state equations are also modified for the following
temperature. Values of the constants n, k and Eg were found cases, in which the syrup feed is pumped into the vessel at
from a single regression analysis of the experimental data and the rate F (kg h−1 ) but the differences are:
were reported differently due to their dependence on the ini-
tial weight, average mean size and particle size distribution • cooling semi-batch: heat is removed;
of the seed crystals used in the experiments. The growth rate • evaporative semi-batch: steam is supplied at the rate E
correlation, based on experimental results of an isothermal (kg h−1 ) to evaporate λE kilogram of water per hour
static crystallisation cannot predict well the performance of (1 > λ > 0);
a dynamic cooling crystallisation; therefore, it must be re- • continuous flow: seed particles are pumped in with the feed
evaluated for different seeding weight and cooling strategies while product and heat are withdrawn.
T.T.L. Vu et al. / Separation and Purification Technology 48 (2006) 159–166 161

Fig. 1. Schematics of batch cooling and evaporative crystallisers.

The state equations and their modification are shown sollac − K(0.0159 + 0.00023T 1.36 )
below. The subscript “f” denotes feed. Eqs. (1a) and (1b)
× (100((x␣ + x␤ )/xw ) − sollac )
define the rate change in mass of water in cooling and sol␣ = (9)
heating semi-batch, respectively. In these equations C with 1+K
the corresponding subscripts are the mass fractions of water, Under the conditions of no nucleation, agglomeration or
␣- and ␤-lactose in the feed. Some common symbols and breakage, in a batch or semi-batch operation, the number of
units are included in the nomenclature list.
Batch Semi-batch
dxw
Cooling ẋw = = −0.05R ẋw = −0.05R + FCwf (1a)
dt
dxw
Heating ẋw = = −0.05R ẋw = −0.05R + FCwf − λE (1b)
dt
Mx␤ Mx␤
ẋ␣ = −Mx␣ + − 0.95R ẋ␣ = −Mx␣ + − 0.95R + FC␣f (2)
K K
x␤ x␤
ẋ␤ = Mx␣ − M ẋ␤ = Mx␣ − M + FC␤f (3)
K K
3xd2 Gxc0
ẋc = R = (4)
xd30
 x␣
n
ẋd = G = kT 100 − sol␣ (5)
xw

Eqs. (4) and (5) are applied in both batch and semi-batch
cases. In Eq. (4) xc0 and xd0 are mass and average size of crystals in the crystalliser remains constant. In a continuous
initial seed particles, respectively. Two constants k and n in run, it is assumed that the number of seed particles in the
the power law function (5) will be re-evaluated in this work to feed stream and the product stream are the same but their
compare with values found in the literature. The mutarotation average sizes and total masses are different. If this condition
rate M and K used in the state equations [6], solubility of is held, at steady state the rate changes in mass of water,
lactose and ␣-lactose [10] are correlated with temperature in dissolved ␣- and ␤-lactose approach zero in a continuous
the following equations. operation. The component balances, Eqs. (1a), (2) and (3)
  can be written in the same fashion as the following water
ximp balance.
M = 9.6 + 0.01 eT/12.4 (6)
xw
0 = −0.05R + F (Cwf − Cwp ) (10)
K = 1.64 − 0.0025T (7)
Since the feed stream is seeded an additional ordinary
sollac = e2.389+0.028T (8) differential equation describing the change in the number of
162 T.T.L. Vu et al. / Separation and Purification Technology 48 (2006) 159–166

seed crystals must be included. At steady state, the change Eq. (13).
in mass of crystals and number of seeds in the vessel also 
approach zero. This implies the numbers of seeds in the feed 
i=n
OFevap = min wt t + ww [W(i) − Wfin ]2
and in the product stream are the same, but the mean size of i=1
the feed seeds and their total mass are smaller. The difference 
in solid content between the product (Ccp ) and feed (Ccf ) 
i=n

streams is shown in Eq. (11). + wCc [Cc (i) − Ccfin ] 2


(13)
i=1

xd2 G wt,w,Cc : weighing constants defined by users.


Ccp − Ccf = (11) The solutions of the first optimal control problem are used
2F
as set point profiles in the following dynamic optimisation
and experiments carried out in the laboratory and pilot plant
2.2. Problem formulation and solving methods described in Section 2.3.

2.2.1. Batch and semi-batch 2.2.1.2. Nonlinear curve fitting. The aim of the second
2.2.1.1. Set-point profile. The aim of the first dynamic opti- dynamic optimisation problem is to re-evaluate the two con-
misation problem is to search for an optimal cooling tempera- stants k and n for the cooling and heating strategies found
ture, or feed rate and evaporation rate profiles (in evaporative above. A nonlinear least square dynamic optimisation prob-
mode) using values of n and k found in the literature or in lem is formulated to fit the model equations to experimental
a single curve fitting [7]. The same technique is applied to data and solved for the constants n and k in Eq. (5). The
optimise performances of a cooling batch, cooling or evap- same constraints described above are applied. The objective
orative semi-batch. To avoid solving the ordinary differen- function can be expressed as:
tial equations (ODEs) required for each recursion, Lagrange  
interpolation polynomials are used to approximate the state   predicted
 j=fin
i=nv 2
variables x (Eqs. (1)–(5)). These approximations can be dif- OFfit = Min  xi (tj ) − ximeasured (tj ) 
ferentiated and back substituted into the ODEs, which are i=1 j=0
converted to an algebraic set. The dynamic optimisation prob- (14)
lem now becomes a normal nonlinear programming prob- In Eq. (14) xi represents the state variables, measurable on line
lem, which can be solved using any existing optimisation or off-line. In this work, solution concentration, solid content
technique. and mean size of crystals are three measured variables.
The constraints commonly imposed on seeded batch
crystallisation include solubility and secondary nucleation 2.2.2. Continuous operation
threshold (SNT) concentration. In particular, Eq. (8) above Simulations of start-up stages must be performed first
and the following derived by Butler [6] are used for since the feed stream is seeded and the number of seed parti-
lactose. cles in the vessel increases with time. A model of a continuous
stirred tank reactor operating at a constant temperature is
solsnt = e2.992+0.0196T (12) applied to describe the performance of the crystalliser at
steady state.
Below the solubility, crystals dissolve instead of growing.
Beyond the SNT concentration, nucleation occurs, result- 2.3. Experiments
ing in downstream processing inefficiencies. Working within
these limits justifies the assumption that the number of seed A 2 L stainless steel vessel, 4 L glass reactor and a 20 L
crystals remains constant through an operation. Some addi- stainless steel jacketed crystalliser were set up in the labora-
tional constraints are required for an evaporative semi-batch tory and the pilot plant, in accord with the schematic shown
since simultaneous syrup feeding and water evaporation in Fig. 1. Lactose was crystallised from high purity syrup at
affect the vessel inventory. The first additional constraint lim- 39 ◦ Brix, 60 ◦ C, generated in upstream units of the pilot plant.
its the total mass (W) in a crystalliser within initial and final Seeds having different median sizes taken from a jet mill,
values: Wi ≤ W ≤ Wfin . Secondly, the solid content (Cc ) in a under sieve 25 ␮m, between sieves 25–38 and 45–53 ␮m,
crystalliser has an upper limit, at which circulation will suffer with two seeding ratios 1.0 and 1.5% (w/w) of crystal-free
Cc = (xc /W) ≤ Ccfin . solution were used in the experiments and simulations of
The target of both heating and cooling problems is the cooling or evaporative operations, batch, semi-batch or con-
minimum operating time but the objective function set for tinuous mode. Cooling crystallisations were conducted in a 2
cooling mode can also be to maximise the growth at a spec- and 20 L stainless steel vessel, thermostated between 10 and
ified time OFcool = max{xc (tfin )}. In contrast the objective 70 ◦ C and equipped with a stirrer. Different cooling and seed-
function of an evaporative semi-batch, referred to as a multi- ing strategies were applied to evaluate the model. Sampling
ple objective function, is much more complicated as shown in was conducted every 30 min for the initial 3 h then hourly
T.T.L. Vu et al. / Separation and Purification Technology 48 (2006) 159–166 163

for 5 h and for the last 3 h of each batch (25 h). The samples slowest temperature drops, which can be achieved manually
were analysed for concentration (◦ Brix), solid content (mass in the laboratory. For a short batch from 10 to 12 h, applying
of lactose crystals/mass of content of the crystalliser), parti- the optimal strategy achieves the highest yield.
cle median size (␮m) and size distribution. For comparison
one evaporative run was conducted isothermally in a 4 L glass 3.1.2. Nonlinear curve fitting
vessel under vacuum, starting at the same initial conditions The optimal cooling trajectory was applied as a set point
applied for cooling. To mimic the real process the final prod- profile in the experiments and in the nonlinear least square
ucts were filtered, washed and dried. The weights of dried dynamic optimisation problem. In this problem three mea-
crystals and the filtrates were recorded to ensure a closed sured variables: solid content, particles median size and
mass balance and to calculate the yields. solution concentration were simultaneously fit to the model
equations, to re-evaluate two constants n and k used in the
growth rate Eq. (6). Experimental data were collected from
3. Results and discussions various scenarios: different batch sizes and seeding and cool-
ing strategies. Fig. 3 shows the best curve fitting of the initial
3.1. Batch cooling operation 12 h, giving n = 2.7 for all the cases investigated here, com-
pared to the value found in the literature varied from 2 to 3.
3.1.1. Set point profiles The value of k varies with the mass and mean size of initial
The cooling profiles, i.e. the solutions of the first dynamic seed crystals but is independent of the size of the crystalliser.
optimisation problem, are dependent on the mass and mean Implementing the optimal cooling strategy (curve 1) with jet-
size of initial seed crystals but not on the size of the crys- milled seeds at 1.5% seeding ratio yields the average value,
talliser. A faster temperature drop is applied for finer mean k = 0.007 ± 0.003; meanwhile fast cooling (curve 2) gives a
size and a larger weight of seeds. Fig. 2 shows the optimal higher value, slow cooling (curve 3) gives a lower k. To min-
cooling profile (1a) of jet-milled seed particles. At the begin- imise error when scaling up the model to industrial batch
ning of a cooling batch, the temperature profiles are restricted crystallisation, k must be re-estimated for selected seeding
by the SNT concentration (Eq. (12)) then later dictated by the and cooling strategies, and most importantly for the type of
mutarotation rate (Eq. (6)). For possible implementation the syrup fed to the crystalliser, coming from the upstream stage.
step profile is approximated by three first order polynomi- This can be achieved inexpensively in the laboratory.
als, labelled as (1b) in the same figure. Curves 1, 2, 3 and Particle size distributions of samples taken from a cooling
4 represent measured temperatures and corresponding solid batch seeded with jet-milled crystals are plotted versus time
contents in the crystalliser when different cooling rates were in Fig. 4 to study the spreading of initially narrow sized seed
implemented. Cooling profiles 2 and 4 are the fastest and population. A log–normal distribution curve is defined by the

Fig. 2. Cooling strategies and solid yields recorded in cooling batch (1: optimal, 2: fast, 3: natural and 4: slow strategies).
164 T.T.L. Vu et al. / Separation and Purification Technology 48 (2006) 159–166

Fig. 3. Solid yields and particle median size in cooling batch (1: optimal, 2: fast and 3: slow strategies; data points represent experimental results).

following equation [11]. particle size distribution of the product after 3 h as shown in
Fig. 4.
CF (ln(d/xd ))2
Fd = √ exp − (15)
σ 2π 2σ 2 3.2. Alternative processes
In Eq. (15), Fd is the relative frequency at size d, σ is the In addition to cooling batch mode the model can be
standard deviation of the distribution and CF is a dimension- extended and applied to semi-batch and continuous opera-
less constant related to the initial seed particles. If the seed tions, which were ignored in the lactose crystallisation liter-
crystals possess a constant relative growth rate then σ and ature.
CF remain constant regardless of the particle mean size. This
assumption does not hold for the first 3 h, while the shape, 3.2.1. Semi-batch: cooling and heating
standard deviation and skewness of the distribution change. In industrial seeded cooling crystallisation, seed crystals
After 3 h, the size distribution shape remains constant; val- and lactose syrup are initially drawn into the crystalliser to
ues of σ and CF reach 0.5 and 5, respectively. These values allow thorough mixing. Heat is then removed in accordance
and the median size can be used to predict the shape of the with the cooling temperature profile while syrup is contin-
uously fed at the maximum rate up to the volume of the
vessel. This process, referred to as semi-batch mode, offers
a higher yield or shorter operating time than a batch perfor-
mance due to the following reasons. Semi-batch operation
starts with a smaller mass of solution but the same mass of
initial seed crystals (xc0 ), therefore the initial growth sur-
face area or the initial seeding ratio is much higher. As the
seeds grow, the supersaturation decreases. Continuous feed-
ing of fresh syrup (without seeds) maintains a high driving
force for crystallisation and constrains the temperature drops
within limits to avoid a number of practical complications
such as non-uniform mixing or fouling the cooling surface
with crystals.
Steps (3.1.1) and (3.1.2) are applied to the semi-batch
cooling case using the modified equations (from 1 to 3). The
Fig. 4. Particle size distributions of jet-milled seeds up to 11 h in semi-batch same value of k and a cooling strategy similar to the batch
cooling crystallisation (data points represent predicted results). case can be used in semi-batch simulations and bench-scale
T.T.L. Vu et al. / Separation and Purification Technology 48 (2006) 159–166 165

Fig. 5. Solid yields and particle median size in semi-batch cooling, heating and continuous cooling operations (1 and 2: semi-batch and 3: continuous mode;
data points represent predicted results).

runs. Experimental results and prediction on both solid yield mentation is more complicated and nucleation is difficult to
and particle size agree well for an 8-h period as shown in control because the gap between solubility and secondary
curve (1), upper graphs of Fig. 5. After 8 h measured particle nucleation threshold concentration is very narrow (from 37 to
size starts to deviate from prediction since it is more difficult 40 ◦ Brix, at 60 ◦ C). Modern techniques to measure solid con-
to avoid nucleation, breakage and agglomeration in a high tent and concentration online as applied in the sugar industry
solid content solution. have not been extended to lactose manufacturing, therefore,
Evaporative semi-batch crystallisation was conducted at control of the lactose evaporative vacuum tank must rely on
a constant temperature and pressure lower than atmospheric a simple conductivity-based scheme. As a result, production
pressure to reduce the boiling temperature of the lactose solu- will be unreliable because the process cannot be exactly mon-
tion. Solving the dynamic optimisation of the evaporative itored, predicted and controlled.
semi-batch case, in which syrup feed is pumped into the ves-
sel, while heat is supplied to evaporate water yields feed and 3.2.2. Continuous operation
evaporation rate profiles. It was difficult to implement both Cooling in continuous mode is a promising alternative,
strategies in a bench scale experiment; therefore heat was which includes two stages, to be investigated. During the
supplied at a fixed rate, while feed was pumped in to main- start-up stage, seeded syrup feed is pumped in while heat
tain a constant level in the vessel. The final products were is removed but no product is withdrawn. The first stage,
filtered, washed, dried and analysed to compare with predic- case (3) in Fig. 5 is similar to the cooling semi-batch case
tion. Curve (2) in Fig. 5 plot simulation results. Between 2 except that seed particles are added in the feed stream. After
and 4 h, an evaporative run could achieve more than a cooling withdrawing the product, it takes about six or seven resi-
batch, which operated for more than 20 h. In cooling, the solid dence times for the solid content to reach steady state as
content cannot reach the limit of 35% while in heating the shown in the lower graphs of Fig. 5. The mean size, how-
solid can easily pass 50% due to the evaporation of water. That ever is only stabilised after 100 h. This indicates that seed
means in the same size crystalliser, heating is more efficient particles are washed out of the tank during a long transition
than cooling. However, operating and controlling an evapo- period. Further more nucleation cannot be avoided if the feed
rative batch while avoiding nucleation poses expensive and syrup at a high temperature (60 ◦ C) is directly introduced to
difficult problems compared with a cooling batch, in which the tank kept at a low temperature (20 ◦ C). A continuous
temperatures are easily measured and controlled. In contrast, stirred tank reactor operating at a constant temperature can-
evaporative crystallisation must be performed isothermally not describe well the performance when nucleation occurs
under vacuum to reduce the boiling temperature. This imple- in the process. A plug flow reactor installed before a contin-
166 T.T.L. Vu et al. / Separation and Purification Technology 48 (2006) 159–166

uous stirred tank reactor is being studied to overcome this Acknowledgements


drawback.
The authors would like to acknowledge Dairy Australia,
Food Science Australia and the Centre for Advanced Food
4. Conclusions Research, University of Western Sydney for their support
of this project. Our special thanks are due to Professor E.T.
In this study the dynamic model of a crystallisation pro- White and Dr. B. Butler, who gave us permission to use infor-
cess producing ␣-lactose monohydrate was derived for these mation in reference [6].
performances: cooling batch, cooling and evaporative semi-
batch, and cooling in continuous mode. The methodology of
formulating and solving the dynamic problems to find the References
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[8] T.T.L. Vu, R.J. Durham, J.A. Hourigan, R.W. Sleigh, Dynamic
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