Blackwell Science, LtdOxford, UKJFPEJournal of Food Process Engineering0145-8876Copyright 2005 by Food & Nutrition Press, Inc., Trumbull, Connecticut.

282107132Original Article FREEZE-DRYING SIMULATIONS.

J.-L. ROBERT and C. RATTI

KHALLOUFI,

SOLID FOODS FREEZE-DRYING SIMULATION AND EXPERIMENTAL DATA

S. KHALLOUFI1, J.-L. ROBERT2 and C. RATTI1,3
1

Soils Science and Agri-Food Engineering Department 2 Civil Engineering Department Laval University Sainte-Foy G1K 7P4 QC Canada
Accepted for Publication June 6, 2004

ABSTRACT This article presents a mathematical model describing the unsteady heat and mass transfer during the freeze drying of biological materials. The model was built from the mass and energy balances in the dried and frozen regions of the material undergoing freeze drying. A set of coupled nonlinear partial differential equations permitted the description of the temperature and pressure proles, together with the position of the sublimation interface. These equations were transformed to a nite element scheme and numerically solved using the Newton-Raphson approach to represent the nonlinear problem and the interface position. Most parameters involved in the model (i.e., thermal conductivity, specic heat, density, heat and mass transfer coefcients etc.) were obtained from experimental data cited in the literature. The dehydration kinetics and the temperature proles of potato and apple slabs were experimentally determined during freeze drying. The simulation results agreed closely with the water content experimental data. The prediction of temperature proles within the solid was, however, less accurate.

INTRODUCTION Freeze drying is a dehydration process where water vapor is removed by sublimation from frozen materials, usually under conditions of low pressure and temperature. The advantage of this process is mainly related to the high nal quality of products (Mellor 1978; Sagara and Ichiba 1994; Krokida and Maroulis 1997). This attribute is due to two main characteristics of freeze
3

Corresponding author. TEL: Cristina.Ratti@sga.ulaval.ca

418-656-2131

4593;

FAX:

418-656-3723;

EMAIL:

Journal of Food Process Engineering 28 (2005) 107132. All Rights Reserved. Copyright 2005, Blackwell Publishing

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S. KHALLOUFI, J.-L. ROBERT and C. RATTI

drying: (1) Water, representing more than 80% of food products, is frozen and therefore cannot serve as a solvent reactant throughout the sublimation process; (2) Process temperatures are low (product temperatures are between -40 to -20C during sublimation and nal temperatures, in the range of 2050C, depending on the heating plate temperature), so the deterioration reactions (i.e., nonenzymatic reactions) are slow or are completely stopped because of weak rate constant (Cheftel et al. 1977). Despite the excellent quality of nal products, the cost of the freezedrying process is fairly expensive (Lombraa et al. 1997; Sadikoglu et al. 1998) and its applicability remains mainly reserved to products of high market value such as pharmaceutical products and some special foods (nutraceutical, baby foods, spices and coffee). This major disadvantage of freeze drying is directly related to the long processing times caused by the high material resistance to heat transfer during the operation (Sagara and Ichiba 1994; Kuu et al. 1995), the sample conguration, its own properties and the operating conditions. In addition, the condenser temperature and the vacuum level should be maintained at their lowest values during the freeze-drying process. Energy constitutes a major cost factor, which is composed of the energy necessary for sublimation and desorption as well as the energy to support vacuum and refrigeration. An important part of previous investigations aimed to reduce freezedrying times and consequently to lower the energy consumption, analyzing the possibilities of controlling the heat intensity and the vacuum pressure and therefore investigating possible ways of optimizing the freeze-drying process. Several studies were carried out in laboratories and in pilot scale plants (Sagara and Ichiba 1994; Kuu et al. 1995; Liapis et al. 1996). Simulation was also used as a preliminary tool for the evaluation of the freeze-drying process. Several theoretical models concerning the heat and mass transfer phenomena during freeze drying can be found in the literature (Karel 1975; Mellor 1978; Liapis and Bruttini 1995a; Lombraa and Izkara 1996; Lombraa et al. 1997). One of the earliest and most known models is that for solids with heat and mass transfer through the dry layer (Karel 1975):
t= L2 rms ( Xo - X f ) 8 Per( Pi - Ps )

(1)

which, because of simultaneous heat and mass transfer process, is equivalent to:
t= L2 rms ( Xo - X f ) 8kd (Ts - Ti )

(2)

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109

Although easy to use, Eqs. (1) and (2) have several key assumptions that are not usually applicable. (1) The maximum allowable surface temperature, Ts is reached instantaneously. (2) The heat output of the external supply is adjusted to maintain Ts constant throughout the drying cycle. (3) Partial pressure in the drying chamber is constant. (4) All the heat is used for the sublimation of water vapor (Karel 1975). More recently, numerical models with highly detailed equations have been developed (Liapis and Bruttini 1995a; Lombraa and Izkara 1996; Lombraa et al. 1997; Brlls and Rasmuson 2002; George and Datta 2002). However, in most cases, adjustable parameters are needed to match the model predictions to experimental data (Liapis and Marchello 1984; Millman et al. 1985; Sharma and Arora 1993; Sadikoglu and Liapis 1997; Sheehan and Liapis 1998; George and Datta 2002). In other cases, no comparison with experimental data is presented (Nastaj 1991; Liapis and Bruttini 1995b). In addition, most of the models were developed for liquids and not for solid products (Sadikoglu and Liapis 1997; Sheehan and Liapis 1998; Brlls and Rasmuson 2002). It is clear that one way to decrease the costs of freeze drying is to reduce the operation time by increasing the temperature and therefore, a precise understanding of the simultaneous heat and mass transfer occurring during the process is required. Thus, the main goal of the present article is to investigate the temperature, the vapor pressure and the water remaining within a solid food during the process through a dynamic and unidirectional mathematical model of the primary stage of freeze drying. The structure of the present work is as follows: (1) a brief description of the physical phenomena taking place during freeze drying, (2) a theoretical analysis of partial differential equations necessary to describe the underlying phenomena in an elementary volume, (3) the numerical solution with details on the building of the computer program and (4) an experimental validation of the model and a discussion of the effect of some important freeze-drying parameters through simulation. MODEL DEVELOPMENT Device Description and Problem Formulation The main components of the freeze-drying device (Fig. 1A) are (1) the heating plates, to ensure the temperature control in the sample; (2) the vacuum pump, to ensure the pressure control in the chamber and (3) the condenser, which condenses the vapor and avoids its passage to the pump. During the freeze-drying process, the product is placed between the heating plates (Fig. 1B). Therefore, a radiant source, as well as heat by

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Upper heating plate Vapor Condenser `

Sample Lower heating plate

Ice

Vacuum pump

B
Upper plate q upper

Top

Sample

Interfaces

Lower plate q bottom

Bottom

FIG. 1. (A) COMPONENTS OF A FREEZE-DRYER. (B) DETAILS ABOUT THE MECHANISMS OCCURRING DURING FREEZE DRYING

conduction from the bottom, is imposed to the material slab. There are two mechanisms of water elimination during freeze drying: sublimation (which eliminates the frozen water) and desorption (which eliminates the bounded unfrozen water). Sublimation occurs at the interface of the ice front as a result of the transferred heat (Simatos et al. 1974). As dehydration proceeds, the ice front retreats and the sublimated water vapor (at the ice front) is removed by diffusion through the porous layer (Liapis and Bruttini 1995a). The water vapor ows through the dried layer countercurrent to the heat ow.

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111

Then, it passes through the chamber to be nally collected on the condenser plate. Theoretical Analysis and Governing Equations The physical model representing the foodstuff being freeze-dried has a rectangular cross-section, with thickness 2E much smaller than the length L and width l (Fig. 2A). The heat and mass transfer occurs in a direction perpendicular to the largest side (Fig. 2A). To simplify the analysis, the following key assumptions were made: (1) One-dimensional heat and mass ow in the normal direction from the ice interface and the surface of the product. (2) During freeze drying, sublimation occurs at the ice front interface, parallel to both bottom and top surfaces and situated at distance S from them (Fig. 2B). (3) The problem is symmetric and the uniform retreating ice front moves on both sides to the centerline at the same speed (Fig. 2A). Some experiments were done to validate this assumption. The results showed that the temperature in the bottom and in the top of the sample were generally comparable. (4) In the dried porous region, the solid matrix and the enclosed vapor are in thermal equilibrium. (5) The thickness of the ice front interface is considered to be innitesimal. (6) At the ice front interface, the water vapor concentration is in equilibrium with the ice. (7) Each frozen and dried region is considered to be homogenous, having uniform thermal conductivity, density and specic heat. (8) Only the primary drying period (free water removed by sublimation) was considered. The secondary drying (removal of the bound water) was neglected, as suggested by Sharma and Arora (1993), Lombraa et al. (1997) and Sheehan and Liapis (1998). The consideration of the secondary drying stage would have required, in addition, the knowledge of sorption isotherms below and above 0C. However, sorption isotherms below 0C are not available in the literature. (9) Conduction was considered as the main energy transfer mechanism in the frozen region, while both conduction and convection are considered in the dried portion. (10) Shrinkage is not considered in this model. Due to the symmetry of the slab, the analysis will be applied only to half of the sample. The equations describing the physical system, as applied to the elementary volume that is shown in Fig. 2B, are as follows:

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z x

A a

E y

B b
0

qxd

mxd Dried zone

dxd qxd+dxd S (t ) qxf dxf qxf+dxf E mxd+dxd

Frozen Fr zone

FIG. 2. (A) GEOMETRICAL DIMENSIONS. (B) DISCRETIZATION USED IN THE NUMERICAL SOLUTION

Dried Layer (a) Temperature prole. The complete energy balance presented by Sadikoglu and Liapis (1997) for the tray freeze-drying process was applied to the freeze drying of a food slab under vacuum (the inert gas ow is negligible).

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113

The ow of vapor through the dry matrix was represented through a permeability-type equation. The resulting equation is thus:
Td Td Pv j j = + t x 1 x x 2 x

(3)

kd PerCpv and j 2 = T Cpd r d Cpd r d d The rst term on the right hand side of Eq. (3) refers to energy transfer by conduction, while the second refers to the energy that is transferred due to vapor ow. The permeability coefcient Per, necessary for the determination of parameter f2 of Eq. (3), was calculated as reported by Simatos et al. (1974) and Liapis and Litcheld (1978):

where j1 =

Per =

M C2 DAB Kn RT C2 DAB + Kn(PT - Pv )

(4)

The Knudsen (Kn) constant was calculated as follows (Liapis and Litcheld 1978; Mellor 1978):
2 8 1 2 M Kn = C1 , where C1 = 3 p r RTd
12

(5)

C2 is a dimensionless constant, which depends on the internal texture of the product (Simatos et al. 1974). According to Gunn et al. (1969), this parameter characterizes the porous medium but does not depend on the gas species present in the matrix. The molecular diffusivity (DAB) of the binary mixture was estimated by the Fuller equation (Skelland 1974): DAB = 1.16 10-4T1.75 (b) Pressure prole.
T Pv Pv = b + b2 d t x 1 x t

(6)

(7)

where b1 =

P PerR and b 2 = v Me Td The permeability value Per, required for the determination of the parameter b1 of Eq. (7), was calculated using Eq. (4).

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Frozen Layer In the frozen region, there is only heat transfer by conduction. Thus, the temperature prole is represented by the following differential expression:
Tf t kf Cp f r f = Tf Tf w x x

(8)

where w =

Boundary Conditions At the surface, = 0 (a) Temperature. The boundary condition at the material surface can be described by:
kd Td = - hT (T - Td [ 0, t ]) x

(9)

where hT is the heat transfer coefcient. Two heat transfer coefcients were considered for the simulations: (1) one was obtained from the following theoretical expression:
hT = sF(T2 + Td2 [ 0, t ])(T + Td [ 0, t ])

(10)

where s is the Stefan-Boltzmann constant and F is the radiation view factor. (2) another was an experimental heat transfer coefcient, which was reported by Wang and Shi (1997, 1998). (b) Pressure. A convection resistance coefcient (hP), which depends on the total pressure (Lombraa and Izkara 1996), was considered for mass transfer at the surface:
Per Pv = hT ( P - Pv [ 0, t ]) x

(11)

At the interface, = S(t) S(t) represents the interface position of the sublimation front, which depends on time. At this position, an additional equation was obtained from the energy balance on a differential element of thickness dS:

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115

DHsub msub = - kd

Tf Td + kf s x x s

(12)

The term on the left-hand side corresponds to the latent heat of sublimation. The right-hand side terms are the conductive heat uxes in and out of the differential element. The mass ux of sublimated vapor can be expressed as follows:
msub = r f WC FF dS dt

(13)

There should be no discontinuity in temperature at the interface (S[t]), thus:

Td
S (t )

= Tf

S (t )

(14)

For vapor pressure calculation, the thermodynamic equilibrium existing between the water vapor and the frozen product. was used at the interface (Clapeyron equation):
Pv
S (t )

B = exp A + T S (t )

(15)

At the center, = E At the matrix center, because of the symmetry, adiabatic or zero heat ux condition can be supposed.
Tf x =0

(16)

Initial Conditions Uniform temperature and vapor pressure are chosen as initial conditions, thus: 0<x<E 0 < x < S(0) Calculation of Water Remaining (a) Initial water. The initial water, (X0) existing in the matrix before freeze drying, is:
X0 = WC r f VT

T(x,0) = Tini P(x,0) = Pini

(17) (18)

(19)

(b) Sublimated water. The sublimated water represents the frozen water that is eliminated from the matrix at each moment. This amount depends on the position of the interface and can be expressed by:

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msub (t ) = WC FF r f l L S(t )

(20)

(c) Remaining water. The amount of remaining water (Xr) is the sum of the frozen water that has not been sublimated yet and the bound water, therefore:
Xr (t ) = WC r f L l( E - FF S(t ))

(21)

The progress of remaining water can be followed by its comparison to the initial water content (water remaining/initial water content, %):
Xr (t ) S( t ) (%) = 100 1 FF X0 E

(22)

MATERIALS AND METHODS Experimental Data Slabs (14-mm and 8-mm thickness) of potato and apple were chosen for freeze-drying kinetic experiments. The samples were frozen in a medical freezer at -40C (Sanyo MDF-235, Japan) and freeze-dried in a Unitop 400 L (Virtis, NY) drying chamber connected to freezemobile 25 EL (Virtis). The frozen samples were placed on the freeze-dryer shelf, initially at -40C. When the condenser temperature was less than -85C, the vacuum pump was turned on. The heating system (1C/min) was started after the total pressure was less than 10 mtorr. The shelf temperature was set at 40C. Each experimental determination of water content, after different process times, was done independently from the others. At the initial time, the 8- or 14-mm-thick food slab was weighed and introduced into the freeze drier. It was left inside the freeze drier for a predetermined process time (18, 10, 12, 14 or 16 h) and then it was removed and weighed. Then the experiment started all over again for another predetermined process time. The experimental data for each process time and for the slab thickness was obtained in triplicate. The maximum process times were 8 and 16 h for an 8-mm or 14-mm-thick slab, respectively. The duration of the freeze drying was calculated from the moment when the heating system was started. To calculate the amount of water that was eliminated, the samples were weighed using a Mettler Toledo balance (PB 1502, 0.01 g, Switzerland) before and after the freeze-drying operation. Once freeze drying ended, the dry matter of each sample was determined in a vacuum oven. The moisture contents of the samples were estimated from the differences between the nal freeze-dried weight and the dry matter. A comparison of the experimental data with the simulation results was done using the ratio percentage Xr(t)/X0 (water remaining/initial water content, %).

FREEZE-DRYING SIMULATION

117

Upper plate

Top

Sample

Thermocouples

Bottom Lower plate

2 3

4 5

Data Logger logger

Computer

FIG. 3. EXPERIMENTAL PROTOCOL FOR MONITORING TEMPERATURE EVOLUTION IN THE SAMPLE DURING THE FREEZE-DRYING PROCESS

The temperature proles during the freeze drying of a 28-mm-thick sample were obtained by placing ve standard 1-mm diameter K-type thermocouples in the product at different locations (shown in Fig. 3): one at the center, two inside the product very close to each bottom and top surface and the last two at half of the thickness. The thermocouple insertion was performed in a fresh food slab before freezing and then the product, with the inserted thermocuple, was frozen. Before the thermocouple insertion, a tiny

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needle was inserted in the product where the thermocouple was to be placed (to serve as a guide in order to ease the thermocouple insertion) up to the position where the thermocouple was supposed to be (i.e., 7 mm for the measurement of the center temperature in a 14-mm-thick slab) and then a determined length of the thermocouple was inserted. The placements of the thermocouples were supposed to be the length up to where the needle guide was inserted. All measures of position and distances were determined by using a micrometer Digimatic (CD 6 B, Mitutoyo Corporation, Japan). During freeze drying, temperature variations were recorded by a digital data logger (21X Micrologger, Campbell Scientic Inc., UT), which was directly plugged to the computer. The temperature acquisition was done at 1-min intervals. Numerical Solution To obtain a nite element (characterized by two node linear 1D element) form of the governing Eqs. (3), (7), (8) and (12), each region (frozen and dried) was divided into n elements of thickness dxd and dxf (Fig. 2B). Eqs. (3), (7) and (8) can be organized in a matrix form (Eq. 23):
Td 0 dt x j 1 x x j 2 x Td = P - b2 1 Pv 0 b1 v 123 4 4 x m t 14444 244444 4 x 3 1
k

(23)

The application of the nite element method transforms the matrices m and k into discrete forms, whose size depends on the number of elements chosen. Then an implicit Euler time marching method is applied, in which the nonlinearity is treated by a Newton-Raphson method. Eventually, the condition (14) is applied (Eq. 24):
[ K d ]n n K d 1 n [ 0]l n

{K d }n 1
0

{K f }l 1

{Rd }n 1 rf (1) ( n + 1) rd K f 1 l DTi = - (24) kd ( n + 1, n + 1) k f (1,1) {DF } [ K f ]l l f l 1 {R f }l 1

[ 0 ]n l {DF d }n 1

where DFd and DFf are the discrete variable increment vectors (Td and Pd for the dried part and Tf for the frozen part), DTi is the increment of the common temperature of the dried and frozen parts, Rd and Rf are the residuals, Kd and Kf are matrices obtained from m and k. Originally, the sizes of the matrices were (n + 1) (n + 1) and (l + 1) (l + 1). By the introduction of the condition (14), the last temperature equation of Kd and the rst of Kf are

FREEZE-DRYING SIMULATION

119

combined to give the central equation of the system (24), which ensures the coupling of the system. Indeed, the matrix system allows calculating the variation of the two parameters (DT and DPv) at a given node as a function of the temperature and the vapor pressure values at the same node and at the neighborhood nodes. A computer program was developed in Matlab 5.2 based on the previously described numerical scheme. The program calculates for each value of time, the temperature and vapor pressure spatial distributions, their average values as well as the ice front position. It also calculates the instantaneous and the cumulative values of the sublimating water. The specic heat, thermal conductivity, density and porosity of the complete physical model were considered constant, but the developed numerical scheme could be easily adapted to use complex expressions involving temperature, pressure- and/or humiditydependent terms. The knowledge of the interface position S(t) has a fundamental importance in solving the freeze-drying problem. Since this position recedes continuously, it adds additional calculations and complexity to the problem. Equation 13 was used to calculate the interface position at each time step (Dt). For this, the program considers the S value as a variable and its calculation is done by iteration using the Newton Raphson method. This method was chosen upon the more traditional methods of evaluating S because it avoids interpolation without increasing the running time. To avoid pronounced gradients and consequently, a high number of iterations, the total pressure variation in the chamber and the vapor pressure in the condenser were approximated at the beginning of each simulation by the following equation:
P(t ) = Pmax - ( Pmax - Pmin )
( Dt + G )

Dt (t + G )

(25)

where Pmax is the pressure at the beginning, Pmin the pressure at the end of the process, Dt the time required for P to be Pmin, t the time and G, a constant. It can be seen from Eq. (25) that if the value of G is low, the end value of pressure will be reached quicker. Several tests were made to assure that this equation does not affect the nal solution. The proposed technique allowed achieving the nal results in reasonable computation times. In addition, preliminary tests showed that in the vicinity of the physical model surface and in the neighborhood of the sublimation front, the temperature (in both zones) and the vapor pressure (in the dried zone) gradients could be very pronounced. This strongly affects the number of iterations. To nd a remedy for this situation, the network-rening technique was used. This method involves more nodes where the gradient is steep and less nodes where

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the gradient is at, through an exponential function. Therefore, the network was rened at each small displacement of the sublimation front. Even if an implicit scheme was used to solve the coupled equations (temperature and vapor pressure), the numerical solution stability was found to be strongly dependent on initial conditions and particularly on the choice of time step (Dt). To avoid the divergence of the solution, the time step (Dt) was continuously adjusted while running the program. After each solution, the Dt was reevaluated as a function of the number of iterations (from an initial 0.01 s step up to 100 s or more) without affecting the solution convergence. To be able to start the numerical calculation, an arbitrary initial thickness of the dried layer was chosen (0.5% of the slab thickness), thus: S(0) = 0.01E (26)

This initial thickness of dry layer should be considered as formed during the start-up of the process before energy is supplied to the sample. This period represents the time required for passing from the atmospheric to the vacuum pressure. Physical Properties and Other Parameters Table 1 shows all the parameters and expressions for physical properties used for the simulations, obtained from published values of similar materials in the literature. It should be signaled, however, that some parameters such as C2 (see Eq. 4) were not easily available in the literature and, in addition, physical properties generally depend on the product composition, the freezedrying device and on operating conditions. Therefore, the value C2 was estimated through preliminary simulations. The nal values of permeability that were obtained using Eq. (4) for the two products (apple and potato) were found to fall within the range of those reported by Kessler (1981) for some food products, corroborating the predictions done on C2.

RESULTS AND DISCUSSION Comparison with Experimental Results Figure 4 shows the experimental freeze-drying curves for 14- and 8-mmthick apple and potato slabs at 40C. As expected, the effect of thickness on the freeze-drying time was marked. Indeed, the sublimation of 50% of the ice in the apple requires about 240 min if the thickness is 8 mm and about 400 min for 14-mm thickness. As can be seen, freeze-drying times did not vary with the square of the thickness. Other authors previously found a linear relation-

TABLE 1. PARAMETERS AND PHYSICAL PROPERTIES USED FOR SIMULATION Apple Values 787.93 2.84 103 1.289 123.17 a = 1.65 10-7 0.0337 90 5 84.36 43 10-6 0.05 0.95 Expressions References

Parameters

Potato

Values

References

rf (kg/m3) Cpf (J/kgK) Kf (W/m.K) rd (kg/m3) Cpd(J/kgK) Kd(W/m.K) (%) FF (g/g) WC (g/g) r (m) C2 (dimensionless)

1022 1.8 103 1.09 180 1.66 103 0.0404 88 4 78.62 48 10-6 0.07

Kerr et al. (1996) Lewis (1987) Mujumdar (1995) Krokida and Maroulis (1997) a = 1.35 10-7. Kostaropoulos and Saravacos (1997) Kessler (1975) Krokida and Maroulis (1997) Rao and Rizvi (1995) Determined for this study Estimated Determined in order to obtained the value of permeability cited by Kessler (1981)

F (dimensionless)

Khallou and Ratti (2002) Rao and Rizvi (1995) Rao and Rizvi (1995) Khallou and Ratti (2002) Kostaropoulos and Saravacos (1997) Kessler (1981) Khallou and Ratti (2002) Rao and Rizvi (1995) Determined for this study Mellor (1978) Determined in order to obtained the value of permeability cited by Kessler (1981) Given References Poling et al. (2001) Poling et al. (2001) Lombraa and Izkara (1996) Wang and Shi (1997, 1998) Litcheld and Liapis (1982) Liapis and Marchello (1984) Sadikoglu and Liapis (1997) Sadikoglu et al. (1998)

FREEZE-DRYING SIMULATION

Common expressions and parameter

Equilibrium equation (vapor-glass) (P in Pa and T in K)

Latent heat of sublimation (DHsub) (kJ/kg). T in K External mass transfer coefcient (hP) (kg/Pa m2.s) P in Pa hT (W/m2.K) Cpv (J/kgK) s (W/m2.K4) R (J/kmol.K) M (kg/kmol)

B Psat = exp A + A = 28.80073 and B = -6142.89 Tsat DHsub = -0.0037T2 + 1.7502T + 2630.4 hP = 15.912 10-3 P-0.7731 6.7 1.6747 103 5.676 10-8 8.314 103 18

121

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100 90 80 Water remaining (X /X0)x100 70 60 50

Potato

14 mm
40 30

8 mm
20 10 0 0 100 200 300 400 500 600 700 800 900 1000

100 90 80 Water remaining (X /X0)x100 70 60 50 40 30 20

Apple

14 mm

8 mm
10 0 0 200 400 600
Time (min) Experimental data (14 mm) Model predictions (14 mm) Experimental data (8 mm) Model predictions (8 mm)

800

1000

1200

FIG. 4. COMPARISON BETWEEN EXPERIMENTAL DATA AND MODEL PREDICTIONS OF FREEZE DRYING OF APPLE AND POTATO (8 AND 14 mm THICKNESS) AT 40C HEATING PLATE TEMPERATURE

FREEZE-DRYING SIMULATION

123

ship between freeze-drying time and thickness, as Sharma and Arora (1995), for yoghurt under different heating transfer modes and Saravacos (1967), in the case of apple and potato. In the literature, however, freeze-drying time is often presented as proportional to the square of the piece size (see Eqs. 1 and 2), because the process is usually explained from the diffusion theory. King (1968) explained the anomaly with respect to pure diffusion theory, based on an externally controlled (boundary layer) freeze-drying process, which could clearly explain the linear relationship between freeze-drying time and product thickness. The simulation of apple and potato freeze-drying kinetics was done by solving the proposed model with the values listed in Table 1. Figure 4 shows a comparison between predicted and experimental results on water remaining in apple and potato as a function of freeze-drying time. As can be seen, the agreement between both values is close, indicating that the present onedimensional model gives reasonably accurate results to predict freeze-drying curves. The RSMEs (root square mean errors) between predicted and experimental data were determined as 18.6 and 45.3 min for 8- and 14-mm-thick apple slabs and 9.7 and 50.8 min for 8- and 14-mm-thick potato slabs, respectively. The main differences between experimental and predicted values were found for thicker slabs at the end of the process. An explanation for this could be (1) the absence of desorption in the model and/or (2) the mass transfer, happening by lateral surfaces, which could be more signicant in the case of thicker slabs. Figure 5 shows the experimental and predicted temperature proles for 28-mm-thick apple and potato slabs. It should be noted that because the present model does not take into account the desorption phase (assumption 8), the comparison will be limited only to the rst stage of freeze drying (from the start of the heating until the complete disappearance of ice). From Fig. 5, it can be seen that (1) The sublimation temperature is seen as a plateau at the rst stage of freeze drying (x = E). The model gives a reasonably good prediction of the sublimation temperature for both products. (2) The temperature predictions, at different locations within the product, substantially underestimates the obtained experimental data. This disagreement can be interpreted from different viewpoints: most physical parameters used in the model were obtained from the literature or predicted from theoretical expressions (hT, k etc.) there was a clear difculty encountered during the experiments to measure an accurate frozen core temperature in specic locations within the sample during freeze drying, particularly because the heat passing through the probe

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S. KHALLOUFI, J.-L. ROBERT and C. RATTI

35 25 15

Temperature (C)

x=0
5

Predicted temperatures x = E/2

5 15 25 35 45 0 500 1000 1500 2000 2500 3000 3500 4000

x=E

Experimental temperatures

Sublimation

Desorption

p Ap

le

35 25 15

Predicted temperatures

Temperature (C)

x=0
5 15 25 35

x = E/2

Experimental temperatures

x=E

t Po
Sublimation Desorption
1500 2000 0 500 1000

at

45 2500

FIG. 5. EXPERIMENTAL AND PREDICTED TEMPERATURE PROFILES DURING FREEZE DRYING OF APPLE AND POTATO

generated some freeze drying around the thermocouple, which probably did not help in reecting the real temperature. the model did not take into account all the phenomena involved (i.e., desorption) the sample was too thick to assume unidirectional heat transfer.

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125

100 90 80 70 60 50 40 30

2E = 14 mm

Water remaining (X /X0) 100

Radiation transfer Thermal resistance transfer

20 10

Experimental data
0 100 90 80 70 60 50 0 200 400 600 800 1000 1200

2E = 8 mm

Water remaining (X /X0) 100

Radiation transfer
40 30

Thermal resistance transfer

20

Experimental data
10 0 0 100 200 300 400 500 600

Time (min)

FIG. 6. COMPARISON BETWEEN PREDICTIONS CONSIDERING AND EXPERIMENTAL HEAT TRANSFER COEFFICIENT AND PURE THEORETICAL RADIATION (8 AND 14 mm THICKNESS APPLE SLABS)

Figure 6 shows the comparison between freeze-dying kinetics that was obtained using theoretical (pure ideal radiation) and experimental heat transfer coefcients. It can be seen that the coefcient, which was experimentally found by Wang and Shi (1997, 1998) and which includes the total heat transfer including radiation, gives much better predictions than the use of the equation for ideal blackbody radiation. For the freeze-drying process, Wolf and Gibert (1998) reported that the heat transfer coefcient

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(hT) depends on pressure and its value varies from 4 W/m2.K at 1 Pa to 50 W/m2.K at 100 Pa. Figure 7A shows that the heating plate temperature signicantly affects the freeze-drying kinetics. The sublimation process nishes at 12.6 h for a heating plate temperature of 70C, while only 47% of sublimation is achieved during the same period if the heating plate temperature is 10C. The impact of the heating temperature on the surface and sublimation temperatures of the sample is given in Fig. 7B. It can be seen that, while increasing the heating plate temperature does not markedly increase the frozen core temperature, the product surface temperature does. This nding can greatly help when optimizing the product quality during freeze drying. Hammami and Ren (1998) indicated that to avoid the collapse phenomena and the quality problems during freeze drying, the temperature of the frozen solid should be below the melting onset temperature and the temperature of the product in the dry zone, below the glass transition of the dry solids (Tgs). Two temperature limits were shown to be essential during the freeze drying of a particular product: the ice melting onset temperature (Tm) and the glass transition temperature of the dry solids (Tgs). Nevertheless, from Fig. 7B, it can be concluded that the second temperature limit (glass transition of the dry solids) is a stronger optimization parameter during freeze drying than the former.

CONCLUSIONS Mathematical simulations were used to predict freeze-drying kinetics and temperature proles of food slabs and to study the impact of some parameters on the process. The nonlinear governing equations were solved numerically and the results were compared to experimental data. The comparison revealed a very good agreement between predicted and experimental freeze-drying kinetics and sublimation temperature, while the predicted temperature proles did not closely represent the experimental data. To improve the prediction of the present model, the following considerations should be taken into account: (1) to include a complex formulation of permeability, (2) to add the second stage (desorption) of freeze drying (3) to consider two different thermal resistances (one for the bottom, taking into account the thermal contact with the heating plate and the other for the top of the sample) and (4) to consider two dimensional transfers. In addition, extra experimental research should be done to determine physical properties, such as thermal conductivity as a function of pressure, C2 coefcient, pore radius and isotherm function at two temperatures (below and up 0C) etc. The simulations showed that the use of an experimental heat transfer coefcient is a better option for simulation than to consider pure radiation

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100

A
90 80

Water remaining (X /X0) 100

70 60 50 40 30 20 10 0 0 40 5 10 15 20 25 30 35 40

Time (h)

B
30

Temperature of product (C)

20

10

-10

-20 0 10 20 30 40 50 60 70 80

Heating temperature (C) Surface of sample Front of sublimation

FIG. 7. (A) EFFECT OF THE HEATING PLATE TEMPERATURE ON FREEZE-DRYING KINETICS. (B) EFFECT OF HEATING PLATE TEMPERATURE ON SAMPLE TEMPERATURE PROFILE

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through a theoretical expression. In addition, the heating plate temperature showed a major effect on freeze-drying kinetics and surface temperature. This simulation program can therefore be used as a tool for the optimization of the freeze-drying process.

NOMENCLATURE

r s DH e C1 C2 Cp DAB E F FF hP hT k L l M m P Per Pini Pmax Pmin q R r S T Tini t Tg Tm V WC

Mass density (kg/m3) Stephan-Boltzmann constant values (J/s.m2.K4) Latent heat (kJ/kg) Porosity Knudsen constant value (m) Dimensionless constant Specic heat (J/kgK) Molecular diffusivity (m2/s) Half the thickness (m) Radiation view factor Frozen fraction of water (kg frozen water/kg total water) Mass transfer coefcient (kg/Pa m2 s) Heat transfer coefcient (J/m2.s.K) Thermal conductivity (J/m.K.s) Length (m) Width (m) Molecular weight (kg/kmol) Vapor ux (kg/s.m2) Pressure (Pa) Permeability (s) Initial pressure (Pa) Pressure at the beginning (Pa) Pressure at the end (Pa) Heat ux (J/s) Gas constant value (J/kmol.K) Pore radius of dried layer (m) Interface position (m) Temperature (K) Initial temperature (K) Time (s) Glass transition temperature (K) Melting temperature (K) Volume (m3) Initial water content (kg water per kg fresh product)

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X x

Amount of water (kg) Spatial position (m)

Subscript d f r s sat sub T v 0 chamber conditions dry frozen remaining solid saturation sublimation total vapor initial

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