Freeze Concentration of Liquid Foods U.I.C.T.

, August 26, 2004
Freeze Drying and Advanced Food technology – S. A. Goldblith, L. Rey and W.W. Rothmayer

Most Liquid foods are very sensitive to thermal treatment. The components of foods are chemically unstable even at moderate temperatures. Product quality and behavioral properties depend upon hygienic processing with good microbiological control at 5-50 deg. Celsius. All aromatic compounds are naturally volatile and can be lost by evaporation. Thus, for high quality concentrates following conditions have to be fulfilled:

 Low

process temperature, short residence time and narrow residence time distribution in the process apparatus.

 Sterile operation  Selective dewatering, all components except water being retained in the concentrate.
Three concentration processes are technically feasible for selective dewatering:

 Evaporation (if necessary with aroma recovery)  Reverse osmosis  Freeze concentration
Evaporation:  In evaporation the volatile aromas are lost with the vapor and can be recovered in a distillation column.  However, the recovery is never above 50% and degradation of aroma compounds also occurs at higher temperatures. Hence the original quality is never fully restored.  Technically, however, evaporation is the best-developed process and also the most economical method of concentration. Reverse Osmosis:

It involves the use of selectively permeable membranes for removal of water. ♦ The driving force is pressure difference across the membrane. ♦ However, membranes with acceptable permeabilities are not very selective and hence the application for dewatering of aroma containing foods remains restricted to a few products. Freeze concentration: Crystal Suspension Feed Crystallizer Separator Ice

3 deg C the concentration becomes 50 wt% and 86 % of the water segregates in the form of ice. increase sharply with decreasing specific area of the crystals. Fig. of separation and especially the capacity of ice liquid separators. Crystallizer design and process conditions in the crystallizer must be directed towards the formation of large and if possible spherical crystals (Of all the geometrical shapes sphere has the least surface area).  Since water is removed from the solution by phase transformation from liquid crystal. °C fully eliminates thermal  Ice crystals of very high purity can be obtained by preventing local supercooling in  The loss of dissolved solids and of aromas is then completely controlled by the perfection of the ice-liquid separation. E.5 wt. 1 Schematic representation of a freeze concentration process  In freeze concentration water is first segregated from aqueous solution by crystallization. leaving a concentrated liquid phase. Theoretical aspects of Crystallization    Water forms a eutectic mixture with dissolved solids at the eutectic temperature. The crystallization process  Ease  The selection of crystallizer depends on the effect of crystallizer on the total cost of freeze concentration process.  The restriction to be imposed on the crystallizer is the required minimum size of the crystals. Therefore. coffee extract and some sugar solutions. by lowering the temperature of apple juice containing 12. and biochemical decomposition reactions. Graph 1 shows experimental freezing curves of a fruit juice. % dissolved solids to an equilibrium temperature of -12. aroma losses by evaporation can be completely avoided. 1.g.  The cost includes the losses of dissolved solids and losses in quality due to aroma losses. This value depends on the process for the separation of crystals and concentrate. .  The concentrated liquid is then separated from ice. the crystallizer. to  The process temperature of the order of –3 to –7 deg.Concentrate Fig. water segregates in the form of ice crystals upon cooling.  The process is suitable for sensitive liquid foods with volatile aromas.

b. mean residence time of the crystals. c. • The growth rate at low supercooling is directly proportional to bulk supercooling. lesser growth of crystals occurs with increase in residence time when bulk supercooling is decreased). the growth in crystal size is not a linear function of residence time in the crystallizer. the surface area of the crystals per unit mass of suspension will increase and hence crystal growth rate will no longer be linearly proportional to the degree of supercooling at specified residence time and rate of heat removal. 2. Combining the above 2 points. instead. if large number of viable crystals are born. dissolved solids concentration (ref.e. Net Nucleation rate  The nucleation rate of ice in liquid foods and in sugar solutions increases with increasing dissolved solids concentration and is proportional to square of bulk supercooling. • At a given rate of heat withdrawal per unit mass of suspension . . low birth rate of viable crystals). Less dependent on the degree of turbulence in the crystal suspension. the mean size of the crystals is primarily dependent on a. Bulk supercooling and d. graph 2). high supercooling needed for high crystal growth rate can only be maintained if the total area of crystals per unit mass of suspension is low. Crystal Growth Rate In continuously operating crystallizers.e. • A lesser than linear effect of residence time on the crystal size can be effected by decreasing the bulk supercooling with increasing residence time of the crystals at constant crystal concentration in a given crystallizer (i. • Obtaining large crystals at an acceptable residence time dictates low net nucleation rate (i. • The method of cooling strongly influences the crystal growth rate and mean crystal size as demonstrated by graph 3.1.

Advantages of direct cooling over indirect cooling:  It eliminates cooling wall and consequently the use of expensive scraped surface heat exchangers. The V.  For large evaporation plants with vapor compression. a bulk temperature will be established between the lower melting temperature of the small crystals and the higher melting temperature of the large crystals. Technical Crystallizers a.  Since the bulk temperature is higher than the melting temperature of the small crystals.  Very few nuclei formed in the cold spots survive the mixing process due to their lower melting temperatures than the larger ones.  The nucleation rate and the degree of supercooling of the cold spots can be decreased by increasing the stirring rate in the crystallizer.V.  The growth of larger crystals at the expense of smaller crystals is known as ripening effect. Crystallizers with direct heat removal:  In vacuum freezers for liquid foods the crystallizing solution boils at an absolute pressure of about 2 mm Hg. will grow  (ref. Disadvantages of direct cooling .  The large crystals. Externally cooled crystallizers a.  Very low energy consumption can be achieved by compressing the water vapor from 2 mm Hg to about 7 mm Hg and using the separated ice crystals as condenser for the compressed vapor.  The melting rate of the subcritical and the growing rate of the supercritical crystals increase with an increase in size difference between the small and large crystals. Crystallizers with indirect heat removal 1.F.  These cold spots contribute much more to nucleation than to crystal growth. (Vacuum Freezing Vapor Compression) process has not yet been applied for freeze concentration of liquid foods.C. these will melt. Internally cooled crystallizers 2.  The size of melting crystals in an adiabatic crystal suspension is called subcritical and that of the growing ones supercritical. on the contrary.  Upon mixing a suspension of small and large crystals. power requirements as low as 8 kWh per 1000 Kg separated ice are reported. graph 4 that shows effect of crystal diameter on melting temperatures). Due to the heat withdrawal from the crystallizer and imperfect mixing of the suspension. 3. Crystallizers with direct heat removal b.  Direct cooling has been extensively studied for seawater desalination. spots with supercooling below the bulk supercooling are formed.

 The advantages of low capital and energy costs have to be balanced against a somewhat lower quality of the concentrated product compared with the quality of concentrate obtained from indirectly cooled crystallizers. aroma losses can be recovered by counter-currently stripping the gas-vapor mixture leaving the condenser with the concentrated liquid leaving the iceconcentrate separator. aromas can be lost. Recovery of Aroma: For most fruit juices.  With the inert gases leaving the vacuum crystallizer. Wet compressor Atmospheric Pressure Inert Gases S T R I P P E R 2 . the aromas will not be condensed in the condenser and will only be removed from the gasvapor mixture by the liquid in the aroma absorber. If the temperature of the condensers is not too low and part of the non-condensables leaving the first section of the aroma absorber are re-circulated through the condenser.

There are 2 classes of crystallizers with indirect heat removal: . So far. Crystallizers with Indirect heat removal. Crystallization b. only indirectly cooled crystallizers have found application in the food industry.DRY COMPRESSOR Water Vapor + aroma CONDENSER S T R I P P E R 1 Concentrate + aroma Inerts + Aroma Concentrated Liquid Feed 2 mm Hg Ice Ice Separator Vacuum Flowsheet of vacuum crystallizer with aroma recovery.

In crystallizers of the first group the liquid is. v. since the crystals are very small. ii. However. Withdrawal of heat through the wall of the crystallizer (Internally cooled crystallizers). b. are taken in the Union Carbide Process which involves the production of large crystals by using a cascade array of crystallizers-separators. contacted with a refrigerated wall. it is mechanically removed in solid slabs as a ‘snow’. turbulence and crystal concentration. Their horizontal scraped surface tubular heat exchanger has an inside diameter of 14 inches. A total residence time of 1. the crystals are produced in horizontal scraped surface heat exchangers. e. The crystal suspension remains only a few minutes in the crystallizer. Most internally cooled crystallizers belong to the second group and produce pumpable suspensions. In another version. Short residence times are also employed in the Gasquet process. Because of the short residence time the product crystals are small.i. d. i. . Struthers advocates the use of stirred but non-scraped indirectly cooled crystallizers. In this way.% alcohol. Longer residence times. and upon complete solidification. and is removed as flaked ice. The crystals formed in the heat exchanger are recirculated through a holding or ripening tank. without stirring. An advantage of this process is simplicity. ii. The nuclei are formed on the cooled wall. The solid layer is removed continuously by a scraper knife. less than 50 microns. driving force. the liquid is sprayed onto a slowly revolving drum or onto internally refrigerated discs. 1. iii. a. and the crystals grow in the slowly stirred bulk of the suspension. the liquid-ice separation poses certain difficulties. It consists of a large stainless steel drum internally cooled and rotating in a trough of the liquid to be concentrated. Example of this type of crystallizer is the Linde-Krause crystallizer. even very dilute solutions can be concentrated in one step to 40 wt. f. Internally cooled crystallizers This class can be divided into crystallizers producing almost completely solidified suspension and a group producing pumpable slurries.% or more. upto several hours.0 wt. g. c.% to 6. vi. Large crystals are obtained by closely controlling temperature. Heat removal from the feed stream to the crystallizer externally (Externally cooled crystallizers). iv. The residence time of the crystals is about 3 h. The crystal suspension remains only a few minutes in the crystallizer.3 h gives spherical crystals with a size ranging from 0.4 to 2 mm while concentrating beer from 3. In yet another process advantage is taken of the ripening effect. In the votator process. Daubron employs vertical ammonia jacketed scraped cylindrical vessels.2 wt.

% glucose solutions.  Strong supercoolings upto 6 deg C appear to be feasible.5h. In the second type. fig.2 mm are obtained with a mean residence time in the crystallizer of only about 0.  In 30% wt. i.  Residence time in the heat exchanger is shorter than in the crystallizer. c. . crystals of about 0.  The liquid from the crystallizer can be recycled to the heat exchanger. iii. b.  Thus the crystal growth occurs mainly in the crystallizer.  Sepial uses a cascade of two internally cooled crystallizers. Recirculation of the whole suspension from the crystallizer to the heat exchanger. Crystallizers producing subcritical crystals in an external heat exchanger. 3). a. If crystallization occurs in the heat exchanger it may block the liquid path in the heat exchanger. local supercoolings in the crystallizer can virtually be suppressed.  Crystal free liquid is partly recirculated from the crystallizer to the heat exchanger. Supercooling of the feed stream in a heat exchanger before it enters the crystallizer. Externally cooled crystallizers This class of crystallizers can be subdivided into three main types.  The heat flux through the wall of the scraped heat exchanger is taken very high which results in a very strong nucleation.  The wall of the heat exchanger is highly polished or coated with a hydrophobic plastic to minimize the chance of primary nucleation and crystallization in the heat exchanger. the whole suspension from the crystallizer is recirculated to the heat exchanger. The crystals are retained in the crystallizer by means of a filter in the suction line.  Using this type of crystallizer.  Lurgi (a firm) uses a scraped surface heat exchanger. ii. The third type of crystallizer produces subcritical crystals in an external heat exchanger (ref. The slurry leaving the heat exchanger is gently mixed with the suspension in the crystallizer. The supercooled crystal free liquid releases its cold in the crystallizer. The majority of the ice crystals are formed in the first crystallizer.2. In the first type. and the crystals are grown to the desired dimensions in the second stage. the feed stream is supercooled in a heat exchanger before it enters the crystallizer.

4. or least partial separation. amounting to less than 0. The extremely small crystals produced in the heat exchanger are fed continuously to the crystallizer. Centrifuges:  The dissolved solids losses in centrifuges are lesser than those in presses.  The larger crystals grow at the expense of the melting of the small crystals. In all separators  the capacity is inversely proportional to the viscosity of the liquid  the capacity is directly proportional to the square of the mean diameter of the crystals.02 deg C.  At a residence time of about 2h. presses can only be used to increase the ice content of the slurry before final complete separation of ice and liquid is effected. spherical crystals of about 1mm are grown from 40 wt% sucrose solution. The heat of melting of the small feed crystals is consumed by the growing large crystals.  At pressures above 100 Kg/cm2 and with long compression times.  Because of these high losses. The separation.  Due to the long residence time in the crystallizer the bulk supercooling is small. Ice-Concentrate Separators Presses Centrifuges Wash Columns Combination of presses and wash columns 1. the amount of occluded liquid can be reduced to about 0. . 2.1 kg/kg ice.  At pressures upto 10 kg/cm2.65 kg remains occluded per kg ice. wash columns. The cost of freeze concentration is strongly affected by the fractional loss of dissolved solids with the ice. Presses: Hydraulic piston presses and screw presses are used in the separation process. where the residence time is at least half an hour. or a combination of two of these devices. The residence time of the crystals in the heat exchanger is only a few seconds. filtering centrifuges.  The loss of dissolved solids is determined by the amount of liquid that remains occluded in the compressed ice cake. The wash water will of course dilute the concentrate. 3. about 0.  The filter cake in the centrifuge can be washed with water or crystal melt. 4.  An increase in the nucleation rate in the heat exchanger causes an increase of the mean diameter of the product crystals. can be performed in presses.

 The diluted ice suspension is completely separated in the wash column.  The liquid separated from the ice in the wash column is fed to the crystallizer.  In continuously operating wash columns the crystal suspension is fed in at one end of the column. Depending on the crystal size and liquid viscosity the loss can be as high as 10% of the solids in the feed.  The concentrated liquid is removed from the column through a filter near the same end by expressing the slurry.  The depth of the region between the part of the bed with still undiluted liquid and the part of the bed with purified crystals is only a few centimeters. The liquid is thereby brought into intimate contact with excess of air.  Wash columns are completely closed and operate without a gas headspace. aroma losses are almost negligible.  In the column the crystals are washed countercurrently with the wash liquid obtained by melting part of the purified crystals leaving the column. Combination of press and wash column (ref. 4). Hence. . fig.  In case of stable displacement of a concentrated liquid the concentration of dissolved solids in the melt of the ice crystals leaving the columns is generally lesser than 10 ppm.  The compact bed of crystals is forced to move towards the other end of the column where the crystals are removed.  The concentrated slurry leaving the crystallizer is partly separated in a press.  The ice cake still containing about 40 wt% occluded concentrate is then dispersed in the feed to the system. Wash Columns: Wash columns facilitate perfect separation of ice and liquid with out any dilution (ref.  Volatile aromas are lost when the liquid is spun off from the filter cake. 5):  It is the most economic process. fig.

The superior quality of freeze concentrated foods has to be paid for by higher dewatering costs. . c.a. 5. b. Higher concentration requires an extra freezing step and thus the cost of concentrate increases. Conclusions: Food liquids can be concentrated economically up to 40-50 wt% dissolved solids in one stage. d. being about a factor of 2 higher than the dewatering costs of evaporation with aroma recovery. The maximum obtainable concentration is controlled by the viscosity of the concentrated product at freezing temperature.

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