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A Model for Real Thermal Control in High-Pressure Treatment of Foods
Laura Otero, Antonio D. Molina-Garc a, Angel M. Ramos, and Pedro D. Sanz*
Instituto del Fr o (CSIC), C/ Jose Antonio Novais, 10, 28040 Madrid, Espan a, and Departamento de Matema tica Aplicada, Facultad de Matema ticas, Universidad Complutense de Madrid, Ciudad Universitaria, s/n. 28040 Madrid, Espan a

A model for the simulation of thermal exchanges in a complete high-pressure equipment was developed. Good agreement between simulated and experimental timetemperature profiles was found during different processes of pressurization and depressurization. The model allows study of the effect of different variables to improve thermal control in the treatments performed. This work involved an important advance in optimization and regulation of high-pressure processes in the food industry.

Introduction
The application of hydrostatic high pressure (HHP) to food processing (mainly as a preservation method and to change the physical and functional properties of food systems) has drawn increasing interest. Nowadays, the number of food industries that have included this technology in their processes has expanded. Nevertheless, high pressure is still a relatively expensive process. It is necessary to optimize it to facilitate generalized use. According to the Pascal principle, high pressure acts instantaneously and uniformly throughout a mass of food independently of its size, shape, or composition, yielding a great advantage to HHP as compared to thermal processing. Nevertheless, pressurization/depressurization induces a temperature increase/decrease due to the work of compression/expansion in both food and pressurizing fluid. The value and sign of these temperature increments depend on conditions such as pressure and temperature, rate of application, composition of the food, and type of pressurization fluid. These increments can be calculated as described by Otero et al. (1). Shimizu (2) found temperature increments as large as 20 C for pressure increments of 200 MPa in vegetable fats. In large volume industrial processes, the filling factor has to be as high as possible, i.e., the pressurizing chamber must be as full of product as possible. Then, the impact of the variation of temperature can be very important and it can take a long time to thermally reequilibrate the vessel. This can possibly give rise to undesired side effects for the food, such as gelification, crystallization, alterations in enzyme activity or protein stability, fat migration, changes in oxidation state, and freezing (3, 4), as well as an increased energy expense in thermal regulation. Nevertheless, this temperature increment is not the only important problem. For a homogeneous food, tem* E-mail: psanz@if.csic.es. Universidad Complutense de Madrid.
10.1021/bp010157a CCC: $22.00

perature will increase uniformly during compression. So, providing that its initial temperature was uniform, it will be higher just after pressurization but still uniform. However, the holding period at high pressure will alter this uniformity, as there will be heat transfer to or from the pressure vessel body and surroundings (5). For heterogeneous foods, their different constituents will increase temperature in different ways altering the thermal uniformity after pressurization. The observed product temperature change with time, as a result of a process of heat transmission, will depend on the thermophysical properties and masses of food and fluid, those of the vessel walls, the heat exchange possibilities inside the vessel (convection, sample mobility), and the heating or cooling power supplied. As de Heij et al. (6) pointed out, the temperature sensor in most HHP systems is placed at the vessel center, hence the hottest point during pressure treatment. Contrary to classical ultrahightemperature sterilization processes, the critical control point (coldest point) is located near the wall of the vessel. Denys et al. (3, 7) have shown the nonuniform temperature distribution in a food model after compression. These authors proved that these thermal gradients are enough to give rise to a nonuniform distribution of enzyme inactivation within the food product. They emphasized that the different pressure-temperature-time profiles generated during a process at different locations in the high-pressure vessel may result in a pronounced nonuniform distribution of enzyme and/or microbial inactivation and nutritional and/or sensorial quality degradation, within the processed product. Despite this, most works on pressure treatment of foods do not control temperature during pressure treatments, and the observed results are attributed to the applied pressure and initial temperature without considering the temperature increase due to compression and the nonuniform temperature distribution during holding time. It is therefore necessary to reconsider the microbiological sterility experiments published in the public domain (6). Farkas and

2002 American Chemical Society and American Institute of Chemical Engineers Published on Web 06/08/2002

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Figure 1. High-pressure system. Circles (T) show the points in which a thermocouple was inserted.

Hoover (5) suggested that the best solution to this problem at this time was a definition of the process using the parameters of initial temperature, compression time, product temperature, process temperature, and process hold-time at pressure. Nevertheless, this cannot be a universal solution when the processes must be repeated in various devices with differing dimensions, pressurizing fluids, and thermoregulating systems. Heat exchange will be obviously different and so will the evolution of temperature in the sample. This work was focused on obtaining a macroscopic model that takes into account all the thermal exchanges in a high-pressure system, to evaluate the impact of the different components and therefore allow regulation of temperature in a given process. At present time there exist some papers (3, 7, 8) about modeling heat transfer during high-pressure processing of foods, but all of them, except ref 8, are focused on the thermal gradients that are established in the sample. So, these models only consider the sample, the high-pressure medium, and the internal wall of the pressure chamber. In our work, we want to stress the great importance of considering the entire high-pressure equipment to make decisions controlling the temperature of a sample during pressure treatment. This thermal control is indispensable for the generalized use of commercial high-pressure treatments.

Material and Methods

The pilot unit (ACB GEC Alsthom, Nantes, France) in Figure 1, used for all experiments, had a cylindrical chamber of 2.35 l (100 mm diameter, 300 mm height). Pressure was increased by pumping fluid in the chamber, which was filled with water acting simultaneously as sample and pressurizing fluid. No lubricant or any other fluid were involved. Liquid water has been chosen both as sample and pressurizing fluid in order to minimize the thermal gradients, due to convective flow, that would be established inside the high-pressure vessel after compression or expansion. Solid samples were avoided for simplicity of this first approach. The chamber was thermoregulated (39 C) by a surrounding coil connected to a heating-cooling water bath (RB-12A, Techne, Cambridge, U.K.). Pressure was applied by a hydropneumatic pump at 2.5 MPa/s up to 400 MPa. Holding times, the time necessary to reequilibrate the vessel at 39 C, varied for each experiment. Temperature was measured in six

locations: two thermocouples were inside the chamber (at its center and at a quarter from its surface), at entrance and exit of the thermoregulating coil, inside the bath, and at an arbitrary point in the surroundings (ambient) (Figure 1). A pressure gauge (type PR811, ASCO Instruments, Chateaufort, France) measured pressure in the circuit and had been conveniently calibrated for its use in this unit. Temperature and pressure were recorded every 3 s by a data acquisition system (Fluke Helios I) connected to a computer equipped with Labtech Notebook software (Laboratory Technologies Corporation, Wilmington, MA). The model was realized using Matlab 6 software, Release 12 (The MathWorks, Inc.; Natick, MA). Modeling included thermoregulating bath, refrigerating fluid (flow, mass, physical properties), vessel steel mass, temperature at entrance and exit of the coil, and ambient temperature. These variables are usually not taken into account when modeling high-pressure systems. It was considered that heat was transmitted by convection (ambient air, fluid in bath and in vessel) and conduction (throughout the different vessel solid layers). Heat transmission standard equations were employed, taking into consideration the different layers of steel comprising the vessel, pipes, etc. Literature heat capacities and thermal conductivities were employed (9). Temperature variations with pressure were calculated as described by Otero et al. (1) and included in the model. The values of the thermophysical variables employed under pressure were calculated using the software implementation by Otero et al. (10). Simulations were performed with Simulink (The MathWorks, Inc.; Natick, MA) using Euler method and a constant size step of 1 s. This allows handling of the nonadiabatic conditions occurring in practice during compression, where a significant part of the energy of the system exits to the water bath and surroundings. Three kinds of experiments were performed to characterize the thermal exchanges in the high-pressure system: (1) Experiments To Test the Model at Atmospheric Pressure. The bath was tempered at 39 C (target temperature), and water was pumped through the coil to heat the high-pressure vessel from ambient temperature up to 39 C. (2, 3) Experiments To Test the Model under Pressure. Compression and Expansion Assays. In compression assays, once the entire system (bath and pressure vessel) was tempered at 39 C, a compression from atmospheric pressure up to 400 MPa (pressures differ in experiments) was performed. Upon compression the vessel temperature increased beyond 39 C. Pressure was hold until recovery of the initial temperature, while temperature-time data were registered. In expansion assays, once the entire system tempered at 39 C, the vessel under pressure (up to 400 MPa, start pressures differ in experiments), a quick release down to atmospheric pressure was performed. As a result of the decompression, temperature in the vessel decreased. Temperature-time data were collected until 39 C was registered again in the vessel. All experiments were performed by duplicate. Agreement between experimental and simulated temperature-time profiles was measured as the mean absolute error. Error ( ) was calculated as:

(simltd temp value - exptl temp value) 100 (%) exptl temp value (1)

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Figure 2. Model for the simulation of thermal exchanges in the complete high-pressure equipment.

When measuring error inside the vessel, two experimental temperature readings (given by two thermocouples) were considered. After verifying that their differences were lower than the thermocouple resolution, their average was taken as the experimental data to calculate error.

Results and Discussion

Figure 2 shows the model built with Matlab/Simulink to simulate the thermal exchange in the high-pressure system. The model takes into account all of the thermal exchanges taking place: (a) in the thermoregulating bath, (b) between the bath pipes and the coil surrounding the vessel, (c) between the steel mass of the vessel and the thermoregulating fluid and ambient, and (d) between the sample and the steel mass of the vessel. Also, as it can be seen in the upper left of Figure 2, the calculation of the temperature variation during the compression or the expansion was included. The model yielded the evolution of temperature with time in four points of the system (inside the high-pressure cylinder, at the entrance and exit of the surrounding coil, and inside the thermoregulating bath) provided with thermocouples to compare experimental data and simulated results. Taking into account all of these parameters allowed us to have a powerful tool to design and control the conditions of a given high-pressure treatment. Figure 3 shows the simulated and experimental timetemperature profiles inside the high-pressure vessel for a heating process from 19 to 39 C at 0.1 MPa. This was the first step to test the complete model at atmospheric pressure. Two experimental time-temperatures corresponded to data from two thermocouples inside the high-pressure cylinder (one located in its center and the other at a quarter from its surface). In Figure 3, only one solid line is seen because both profiles overlapped on time. The maximum absolute temperature difference between them was always lower than the thermocouple resolution. This fact shows the high convection existing inside the high-pressure vessel that resulted in a quasihomogeneous liquid temperature. Agreement between

Figure 3. Experimental (-) and simulated ( ) time-temperature (s-C) profiles inside the high-pressure vessel for a heating process from 19 up to 39 C at atmospheric pressure. Ambient temperature was 19 C.

simulated and experimental time-temperature data inside the high-pressure cylinder was good, and the mean absolute error was 1.1%. Compression assays showed that temperature increments in the sample after compression were significant and always must be taken into account. A larger rise in temperature after compression occurred for the largest pressure increase (400 MPa) as expected. Figure 4 shows the simulated and experimental (two overlapped curves) time-temperature profiles inside the high-pressure vessel for a compression assay from 0.1 to 400 MPa and the holding time necessary to recover 39 C in the sample. About 20 min was necessary to dissipate heat inside the high-pressure vessel and reequilibrate its temperature to 39 C. Simulated and experimental values of temperature inside the vessel and sample appear to agree satisfactorily for compression and holding times. The mean absolute error was 0.5%, and the maximum absolute error was 2.3%. A mean absolute error larger than 1% was not found in any experiment. Agreement between the simulated and experimental temperature values in

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Figure 4. Experimental (-) and simulated ( ) time-temperature (s-C) profiles inside the high-pressure vessel for a compression from 0.1 up to 400 MPa. Sample inside the vessel was liquid water that acted simultaneously as compressing fluid. The high-pressure vessel was thermoregulated at 39 C by a surrounding coil connected to a bath.

Figure 6. Simulated temperature evolution after compression from 0.1 up to 400 MPa in the water inside the high-pressure cylinder. (-) All of the high-pressure system (sample and steel mass of the vessel) was tempered at 40 C. (- -) Sample inside the high-pressure vessel was tempered at 40 C, but its steel mass is at 30 C.

Figure 5. Experimental (-) and simulated ( ) time-temperature (s-C) profiles inside the high-pressure vessel for an expansion from 400 down to 0.1 MPa. Sample inside the vessel was liquid water that acted simultaneously as compressing fluid. The high-pressure vessel was thermoregulated at 39 C by a surrounding coil connected to a bath.

the entrance and exit of the surrounding coil (mean absolute error of 0.4% and 0.5%, respectively) and in the thermoregulating bath (mean absolute error of 0.1%) was always better than inside the vessel. Figure 5 shows the time-temperature profiles for an expansion from 400 MPa down to atmospheric pressure with corresponding holding times. Again, good agreement was found between the experimental values and those given by the model. A mean absolute error of 0.4% was found in the sample, 0.3% at the entrance, 0.4% at the exit of the surrounding coil, and 0.1% in the thermoregulating bath. When high-pressure processing is applied to foods as a preservation method, temperature distribution must be determined in the food and reproduced each treatment cycle if temperature is an integral part of the HHP microbial inactivation process specification (5). This can become a difficult task if the thermal behavior of the high-pressure system is not known or controlled. Typical pressure treatment times for extending shelf life of foods oscillate between a few minutes up to half an hour. Shorter times are strongly preferred by the industry mainly because of economical limitations. As Figure 4 shows, 20 min was necessary to recover the

initial temperature in the vessel after compression. Assuming that the bath temperature was the desired condition for the treatment, the whole process would take place over this temperature. Worse results can be expected in real industry conditions, when the pressure chamber would contain a mixture of pressurizing liquid and food containers, with different thermal properties. Important thermal gradients will be established, also, among these components. Nevertheless, a model that takes into account all the thermal exchanges in the highpressure system would allow definition of the appropriate conditions to control exactly the temperature of a given treatment. Figure 6 shows the result of simulating a high-pressure treatment of 400 MPa/10 min at 40 C. Special consideration has been given to the initial temperature in the vessel steel mass (for our system, about 390 kg). Increasing its temperature from 22 C (ambient temperature) to 40 C requires around 3.5 106 J. The evolution of temperature inside the vessel after compression will depend on the temperatures of both sample and steel mass of the vessel. Figure 6 shows the temperature evolution when the starting conditions were sample and steel mass at 40 C and when they were sample at 40 C and steel mass at 30 C. Both temperature profiles evolve in different ways and in both cases out of the 40 ( 1 C threshold drawn in Figure 6, during the whole holding time. Figure 7 shows the result of simulating high-pressure treatments under three different thermal control conditions, intending to approach a temperature as close as possible to 40 C during holding time. Curve 1 shows the case in which a compression from 0.1 up to 400 MPa with a holding time of 10 min was simulated, starting from a uniform temperature in sample, steel mass, and water bath of 40 C. Curve 2 shows the same pressure process, but the starting conditions were sample, bath, and steel mass at 37 C. At the moment of compression, the target temperature in the bath was switched at 45 C. Curve 3 shows the same process and conditions, but the heating power of the bath had been increased from 900 to 1200 W. Curve 4 simulates the same process, but two baths were employed. A water bath set at 30 C was equilibrated with sample and steel mass. Then pressurization took place, and the second bath, set at 80 C, replaced the original one. The figure allows judging of the deviation from the target temperature (40 C) of the sample

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enables counterbalancing the pressure-induced temperature variation. The need to include all elements involved in the thermal regulation of a pressurization process is indication that for each particular assembly the model must be remade, taking into consideration materials, dimensions, cooling and heating power, etc.

Acknowledgment
This paper was carried out with the support of the Spanish Plan Nacional de I+D+I (2000-2003) MCYT through the AGL2000-1440-C02-01 project.

References and Notes

(1) Otero, L.; Molina-Garc a, A. D.; Sanz, P. D. Thermal effect in foods during quasi-adiabatic pressure treatments. Innovative Food Sci. Emerging Technol. 2000, 1, 119-126. (2) Shimizu, T. High-pressure experimental apparatus with windows for optical measurements up to 700 MPa. High Pressure Biotechnol. 1992, 224, 525-527. (3) Denys, S.; Van Loey, A. M.; Hendrickx, M. E. A modeling approach for evaluating process uniformity during batch high hydrostatic pressure processing: combination of a numerical heat transfer model and enzyme inactivation kinetics. Innovative Food Sci. Emerging Technol. 2000, 1, 5-19. (4) Chevalier, D.; Le Bail, A.; Chourot, J. M.; Chantreau, P. High-pressure thawing of fish (whitting): Influence of the process parameters on drip losses. Lebensm.-Wiss.-Technol. 1999, 32, 25-31. (5) Farkas, D. F.; Hoover, D. G. High-pressure processing. J. Food Sci. Suppl.: Kinetics of Microbial Inactivation for Alternative Food Processing Technologies 2000, 47-64. (6) De Heij, W. B. C.; Schepdael, L. J. M. M.; van den Berg, R. W. Increasing preservation efficiency and product quality through homogeneous temperature profiles in high-pressure application. In XXXIX European High-Pressure Research Group Meeting: Advances on High-Pressure Research, September 16-19, 2001, Santander (Spain). (7) Denys, S.; Ludikhuyze, L.; Van Loey, A. M.; Hendrickx, M. E. Modeling conductive heat transfer and process uniformity during batch high-pressure processing of foods. Biotechnol. Prog. 2000, 16, 92-101. (8) Otero, L.; Molina, A. D.; Sanz, P. D. Thermal control simulation in high-pressure treatment of foods. In XXXIX European High-Pressure Research Group Meeting: Advances of High-Pressure Research, September 16-19, 2001, Santander (Spain). (9) Haberman, W. L.; John, J. E. A. Engineering Thermodynamics with Heat Transfer, 2nd ed.; Allyn and Bacon: Boston, 1992. (10) Otero, L.; Molina, A. D.; Sanz, P. D. Some interrelated thermophysical properties of liquid water and ice I: a userfriendly modelling review for food high-pressure processing. Crit. Rev. Food Sci. Nutr. 2002, in press.

Figure 7. Simulated temperature evolution after compression from 0.1 up to 400 MPa in the water inside the high-pressure vessel. (1) The whole system was tempered at 40 C. (2) The whole system was tempered at 37 C and at the compression the target temperature of the bath was settled at 45 C. (3) The same process as curve 2 but increasing the heating power of the bath from 925 to 1200 W. (4) Two baths: one at 30 C and the other at 80 C. Initially the system was tempered at 30 C and connected at the first bath. At the compression the highpressure system was connected to the second bath.

during holding time. The last solution is the only one that maintained the sample at 40 ( 1 C during holding time. When working with solid samples, without the thermal equilibrating effect of convection, it is necessary to include a numerical conductive heat transfer model to reproduce the thermal gradients established inside the sample. This is especially important when the treatments applied involve a preservation objective. In these cases it is necessary to be sure of the entire sample mass having reached a given temperature for a given time.

Conclusions
The model presented reproduced the thermal behavior of the high-pressure system at different points satisfactorily. The agreement between simulated and experimental temperature-time profiles was good even when compressions or expansions were realized. The model described our particular high-pressure system and allowed a study of the effect of different variables implied in it (thermoregulating fluid, flow, target temperature, heating/cooling power of the bath) and its variation in order to have a better thermal control in the treatments performed. Considering not only the pressure vessel but the external thermal exchanges, the ambient and the thermoregulating system allows a realistic prediction of the possibilities of thermal control of the process and

Accepted for publication April 15, 2002. BP010157A