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c
_
7
Here the symbols have the following meaning:
DE
v,e
is the activation energy at equilibrium, J mol
1
.
X and X
e
are the moisture content of the particle and the mois-
ture content at equilibrium respectively, kg kg
1
.
The coefcients a, b and c are tted parameters and were cited
to be 0.998, 1.405 and 0.930, respectively, for skim milk (only) in
Patel & Chen, 2005. This equation is likely to be different for other
materials.
2.3.1.3. Critical assessment of CDC and REA approaches. Langrish and
Kockel (2001) used computational uid dynamics modelling to as-
Table 2
Difference between the experimental and predicted results of using both CDC and
REA for milk powders in terms of temperatures and moisture contents (Roos and
Karel, 1991)
REA CDC
T (C) wt% T (C) wt%
Skim milk 1.6 1.1 3.6 3.8
Whole milk 2.0 1.6 3.4 2.9
S. Wang, T. Langrish/ Food Research International 42 (2009) 1325 17
sess the CDC approach for drying of milk, when considering the
data from the literature, nding that the linear falling-rate curve
was an acceptable approximation for most of the data. Patel and
Chen (2005) compared results from simulations using CDC and
REA models. They claimed that REA is a better approach than
CDC since it allows for initial (transient) adjustment periods, par-
ticularly in cases with high relative humidities and high feed con-
centrations. For other conditions, it was concluded that both
methods give similar results. The simulation results were not com-
pared with any experimental data. Both of the lumped-parameter
approach models assume that no segregation occurs within the so-
lid and that the concentrations of the components are the same
throughout the particles.
Chen and Lin (2005) compared the simulated results using both
CDC and REA and compared both simulated results with experi-
mental results for the drying of whole and skimmilk droplets. They
found that the predictions from the REA model are closer to the
experimental results from using CDC. This is shown in Table 2.
Although the predicted results of the REA model are closer to
the experimental results than the results predicted by the CDC
model, the difference is small between both predictions, since this
difference remained under 5% for both models. Chen and Lin
(2005) agreed that, although simple, the CDC provides a good
approximation to experimental results. Furthermore, it was also
recognised that the REA predicts an initial activation energy that
is higher than the actual one because, in the initial drying period,
the milk droplets behave similarly to water, where the activation
energy of drying is close to zero. The REA over predicts this value,
thus causing the initial drying rate to be underestimated, which
may cause the predicted temperature of the droplet to rise faster
than it really does. In their studies, Chen and Lin (2005) found that
this initial period of time, where over-prediction of the activation
energy occurs, is approximately the rst 10% of the total drying
time.
2.3.1.4. Short-cut approach of Thijssen & Coumans (1984). This ap-
proach, which is not widely used, is based on the similarity of
the shapes for the moisture content proles during the diffusional
drying process, assuming that drying occurs by diffusion. In the ini-
tial (penetration period) stages of drying, the moisture-content
proles penetrate, with a similar shape, to the centre of a material,
while during the so-called regular regime, the moisture-content
proles are also self-similar, but decreasing in magnitude through-
out the material, as shown in Fig. 1. More description of this ap-
proach and further details are given in the work of Keey (1992).
Not only is this short-cut approach based on the average mois-
ture content of the material, but it is also limited in assuming that
only diffusion occurs. Like the CDC and REA approaches, the
lumped-parameter nature of the approach means that it is not nor-
mally appropriate to the drying of multi-component mixtures.
2.3.2. Distributed-parameter approaches
Distributed-parameter approaches allow for different regions
within a drying material to contain different concentrations of
the components, with different physical properties. When applied
to the spray drying of milk particles, this means that the different
layers of the spray-dried milk particle may contain different con-
centrations of the components, such as fat and protein. This ap-
proach is therefore, consistent with the observed component-
migration phenomenon (Adhikari et al., 2007; Kim et al., 2003; Nij-
dam & Langrish, 2006). Modelling of the component-migration
process has been attempted by some researchers to predict the
product composition proles. The equations which they have used
are the MaxwellStefan and NernstPlanck equations. These works
are described in more detail next.
2.3.2.1. Diffusion of salt and water in cheese. Morison and Payne
(1999) have modelled the diffusion process of salt and water in
cheese. In this model, they assumed salt to be a single solute and
all other components of cheese to be solids. They modelled the dif-
fusion of salt through water and water through the solids using a
form of the MaxwellStefan equation, as shown in Eq. (8).
n
j1
ji
x
i
J
mj
x
j
J
mi
c
i
D
ij
x
i
RT
r
T;P
c 8
Here the symbols have the following meaning:
x
i
is the mole fraction of specie i.
J
mj
is the total molar ux vector in three dimensions
(mol m
2
s
1
).
D
ij
is the MaxwellStefan diffusivity between species i and j
(m
2
s
1
).
R is the ideal gas constant (8.314 J mol
1
K
1
).
T is the temperature (K).
c
i
is the molar chemical potential of species i (J mol
1
).
r is the Laplacian operator.
This equation has been rearranged to give the formshown in Eq.
(9).
J
n
cB
1
Crx 9
Fig. 1. Moisture-content proles during the diffusional drying of a material,
showing the penetration period and regular regime in the short-cut approach of
Thijssen and Coumans (1984).
Fig. 2. Predictions of salt and moisture concentrations as functions of time,
compared with experimental data for cheese (Morison and Payne, 1999).
18 S. Wang, T. Langrish/ Food Research International 42 (2009) 1325
Here the symbols have the following meaning:
J
n
is the molar diffusional ux vector in three dimensions of spe-
cies with respect to species n (mol m
2
s
1
).
c is the total molar concentration (mol m
3
).
Morison and Payne (1999) used estimated diffusion coefcients
of water and salt through solid cheese from the literature and com-
pared the modelled salt and moisture content with the experimen-
tal data. This comparison is shown in Fig. 2.
As observed in Fig. 2, the model predicted changes in moisture
and salt concentration similar to those observed in the experi-
ments. The small differences were attributed to the inaccuracy
of the literature diffusion coefcients (Morison & Payne, 1999).
This shows that the MaxwellStefan equation is suitable for the
modelling of component migration within cheese. Although this
work attempted the modelling of diffusion of both water and salt
through cheese, it assumed that all other components of the
cheese were in the solid form and thus cannot segregate. This
model describes a system where water and solutes migrates
through a solid matrix, and thus it is difcult to apply it directly
to the spray-drying process, which involves droplets of solution
drying to form particles. The solute in this application of the
model was primarily salt, not surface-active material like dis-
solved casein.
2.3.2.2. Diffusion in the production of supported coimpregnation
catalysts. In the production of supported coimpregnation cata-
lysts, drying conditions may be controlled to produce different
catalyst distributions (Lekhal, Glasser, & Khinast, 2001). During
impregnation, a support is rst soaked in the solution of the pre-
cursor of catalyst. The precursor diffuses into the support and is
adsorbed into the support; the solvent is then evaporated off.
Multi-component diffusion can be controlled to produce catalyst
proles, such as egg-shell, egg-white, egg-yolk and uniform distri-
butions. Egg-shell and egg-yolk refer to situations where the con-
centrations of the various components differ throughout the
particles. Lekhal et al. (2001) modelled the multi-component dif-
fusion and convective process using the NernstPlanck equation
as shown in Eq. (10).
N
l;i
D
l;i
rc
l;i
c
l;i
z
i
D
l;i
F
RT
r/ c
l;i
KK
l;eff
g
l
rP
l
10
Here the symbols have the following meaning:
N
l,i
is the ux of each component (kg m
2
s
1
).
D
l,i
is the diffusion coefcient of the ionic species in the solvent
(m
2
s
1
).
F is Faradays constant (96,500 C mol
1
).
ru is the electrostatic potential gradient (V m
1
).
K and K
l,eff
are the intrinsic and relative permeabilities of the
liquid phase, respectively (m
2
).
c
l,i
is the molar concentration of the specie i in liquid phase,
mol m
3
.
z
i
is the particle charge.
P
l
is the liquid pressure (Pa).
g
l
is the viscosity of the liquid phase (Pa s).
The NernstPlanck equation is used in this case, since the solu-
tion used in the production of coimpreganation catalyst contains
ionic solutes. This model allows the segregation of the solutes by
modelling the multi-component diffusion process. The model,
however, needs signicant adaptation to predict segregation in
the spray-drying process, since it models the diffusion process of
ionic solutes and not proteins and sugars in its current form. It also
does not currently include surface-active components.
2.3.2.3. Drop drying models for carbohydrate solutions. The drying of
drops of solutions has been modelled in many papers for carbo-
hydrates in order to investigate surface stickiness (Adhikari,
Howes, & Bhandari, 2006; Adhikari et al., 2003; Adhikari et al.,
2004). The materials that were investigated include sucrose, glu-
cose, fructose, citric acid and maltodextrin. The distributed-
parameter models used for these works were similar to each
other, in that they were all based on moisture diffusion through
solids. The model divides each droplet into layers, and evapora-
tion only occurs on the surface. The droplet is assumed to be a
non-hollow solid sphere (made of the solutes) and moisture dif-
fuses from the centre to the surface before evaporating. The dis-
solved solutes do not diffuse through the droplet, thus only the
concentration of moisture is different between different layers
of the droplet. The ux equation at the surface is shown below
for water (Adhikari et al., 2003).
N
l;i
k
g;i
A
p
M
w
R
P
atm
T
av;film
ln
1 P
v;db
=P
T
1 P
vs;Td
=P
T
_ _
11
Here the symbols have the following meaning:
k
g;i
is a corrected mass-transfer coefcient (m s
1
).
A
p
is the surface area of droplet (m
2
).
R is the gas constant (J mol
1
K
1
).
T
av,lm
is the lm temperature, the average temperature of the
uid lm in the boundary layer outside each particle (K).
P
atm
, P
v,db
and P
vs,Td
are atmospheric, vapour and saturated
vapour pressures, respectively (Pa).
Adhikari et al. (2003) used the model to estimate the moisture
content at the surface of the dried particle and thus predict the
glass-transition temperature T
g
, which was used as an indicator
of stickiness. They found that this distributed-parameter model
predicted the moisture content of the particles well, with an aver-
age error of 4.56%. Using the model they predicted that maltodex-
trin alters the surface stickiness of the products and thus is an
effective drying aid (Adhikari et al., 2003).
This distributed-parameter approach to modelling predicts dif-
ferences in moisture content in different regions of the particle,
thus predicting different surface stickiness than for the bulk of
the particle. However, the model does not currently allow for sol-
ute diffusion within the particle, since only moisture diffusion is
included. Thus this model cannot be used to predict segregation
of soluble components during spray drying.
2.3.2.4. Amodel for solid formation in spray drying. Seydel, Sengespe-
ick, Blomer, and Bertling (2004) proposed a mathematical model
Fig. 3. Solids formation processes in a spray-dried particle (Seydel et al., 2004).
S. Wang, T. Langrish/ Food Research International 42 (2009) 1325 19
for solid formation during spray drying. In this work, they based
the model for the drying process on the following scenario:
1. Evaporation occurs on the surface boundaries, causing forma-
tion of shell of solids. The formation of solids is based on nucle-
ation of crystals. The permeability of this shell depends on
whether it is made up of crystals or a lm.
2. A bubble can form in the drop, which consists of the drying gas.
This gas can escape the drop if the shell is permeable or remain
trapped if the shell is impermeable.
3. If the bubble remains trapped, the gas expands due to the
increase in temperature and causes ballooning of the particle.
If the shell is rigid, rupture of the shell occurs.
4. If rupture does not occur, the particle shrinks back to the origi-
nal size as the temperature drops.
The model is illustrated in Fig. 3.
Here the symbols have the following meaning:
r
i
is the inner radius of the droplet as well as the radius of the air
bubble (m).
r
old
and r
new
are the initial radius before expansion and nal
radius after expansion of the air bubble, respectively (m).
D is the diffusion coefcient of the liquid phase in the drop
(m
2
s
1
).
v is the velocity of component convection (m s
1
).
w
L
and w
G
are the weight percentages of the solvent and the
solute, respectively.
q
L
and q
G
are the densities of the solvent and the solute, respec-
tively (kg m
3
).
The mass ux equation for this model is shown below.
N
oqw
G
1e
ot
1
r
2
or
2
qw
G
v1e
or
..
convection
1
r
2
o
or
r
2
1eDq
ow
G
or
_ _
..
diffusion
oq
0
e
ot
..
phase transformation
oqw
G
1e
or
dr
i
dt
r r
i
t
r
a
t r
i
t
dr
a
dt
dr
i
dt
_ _ _ _
..
pseudo-convection
12
where
e is the volume fraction of the liquid phase (m
3
m
3
).
q is the density of the pure component (kg m
3
).
Seydel et al. (2004) used this model to predict the conditions
under which the formation of a bubble in a droplet is favoured.
They suggested that hollowed particles are formed preferentially
at high temperatures and with materials having low diffusivity.
Formation of full particles is favoured when lower temperatures
and high diffusivity materials are used. Seydel et al. (2004) ex-
plained that this is due to more even distribution of concentrations
in droplets when a material has a high diffusion velocity. They also
explained that lower temperatures allows more time for this distri-
bution to occur due to slower drying.
The model is a distributed-parameter approach, since it evalu-
ates component concentrations at different distances from the cen-
tre of the droplet. However, in their studies, Seydel et al. (2004)
emphasised the occurrence of hollowed particles and did not at-
tempt to predict the degree of component segregation. Similar to
the work done by Adhikari et al. (2003), this model includes diffu-
sion in a two-phase system (i.e. a liquid phase through the solid
shell) but does not account for the diffusion of solutes within the
solvent in the liquid phase. This means that only water is allowed
to migrate within the particles and that the solutes are assumed to
be xed in their positions. Hence, the model, in its present form,
does not allow for migration of solutes and cannot predict segrega-
tion. The model also addressed the solids-formation process using
crystal nucleation and growth approaches, but many of the prod-
ucts from spray drying are amorphous in nature (White & Cake-
bread, 1966). The extent of crystallization for these particles may
not necessarily be complete in spray drying.
2.3.2.5. Distributed-parameter model for the drying of timber. Nij-
dam, Langrish, and Keey (2000) modelled the drying process of
softwood board using a one-dimensional distributed-parameter
approach. In this model, both uxes of moisture in the vapour
phase and the liquid phase were considered. There are two types
of ux for liquid moisture, the convective uxes caused by capil-
lary pressure and the diffusive uxes caused by concentration dif-
ferences. Gaseous transport mechanisms include gas convection,
vapour and air diffusion. These ux equations are shown below
(Nijdam et al., 2000).
j
wv
q
v
e
k
g
l
g
oP
g
oz
P
g
RT
D
g
M
v
e
_ _
o
oz
P
v
P
g
_ _
13
j
a
q
a
e
p
g
l
g
oP
g
oz
P
g
RT
D
g
M
a
e
o
oz
P
a
P
g
_ _
14
j
wf
q
l
p
l
l
l
o
oz
P
g
P
c
15
Here the symbols have the following meaning:
j
wv
, j
a
and j
wf
are the uxes of the water vapour, the air and the
free (unbound) water, respectively (kg m
2
s
1
).
q
v
, q
a
and q
l
are the densities of the vapour, the air and the
liquid, respectively (kg m
3
).
p
g
and p
l
are the permeabilities of the moist solids to gas and
liquid ows, respectively (m
2
).
l
g
and l
l
are the dynamic viscosities of the gas and the liquid,
respectively (kg m
1
s
1
).
P
g
, P
c
, P
v
and P
a
are the gas, capillary, vapour and air pressures,
respectively (Pa).
D
g
is the gas diffusion coefcient (m
2
s
1
, or kg m
1
s
1
when
multiplied by the component density).
M
v
and M
a
are the molar masses of the vapour and the air,
respectively (kg mol
1
).
e is the void fraction (m
3
m
3
).
In this model, Eqs. (13) and (14) describe the ux of the airva-
pour movement through the wood bres and Eq. (15) describes the
movement of unbound water. The model simulates uxes of both
liquid and gases that move through the solid wood bres and thus
is signicantly different to the case of spray drying, where droplets
of solution are dried and form solids. The components that are in-
cluded in the simulations are those for the water vapour, liquid
water, wood and air.
2.3.2.6. Modelling of segregation using slab experiments. Meerdink
and Riet (1995) compared experimental results from drying slabs
of agar, containing a ternary system of water, sucrose and casein,
with the simulated result from a multi-component diffusion mod-
el. The equations in their model follow:
oC
w
ot
o
or
E
ww
oC
w
or
o
or
E
ws
oC
s
or
16
oC
s
ot
o
or
E
ww
oC
w
or
o
or
E
ss
oC
s
or
17
20 S. Wang, T. Langrish/ Food Research International 42 (2009) 1325
Here the symbols have the following meaning:
C
w
and C
s
are the molar concentrations of water and sucrose,
respectively (mol m
3
).
t is the drying time (s).
E is an element of matrix of transformed diffusion coefcients
(m
2
s
1
).
Since the model was written to simulate a slab-drying experi-
ment, water is assumed to evaporate froma front that progressively
withdraws into the slab as evaporation continues, leaving behind a
slab consisting of the dry solutes. The model does not include the
surface activity of casein and only considers the segregation due
to the differences in the diffusion rate between sucrose and casein
towards the centre. This model also does not explicitly account for
the effect of the differences in solubilities of the solutes. Instead, it
assumes that the diffusivities of solutes are dependent on the mois-
ture content. This means that, whenthe moisture content decreases,
the diffusivities of the solutes also change and, in the limit of no
water present, the diffusion coefcients approach zero. Although
this approach simulates the diffusion process as the concentrations
of solutes increase due to evaporation, it also implies that the
solutes that have precipitated (as solids within the spray-dried par-
ticles) continue to diffuse slowly as long as small amounts of mois-
ture are present. This is unlikely to be true when the solutes have
precipitated out of solution as solids (Cussler, 1997).
2.3.2.7. Critical analysis of existing models of drying for the purpose of
predicting component segregation. The existing models of drying re-
viewed above are summarised in Table 3.
As stated in Table 3, the lumped-parameter models do not allow
for the migration of dissolved components of milk. These lumped-
parameter approaches to modelling the spray-drying process can
still be used to predict the overall drying kinetics. They involve less
experimental effort to use than distributed-parameter models, in
that fewer experiments are required to quantify the tted param-
eters. However, they effectively assume that the concentrations of
various components within the particles are the same, which
means that these models cannot predict the occurrence of compo-
nent segregation.
Most of the distributed-parameter models fromthe literature do
not account for or allow for the phenomenon of the migration of
dissolved components of milk during drying, as observed. These
models generally assume that the dissolved components are in so-
lid formand that water diffuses through them(Adhikari et al., 2003;
Morison & Payne, 1999; Seydel et al., 2004). The models of Lekhal
et al. (2001) and Nijdam et al. (2000) both describe systems where
water and solutes may diffuse through solid matrices and allow
segregation to occur through multi-component diffusion. These
systems are different to the case of spray drying, in that droplets
are formed initially in spray drying, which then solidify as water
is evaporated. Thus these models cannot currently be used to pre-
dict the extent of component segregation in spray drying. Both
the distributed-parameter models set up by Seydel et al. (2004)
and Meerdink and Riet (1995), to simulate the spray-drying pro-
cess, allow for component migration through diffusion. However,
they do not yet account for surface-active components. Both mod-
els also do not account for the effects of different solubilities of the
solutes explicitly. To understand and predict this, a new distrib-
uted-parameter model needs to be set up to study the mechanisms
of diffusion for not only the solvent, but also the dissolved compo-
nents. The effects of different solubilities of solutes and surface-ac-
tive components also need to be incorporated into this new model.
2.4. A new distributed-parameter multi-component model
To understand the mechanisms of component segregation and
thus predict the surface properties of spray-dried products, a
new distributed-parameter model need to be developed. This mod-
el need to allow for the diffusion of all dissolved components,
while also taking the effects of their solubilities and surface-active
properties into account. These migration mechanisms are ex-
plained in detail next.
2.4.1. The diffusion process
Diffusion plays an important part in both hypotheses two and
three. In hypothesis two, the diffusivities of different components
affect the order in which they are segregated. In hypothesis three,
diffusion of protein to the surface may be the rate-limiting step. In
order to better understand the process for spray-drying liquid
products, the diffusion process needs to be studied in detail and
modelled.
All forms of the diffusion equation calculate the ux using a
driving-force term, such as the difference in concentration and a
diffusion coefcient. The diffusion coefcient for mass transfers
in a liquid can be estimated using the StokesEinstein equation
as shown in Eq. (18) Cussler, 1997.
D
K
B
T
6plR
0
18
Here the symbols have the following meaning:
R
0
is the component particle size (m).
D is the diffusion coefcient (m
2
s
1
).
K
B
is Boltzmanns constant (1.38 10
23
J K
1
).
T is the temperature (K).
Table 3
Existing drying models in the literature and the experimental work involved when using these models
Existing models Description Experimental determination of parameters
CDC (lumped-parameter) Shape of drying curve independent of drying conditions Need to measure drying-rate curves under different drying conditions
as well as different sample congurations to assess the shape of drying
curves
Lumped-parameter model does not predict segregation of
components
REA (lumped-parameter) Activated rate process with DE
v
representing the increase
in difculty of removing water from the particle as the
moisture content deceases
Relationship of DE
v
with moisture content needs to be determined. In
theory, only one experiment is needed, but in practice experiments are
required to check if DE
v
values are unique for different drying
conditions and congurations of samples Lumped-parameter model does not predict segregation of
components
Existing distributed-parameter
approach for spray drying
Diffusion of water from centre to surface. Moisture content
is allowed to be different through the particles
Experiments are required to estimate all parameters used in the model.
More experiments are needed than the number of parameters
Solubilities of dissolved components and surface activity
are not considered
S. Wang, T. Langrish/ Food Research International 42 (2009) 1325 21
l is the viscosity of the solvent (kg m
1
s
1
).
This equation suggests that diffusion coefcients increase with
temperature and decrease with solvent viscosity and the size of the
molecule. Diffusion is often accompanied by convection, and the
total mass ux is the sum of the ux due to diffusion and the ux
due to convection, as explained by Cussler (1997).
Some suitable equations, which include both convective and
diffusion components, are shown in Table 4.
In these equations, n is the total ux, j is the ux due to diffu-
sion, v is the average solute velocity, c is the local concentration,
V is the volume average velocity and y is the molar average velocity
(Cussler, 1997).
2.4.2. Diffusion coefcients
Many attempts have been made to determine the diffusion
coefcients for a large variety of solutes. Some of these solutes in-
clude components of milk, carbohydrates and amino acids. Some of
these coefcients may be estimated using the StokesEinstein
equation, while others have been experimentally quantied by
experimental methods, such as the Taylor dispersion method.
The source, species and descriptions of the diffusion coefcients
quantied in the literature for carbohydrates, protein and fat are
summarised in Table 5. Some of these works are further explained
next.
2.4.2.1. Milk components. As mentioned before, Kim et al. (2003)
have estimated the diffusivity ratios for the different components
of milk using Eqs. (18) and (19). Eq. (18) is the StokesEinstein
equation, as previously mentioned.
D
i
D
lactose
R
0;lactose
R
0
; i
_ _
n
19
Here i is the component and n = 1, 2 or 3.
The estimated diffusivity ratios are summarised in Kim et al.
(2003), who then explained that according to this equation, and
its empirical extensions (for higher concentrations), the diffusion
coefcient can be proportional to R
n
0
(n = 1, 2 or 3). This means
that the diffusion coefcient is inversely related to the size of the
solute particles (to some power) and thus the diffusivity ratios be-
tween lactose and other components can be estimated by Eq. (19).
This information is shown in Table 6.
Table 4
Examples of some diffusion equations (Roos, 1995)
Choice Total ux Diffusion equation Reference velocity Best used for
Mass n
1
j
m
1
c
1
v j
m
1
q
1
v
1
v Dqrx
1
v x
1
v
1
x
2
v
2
qv n
1
n
2
Constant density liquids; coupled mass and momentum
transport
Volume n
1
j
1
c
1
v
0
j
1
c
1
v
1
v
Drc
1
v
0
c
1
V
1
v
1
c
2
V
2
v
2
V
1
n
1
V
2
n
2
For constant density liquids and for ideal gases; may be used
either mass or mole concentration
NernstPlanck ry
1
y
1
y
2
D
v
2
v
1
none Suitable for ionic solutes in electrolyte
Table 5
Summary of sources, species and description of diffusion coefcients estimated in the existing literature
Source Species Description
Hennings et al. (2001) and Kim et al. (2003) Free fat Diffusion coefcients estimated based on size of particles using Eq. (2)
Fat globules
Casein micelles
Casein sub-units
Whey protein
Lactose
Salts
Chen and Lin (2005) and Ribeiro et al. (2006) Lactose Diffusion coefcients measured experimentally for different temperatures and concentrations
Sucrose
Thijssen and Coumans (1984) and Wu et al. (2001) L-Proline Diffusion coefcients measured experimentally for different concentrations
L-Threonine
L-Arginine
Table 6
Relative sizes of molecules and other components in milk and their diffusivity ratios
in an aqueous solution (Hennings et al., 2001)
Type of particles Size (diameter, m) Diffusivity ratio
R
1
0
R
2
0
R
3
0
Free fat >10
5
>10
4
>10
8
>10
12
Fat globules 10
5
10
6
10
4
10
8
10
12
Casein micelles 10
7
10
8
10
2
10
4
10
6
Casein sub-units 10
8
10
9
10
1
10
2
10
3
Whey protein 10
8
10
9
10
1
10
2
10
3
Lactose 10
9
10
10
1 1 1
Salts 10
9
10
10
1 1 1
Table 7
Mutual diffusion coefcient of aqueous lactose solution and the respective standard deviations, D S
D
, at different temperatures and concentrations (Chen and Lin, 2005)
s (mol/dm) Dc (mol/dm
3
) D S
D
(10
9
m
2
s
1
)
T = 298 K T = 303 K T = 308 K T = 312 K T = 318 K T = 328 K
0.001 0.568 0.035 0.643 0.010 0.723 0.010 0.789 0.030 0.862 0.057 1.060 0.099
0.005 0.005 0.565 0.040 0.639 0.011 0.720 0.085 0.785 0.025 0.855 0.082 1.058 0.074
0.010 0.01 0.541 0.037 0.631 0.012 0.708 0.035 0.774 0.040 0.850 0.031 1.044 0.009
0.100 0.06 0.541 0.012 0.602 0.005 0.677 0.027 0.740 0.033 0.785 0.023 1.018 0.009
22 S. Wang, T. Langrish/ Food Research International 42 (2009) 1325
As shown in Table 6, the diffusivity ratio of free fat to lactose is
the lowest of all the components, which suggests that its diffusion
rate is the slowest. This component is followed by fat globules,
which is the next in order of diffusivity ratio. The diffusivity ratios
are order of magnitude estimates based on approximate sizes of
the particles. Given the absolute values of the diffusion coefcient
of lactose, the diffusion coefcients of the individual components
can then be estimated.
2.4.2.2. Carbohydrates in aqueous solutions. Ribeiro et al. (2006)
have measured the diffusion coefcients of lactose, sucrose, glu-
cose and fructose in aqueous solutions using the Taylor dispersion
method. In this method, a small amount of solution is injected into
a carrier solution of a slightly different concentration, which is
owing in a laminar stream through a long capillary tube. As the
carrier solution ows along the tube, the change in the concentra-
tions caused by the diffusion of the solute is measured by a refrac-
tometer at the end of the tube. These results are then used to nd
the diffusion coefcients of the solute. The experiments were con-
ducted in concentrations between 0.001 to 0.1 mol/L, and temper-
atures between 298.15 K and 328.15 K. The experimental results
for the diffusion coefcients of lactose and sucrose in aqueous
solutions at different temperatures are reported in Tables 7 and 8.
As observed in both Tables 7 and 8, the diffusion coefcients of
both sugars increase with temperature and decrease with increas-
ing concentrations. The diffusion coefcient of lactose is slightly
higher than that of sucrose at the same conditions, for example,
at 0.001 M and 298.15 K, D
lactose
is 0.568 10
9
m
2
s
1
and D
sucrose
is 0.525 10
9
m
2
s
1
. The small difference between the values
probably reects the fact that the sugars have different structural
arrangements, despite having the same molecular formula.
Wu, Ma, Liu, & Li, 2001 have also measured diffusion coef-
cients of sucrose in more concentrated solutions at 298.15 K. The
results are shown in Table 9.
As observed in Table 9, the diffusion coefcient of sucrose de-
creased from 5.22 10
6
cm
2
s
1
to 2.88 10
9
cm
2
s
1
as the
concentration increased from innite dilution to 0.772 M. This
trend is similar to that observed by Ribeiro et al. (2006). For the dif-
fusion coefcient at 298.15 K and 0.1 M, the value reported by
Ribeiro et al. (2006) is 0.504 10
9
m
2
s
1
, while that reported
by Wu et al. (2001) is 0.490 10
9
m
2
s
1
. The values are close
and consistent with each other.
2.4.2.3. Amino acids. Cussler (1997) has explained that, since amino
acids contains side chains which end in amino and carboxylic acid
groups, their diffusion coefcients are likely to be pH dependent.
This is because, at low pH, the amino groups become positively
charged (NH
3
) and the carboxylic group becomes negatively
charged (COO
A3
] is the thermodynamic factor.
In their work, Wu et al. (2001) found the value of A
1
, by tting
the empirical results, to be 0.4655371, A
2
to be 0.3065743 and
A
3
to be 0.05312948. These parameters could be potentially ex-
tended to other non-electrolytes. Although quantied, the values
of the parameters were not compared with any existing literature
values.
For the purpose of this model, the diffusion coefcients of case-
in have been estimated using the method shown in Kim et al.
(2003), since no experimental value for the diffusion coefcient
of casein is available. To ensure consistency, the diffusion coef-
cient of lactose has also been estimated using the same method.
This is justied because, even though these values might not be ex-
act, they are of a similar order of magnitude to the experimental
values. The experimental results found by Ribeiro et al. (2006)
range between 0.5 10
9
and 1.1 10
9
m
2
s
1
, in comparison
with the range of 10
9
10
10
m
2
s
1
, as estimated by Kim et al.
(2003). The ranges overlap, and thus it is suggested that the esti-
mated diffusion coefcients are initially sufcient for modelling
purposes.
2.4.3. Implementations of surface activity effects
Kim et al. (2003) have described the third hypothesis for com-
ponent migration as being caused by surface activity. In this
hypothesis, the proteins in the regions near the liquid/air interface
of the droplet absorb preferentially to the surface of the particles
and form a monolayer. This monolayer of protein then dries up
upon initial heating and thus deprives the solution near the surface
of any dissolved protein. This causes a concentration gradient
through the droplet and drives diffusion of protein from local re-
gions in the droplet towards the surface. It is possible that the
majority of the surface-active component may diffuse towards
the surface. The surface-active solute will be present in the solu-
tion/solid matrix within the droplet during drying. The surface
activity of the proteins may result in them being pulled to the sur-
face rapidly and precipitating, possibly causing the concentration
of the solute in the liquid to be low under the surface region. This
then simplies the effect of the surface tension to that of diffusion
of the surfactants from the centre to the surface of the droplet, as
assumed by Meerdink and Riet (1995).
To model the effect of the surface activities of the proteins, the
process of the initial formation of the monolayer must be consid-
ered. Graham and Phillips (1979) investigated the rate of migration
of casein to the surface from a bulk solution. In their experiment,
they introduced a homogenous solution of casein into a container
and monitored the changes in surface concentration casein at dif-
ferent times. The path length for the diffusion of casein was 1 cm,
and the experiment was performed at 20 C. These workers found
that casein reached 90% of its nal surface concentration in
approximately 4 h and that the rate of change of surface concentra-
tion in this region is diffusion controlled. This information can be
used to estimate the time needed for casein in the layer immedi-
ately below the surface to diffuse to the surface in the new distrib-
uted-parameter model, where the diffusion coefcient may be
assumed to be directly proportional to the absolute temperature,
according to the StokesEinstein equation. From the residence
time of particles in the spray dryer, the maximum path length
for the diffusion of the proteins can then be estimated. This path
length can then be compared with the thickness of the surface
layer in the distributed-parameter model to ensure that all of the
protein from this shell can migrate to the surface during spray
drying.
3. Conclusions
To improve the spray-drying process of sticky materials con-
taining low molecular weight sugars and organic acids, the segre-
gation process of the components in the particles has been
discussed. Existing evidence for component segregation in milk
powder has been reviewed, and the hypotheses for this process,
namely crust formation, solubility and surface activity, have also
been explored. To assess the conditions under which these pro-
cesses are dominant, simulations of particles drying in spray dryers
need to be carried out. Existing lumped-parameter approaches, as
well as distributed-parameter approaches, have been reviewed. A
new distributed-parameter model needs to be developed to allow
for the segregation of multiple components, as well as accounting
for their solubility and surface activities. This new model can then
24 S. Wang, T. Langrish/ Food Research International 42 (2009) 1325
be used to predict the surface as well as the bulk properties of the
products. To evaluate the effectiveness of using additives as drying
aids during spray drying, previous research has been reviewed,
suggesting that very low amounts of casein (1% overall) are re-
quired to dominate the surface composition of the particles, but
the effect of casein additives on the overall yield has not been mea-
sured yet. To further understand the effect of the casein on the
spray-dried products, there is a need to quantify the yields using
small amounts of casein as additives in spray drying and to assess
the effects of different operating conditions during spray drying on
the segregation. In addition, the most effective proteins, and the
reasons for their effectiveness, need to be assessed, since whey
proteins and casein have different properties.
References
Adhikari, B., Howes, T., & Bhandari, B. R. (2006). Use of solute xed coordinate
system and method of lines for prediction of drying kinetics and surface
stickiness of single droplet during convective drying. Chemical Engineering and
Processing, 46(5), 205419.
Adhikari, B., Howes, T., Bjandari, B. R., & Troung, V. (2004). Effect of addition of
maltodextrin on drying kinetics and stickiness of sugar and acid-rich foods
during convective drying experiments and modelling. Journal of Food
Engineering, 62(1), 5368.
Adhikari, B., Howes, T., Shrestha, A., & Bhandari, B. R. (2007). Effect of surface
tension and viscosity on the surface stickiness of carbohydrate and protein
solutions. Journal of Food Engineering, 79(4), 11361143.
Adhikari, B., Howes, T., & Troung, V. (2003). Surface stickiness of drops of
carbohydrates and organic acid solutions during convective drying:
Experiments and modelling. Drying Technology, 21(5), 839873.
Australian Bureau of Statistics. The Australian Dairy Industry. <http://
www.abs.gov.au/ausstats/abs@.nsf/Previousproducts/1301.0Feature%20Article-
182004?opendocument&tabname=Summary&prodno=1301.0&issue=2004&
num=&view=> Accessed 14.11.07.
Bhandari, B. R., Datta, N., Crooks, R., Howes, T., & Rigby, S. (1997). A semi-empirical
approach to optimise the quantity of drying aids required to spray dry sugar-
rich foods. Drying Technology, 15(10), 25092525.
Bhandari, B. R., & Howes, T. (1999). Implication of glass transition for the drying and
stability of foods. Journal of Food Engineering, 40(12), 7179.
Cano-Chauca, M., Stringheta, P. C., Ramos, A. M., & Cal-Vidal, J. (2005). Effect of the
carriers on the microstructure of mango powder obtained by spray drying and
its functional characterization. Innovative Food Science and Emerging
Technologies, 6(4), 420428.
Chan, H.-K. (2006). Dry powder aerosol drug deliveryOpportunities for colloid and
surface scientists. Colloids and Surfaces A: Physiochemical Engineering Aspects,
284285(A), 5055.
Chen, X. D., & Lin, S. X. Q. (2005). Air drying of milk droplets under constant and
time-dependent conditions. American Institute of Chemical Engineers Journal,
51(6), 17901799.
Chidavaenzi, O. C., Buckton, G., & Koosha, F. (2001). The effect of co-spray drying
with polyethylene glycol 4000 on the crystallinity and physical form of lactose.
International Journal of Pharmaceutics, 216, 4349.
Cussler, E. L. (1997). Diffusion mass transfer in uid systems (2nd ed.). Cambridge
University Press (pp. 114119).
Faldt, P., & Bergenstahl, B. (1994). The surface composition of spray-dried protein
lactose powder. Colloids and Surfaces A: Physicochemical and Engineering Aspects,
90(23), 183190.
Graham, D. E., & Phillips, M. C. (1979). Proteins at liquid interfaces: 1. Kinetics of
adsorption and surface denaturation. Journal of Colloid and Interface Science,
70(1), 403414.
Hennings, C., Kockel, T. K., & Langrish, T. A. G. (2001). New measurements of the
sticky behaviour of skim milk powder. Drying Technology, 19(34), 471484.
Keey, R. B. (1978). Introduction to industrial drying operations. Oxford: Pergamon (pp.
154156).
Keey, R. B. (1992). Drying of loose and particulate materials. New York: Hemisphere.
Keey, R. B., & Suzuki, M. (1975). On the characteristic drying curve. AIChE Symposium
Series, 73(163), 4756.
Kim, E. H.-J., Chen, X. D., & Pearce, D. (2003). On the mechanisms of surface
formation and the surface composition of industrial milk powder. Drying
Technology, 21(2), 265278.
Kuo, M., DSouza, A. J. M., Tep, V., Gordon, M. S., Schiavone, H., Charan, C., et al.
(2007). Preparation of stable and dispersible dry powder aerosol formulations by
spray drying. San Carlos, California/Lawrence, Kansas: Inhale Therapeutic
Systems, Inc./The University of Kansas (<http://www.nektar.com/pdf/
dried_powder.pdf> Accessed 14.11.07).
Langrish, T. A. G., & Kockel, T. K. (2001). The assessment of a characteristic drying
curve for milk powder for use in computational uid dynamics modelling.
Chemical Engineering Journal, 84(1), 6974.
Lekhal, A., Glasser, B. J., & Khinast, J. G. (2001). Impact of drying on the catalyst
prole in supported impregnation catalyst. Chemical Engineering Science, 56(15),
44734487.
Masters, K. (1996). Deposit-free spray drying: Dream or reality. In Proceedings of the
10th international drying symposium, IDS96, Krakow, Poland, 30 July2 August
1996 (Vol. A, pp. 5260).
Meerdink, G., & Riet, K. v. (1995). Modelling segregation of solute material during
drying of liquid foods. AIChE Journal, 41(3), 732736.
Morison, K. R., & Payne, M. R. (1999). A multi-component approach to salt and water
diffusion in cheese. International Dairy Journal, 9(12), 887894.
National Honey Board, Dried Honey Product. <http://www.honey.com/downloads/
driedhoney.pdf> Accessed 05.10.07.
Nijdam, J. J., & Langrish, T. A. G. (2006). The effect of surface composition on the
functional properties of milk powder. Journal of Food Engineering, 77(4),
919925.
Nijdam, J. J., Langrish, T. A. G., & Keey, R. B. (2000). A high-temperature drying model
for softwood timber. Chemical Engineering Science, 55(18), 35853598.
Patel, K. C., & Chen, X. D. (2005). Prediction of spray-dried product quality using two
simple drying kinetic models. Journal of Food Process Engineering, 28(6),
567594.
Ribeiro, A. C., Ortona, O., Simones, S. M. N., Santos, C. I. A. V., Prazeres, P. M. R. A.,
Valente, M. J. A., et al. (2006). Binary mutual diffusion coefcient of aqueous
solutions of sucrose, lactose, glucose and fructose in the temperature range
from (298.15 to 328.15) K. Journal of Chemical and Engineering Data, 51(5),
18361840.
Roos, Y. H. (1995). Characterization of food polymers using state diagrams. Journal
of Food Engineering, 24(3), 339360.
Roos, Y. H., & Karel, M. (1991). Plasticizing effect of water on thermal behaviour and
crystallization of amorphous food models. Journal of Food Science, 56, 3843.
Roustapour, O. R., Hosseinalipour, M., & Ghobadian, B. (2006). An experimental
investigation of lime juice drying in a pilot plant spray dryer. Drying Technology,
24(2), 181188.
Seydel, P., Sengespeick, A., Blomer, J., & Bertling, J. (2004). Experiment and
mathematical modeling of solid formation at spray drying. Chemical
Engineering and Technology, 27(5), 505510.
Tan, J. P. K., Goh, C. H., & Tam, K. C. (2007). Comparative drug release studies of two
cationic drugs from pH-responsive nanogels. European Journal of Pharmaceutical
Sciences, 32(45), 340348.
Thijssen, H. A. C., & Coumans, W. J. (1984). Short-cut calculation of non-isothermal
drying rates of shrinking and non-shrinking particles containing an expanding
gas phase. In Proceeding of the 4th IUFRO international drying symposium, IDS 84,
Kyoto, Japan (Vol. 1, pp. 2230).
Truong, V., Bhandari, B. R., & Tony, Howes (2005). Optimization of cocurrent spray
drying process for sugar-rich foods. Part IIOptimization of spray drying
process based on glass transition concept. Journal of Food Engineering, 71(1),
6672.
White, G. W., & Cakebread, S. H. (1966). The glassy state in certain sugar containing
food products. Journal of Food Technology, 1(1), 7382.
Wu, Y., Ma, P., Liu, Y., & Li, S. (2001). Diffusion coefcients of L-proline, L-threonine
and L-arginine in aqueous solutions at 25 C. Fluid Phase Equilibria, 185(12),
2738.
S. Wang, T. Langrish/ Food Research International 42 (2009) 1325 25