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Crystallization and Drying of Milk Powder in a MultipleStage Fluidized Bed Dryer

Nima Yazdanpanah & Tim A. G. Langrish
a a a

Drying and Process Technology Group, School of Chemical & Biomolecular Engineering, The University of Sydney, New South Wales, Australia Version of record first published: 27 Jun 2011.

To cite this article: Nima Yazdanpanah & Tim A. G. Langrish (2011): Crystallization and Drying of Milk Powder in a MultipleStage Fluidized Bed Dryer, Drying Technology: An International Journal, 29:9, 1046-1057 To link to this article: http://dx.doi.org/10.1080/07373937.2011.561461

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Drying Technology, 29: 10461057, 2011 Copyright # 2011 Taylor & Francis Group, LLC ISSN: 0737-3937 print=1532-2300 online DOI: 10.1080/07373937.2011.561461

Crystallization and Drying of Milk Powder in a Multiple-Stage Fluidized Bed Dryer

Nima Yazdanpanah and Tim A. G. Langrish
Drying and Process Technology Group, School of Chemical & Biomolecular Engineering, The University of Sydney, New South Wales, Australia

The rationale of this study has been to use uidized beds to crystallize amorphous spray-dried skim milk powders with multiple stages of processing at different temperatures and humidities with the aim of rapidly making mostly crystalline powders. This paper discusses the performance of a multiple-stage uidized bed dryer, and a combination of crystallization of lactose in spray drying at high humidity (lactose nuclei formation) and subsequent uidized bed drying. Two different combinations of spray dryer and multi-stage uidized-bed dryer have been suggested to crystallize lactose in skim milk powder. The results show signicant improvements in the crystallinity of the powders. Moisture sorption test and X-ray diffraction analysis were used to assess the crystallinity of the powders. The processed powders that were crystallized in a humid-loop spray drying combined with a two-stage uidized-bed dryer/crystallizer showed 92% improvement in lower amorphicity by processing at different stages of 70 C, 50% RH and 80 C, 50% RH for 15 minutes. The conventionally spray-dried powders that were crystallized in a three-stage uidized-bed dryer/crystallizer showed 87% improvement in lower amorphicity (less moisture sorption) by processing at different stages of 60 C, 50% RH; 70 C, 40% RH; and 80 C, 40% RH for 20 minutes. The multiple-stage uidized bed system showed distinctive potential to crystallize lactose signicantly in skim milk powder using an industrial-feasible process. Keywords Crystallization; Fluidized-bed dryer; Lactose; Milk powder; Spray drying

INTRODUCTION An important application for studying the solid-phase crystallization process in spray and uidized-bed drying is the production of milk powder in an industrial process conguration. Spray drying is a very signicant part of milk powder production where most of the powders specications and properties are determined to a large extent,[13] while post processing in uidized beds could modify them. Although the main morphological structure forms in the spray-drying chamber, uidized bed drying has the potential to improve powder crystallinity.[46]
Correspondence: Nima Yazdanpanah, Drying and Process Technology Group, School of Chemical & Biomolecular Engineering, The University of Sydney, New South Wales, Australia; E-mail: nima.yazdanpanah@sydney.edu.au

More than 3.5 million tonnes of milk powders were produced in the year 2009, and 2.8 million tonnes were exported from main producer countries such as Australia and New Zealand, which export 45% of the total world milk powder market. Processing, storage times, and handling of these spray-dried powders are very sensitive to the storage conditions, due to the presence of amorphous lactose in spray-dried milk powders that are produced by conventional drying facilities. The physical and thermodynamical states of milk powder, like the crystallinity of the powders, strongly depend on the process conditions, which can cause unstable powders. The unstable state of powders (amorphicity) causes some changes during storage, such as stickiness, caking, degradation, and nonenzymatic browning.[7,8] The transition from an amorphous solid-state to a viscous rubbery state occurs at the temperature known as the glass-transition temperature (Tg). The presence of plasticizers, moisture in this case, reduces the glass-transition temperature, and the crystallization of lactose occurs at temperatures that are above the glass-transition temperature.[911] Among the different ingredients of milk powders, amorphous lactose is the most hygroscopic and unstable material. By sorbing moisture, the amorphous lactose becomes sticky, and forms bridges with other particles that leads to caking, forming a product that is non-free-owing and difcult to handle.[12] Lactose is more stable in the crystalline alpha monohydrate form; and crystalline lactose or crystallized lactose-containing powders are free-owing and have little tendency to agglomerate. With the presence of sufcient moisture in powders, this transition can take place during spray drying and=or uidized-bed drying when the process temperature is much higher than the glass-transition temperature. Therefore, the powders can be dried and crystallized simultaneously. Many researchers have recommended that the amorphous-lactose fraction could be treated in a crystallization facility after spray drying to crystallize lactosecontaining powders, thus improving the physical properties of powders such as caking and agglomeration.[4,5,13]

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Yazdanpanah and Langrish[4] have suggested continued crystallization in a uidized bed dryer=crystallizer after spray drying of skim milk powders; and Hynd[14] has suggested a belt crystallizer after spray drying for whey powder. Currently, uidized-bed processing is widely employed after spray drying in dairy processing to agglomerate, instantize, and dry powders where it may be possible to perform further crystallization. Most of the research thus far has been aimed at post-crystallizing whey powders,[5,14] or pre-crystallizing them by high shear forces,[15] but the recommended processes were time-consuming and may not be suitable for industrial applications. Fluidization of amorphous powders is very sensitive to process parameters like temperature, air velocity, and humidity.[5,16] A signicant problem with the uidization of milk powder and other lactose-containing powders using hot humid gas is the stickiness of powders. A commonly found problem is the collapse of the bed being processed at high relative humidities, resulting in cake formation from the cohesion of all the particles in the bed and increased stickiness of amorphous powder at elevated humidities.[17,18] Although the highest temperature and humidity give the greatest crystallinity in the least time,[10,19] it is not possible to uidize hygroscopic=amorphous lactosecontaining powders at these high temperatures and high humidities. For instance, Ibach et al.[19] demonstrated that whey powder can crystallize at a relative humidity of 85% and a temperature of 100 C in just 1 minute, while Nijdam et al.[5] showed that it was impossible to uidize whey powder under those conditions. However, the upper limit of processing at high temperature and humidity depends on the amount of amorphous component in the powders. Therefore crystalline powders or partially crystallized powders from spray drying can be uidized at higher temperatures and humidities that boost the crystallization rate and reduce the processing time. In recent work, highly humidied hot air was used to crystallize lactose and lactose in skim milk powders in a vibrated uidized bed;[4] however, the one-hour processing time is not sufciently short for industrial interest. The powders that were crystallized by that technique showed a high degree of developed crystallinity. Recently Islam et al.[20] have suggested a new technique called Humid Loop to spray-dry lactose, which uses highly humid air to obtain highly crystalline lactose from spray dryers. Although the effects of other components, like proteins, on the crystallization rate, kinetics, crystal shapes, and distributions have not been explained yet, this technique could also possibly apply to other lactose-containing powders. GEA=Niro is proposing a similar closed-cycle layout for solvent recovery using nitrogen. Although the conguration is similar, the process conditions and aims are different, and the conditions are unlikely to lead to the crystallization of amorphous solids.[21]

This work investigates the crystallization of milk powder in a multiple-stage uidized-bed system and combined multiple-stage uidized-bed system with spray drying of milk in hot humid air. The aim of this paper is to attempt to crystallize amorphous lactose in milk-powder drying, improving physical properties in a timely process with an industrial approach. MATERIALS AND METHODS Commercial Skim Milk Powder (CSMP) Skim milk powder (Coles, New Zealand, Batch No 9199) with 4.1% w w1 moisture (dry basis) and an average particle size of 120 mm was used as a reference material, being a typical commercial skim milk powder (CSMP). This material was compared with the products of this experiment. Fresh Liquid Skim Milk, 35% (W W1) Concentrate Skim Milk Slurry and Fresh Spray-Dried Milk Powder Concentrated milk (3045% solid content) that is prepared by falling lm evaporators is used in dairy plants to feed industrial spray dryers.[22] To mimic the industrial conditions and to obtain larger particles, the concentrated feed for spray drying was prepared by reconstitution of fresh spray-dried milk powder to particular concentrations. Results of recent publications regarding the surface composition of spray-dried milk powder[2] show that the re-spray drying of reconstituted solutions maintained the characteristic physical properties of fresh milk. Fresh skim milk (0.1 g fat.100 mL1 from local suppliers, Coles, Australia) was fed into a Buchi B-290 spray dryer (Buchi Labortechnik, Switzerland) with an inlet air temperature of 140 C and an outlet air temperature of 67 C. The powders were collected from the collection vessel at the bottom of a cyclone and immediately reconstituted with distilled water at 25 C to a concentration of 35% w w1. This reconstituted slurry was fed again to a Buchi B-290 spray dryer (Buchi Labortechnik, Switzerland) with an inlet air temperature of 140 C and an outlet air temperature of 79 C. The powders were collected from the collection vessel at the bottom of a cyclone and were immediately fed to the uidized-bed dryers for the experiments. Moisture Sorption Tests Moisture sorption behavior was studied with two repeat samples of the CSMP, powders produced from conventional spray drying (lab scale) and processed powders from the proposed set-up. A mass of 11.5 grams of the powder was placed on a 10-mm-diameter borosilicate glass Petri dish with a nearly monolayer particle thickness, and the mass change as a function of storage time was recorded once per minute over a period of two to three days to reach a constant mass by using an analytical balance (0.0001 g,

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Mettler Toledo, AB 204-S, Switzerland). The sample and the balance were placed in a sealed sorption box where the relative humidity (7075%RH) and the temperature (24.525 C) were kept constant using a saturated salt solution of sodium chloride and electric light bulbs, respectively. The levelling off of the curve indicates the end of the crystallization process.[23] Oven Drying The free moisture content (dry basis) was measured by weighing 3 g of a sample before and after drying in an oven (Labec, Australia) at 85 C for two days. The skim milk was dried at a temperature of 85 C, as suggested by DIN 10321, instead of 102 C as suggested by IDF standard 26A:1993, to prevent degradation and browning of the skim milk powder.[24,25] The measured moisture content of the skim milk were adjusted by adding 0.371% (w w1) to the moisture content determined by the decrease in mass, to compare with moisture contents of material dried at 102 C, as recommended by De Knegt and Van Den Brink.[26] Each test was carried out in duplicate. Scanning Electron Microscopy A scanning electron microscope was used to observe the powders in terms of the surface and bulk structures. The samples were prepared by placing a small amount of sample on a carbon tape that was placed on an aluminium sample disc. The sample was coated by a standard 30 nm gold layer to produce the conductive surface (Emitech, K550X, Quorum Technologies, UK). The electron micrographs were produced using a Zeiss ULTRA plus (Carl Zeiss SMT AG, Germany) scanning electron microscope (SEM) in secondary electron mode with operating conditions of 5 keV. A range of 500 to 70,000 times magnication was used in the images. X-Ray Diffraction (XRD) X-ray Diffraction (XRD) was conducted using a Siemens D5000 diffractometer. The scanning range was set to 550 , the step size was 0.02 with a scanning rate of 1 step=s, and the operating conditions were 40 kV and 30 mA. EVA evaluation program (DIFFRAC Plus, Bruker analytical X-ray system, GmbH) was used for peak searching as part of quantitative crystallinity analysis. PROCESS (DRYING/CRYSTALLIZATION) SET-UP Actual Laboratory Fluidized Bed Set-Up (One Module) The same uidized bed dryer=crystallizer apparatus that was used for the previous study was employed here.[4] A vibrated uidized bed (Fig. 1 has been used to uidize the powders with hot humid air. A variable speed centrifugal fan (0.75 kW motor and 50 cm fan diameter, Western Electric Australia, ABB speed controller), a counter-current

FIG. 1. A schematic diagram of the uidized-bed system (one module) taken from Yazdanpanah and Langrish.[2]

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humidier column (a packed-bed vessel with circulating hot water (Thermoline, Australia), constructed in our laboratory), and a 1 kW electrical heater coil (constructed in our laboratory) have been used to generate the hot humid air. The supplied air was able to be conditioned to have a temperature range from 25 to 100 C, a relative humidity from 10 to 95%, and a uidization air velocity within the uidization column from 0.1 m s1 up to 5 m s1 at ambient conditions. The inside diameter of the uidized bed column is 100 mm with a height of 50 mm. A stainless-steel mesh (45 mm) plate with a diameter of 100 mm (Endecotts, UK) has been used as a bed support (air distributer). A small vibrated motor (IKA-werk, Germany) with a 2 cm unbalanced crankshaft was joined to the column and used to agitate the bed at 500 Hz to break up the channels in the bed during processing and create smooth uidization. The uidization column wall and bed support have been made from stainless steel. Heating insulation has been used on all pipes and connections between the humidier, the electrical heater, and the uidized-bed chamber and uidized-bed body. Five RTD thermocouples (Pyrosales, Australia) have been connected to the system to measure the temperature of the humidier, the air heater, the inlet uidization air (dry-bulb), the wet-bulb temperature of the inlet air to the uidization chamber and the outlet air. All sensed temperature data were transferred to a computer by a data logger (Datataker DT-505, Datataker Pty Ltd, Australia). The dry-bulb and wet-bulb temperature of the uidization air have been reported here. The wet-bulb temperatures of the inlet air were measured, and the dry-bulb temperature of the outlet air was also measured. No signicant temperature difference was noticed between the inlet and outlet dry-bulb temperatures in the well-insulated short uidized bed. No signicant differences were found between the inlet and outlet wet-bulb temperatures, because typically 1 g of moisture was adsorbed or desorbed in a 20-minute period, during which 2.3 kg of air (0.2 m=s through 10 cm diameter bed during 20 minutes) owed through the bed. The whole set-up was run for two hours to reach steady state (temperature and humidity) before

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feeding the powders, and all inlet process variables were normally kept constant during each experiment. The aeration time for uidizing the samples was up to one hour, and during this time material was well agitated with continuous vibration. Actual Laboratory Spray Dryer As the conventional spray-dryer method (lab scale), a Buchi B-290 mini-spray dryer (Buchi Labortechnik, Switzerland) with an inlet air temperature of 140 C, an outlet air temperature of 79 C, a feed pump rate of 25% (8 mL min1), and an aspirator rate of 80% (28 m3 h1), a rotameter setting of 55 mm (1 m3 h1) for the atomizing air ow, was used to dry a 35% concentrate solution of milk=s. This set-up was used to directly feed the multiple-stage uidized-bed dryer. To partially crystallize milk powder by spray drying with high humidity air, the same spray dryer was retrotted with a closed loop for the inlet=outlet air through a Humid Loop. This Humid Loop has been described in the work of Islam et al.,[20] and it allows high humidities to be controlled during spray drying and crystallization. The dryer was allowed to reach steady state for both humidity and temperature for at least 30 minutes with water spraying before the concentrated milk was sprayed. The exhaust gas was re-circulated to the dryer inlet after passing through the uidized-bed dryers=crystallizers and condenser unit. The cooling water ow rate (% 90 ml min1) through the copper helix coils within the condenser unit was controlled at such a rate that the relative humidity of the air into the spray dryer was %7580%. Potential Industrial Combined Process Set-Up Many combined congurations of spray drying and uidized bed drying equipments are being used in milk powders plants[22] and other drying facilities. These combined congurations have been suggested to improve the quality of products, to ease drying process, to reduce energy consumption, and to have better process control.[2730] Figure 2 shows a possible conguration of the crystallization system for continuous drying and crystallization of 35% concentrated milk solution with partial crystallization in a Humid Loop spray drying and two-stage uidized bed. The process included a common spray dryer that sucks the inlet air (drying air) from the condenser that controls the humidity of the Humid Loop, and two modules of uidized beds that crystallize lactose in milk powders by post-processing of spray-dried powders. Different combinations of temperature and humidity were used in each module so that the last stage was working at the highest temperature and humidity. The concept of using the different stages of crystallization and the different settings of temperatures and humidities will be explained in the following section. The partial crystallization of lactose in

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FIG. 2. A schematic diagram of milk powder drying and crystallization in a closed cycle with a two-stage uidized-bed system.

milk powder that had been done in the spray dryer chamber (with a Humid Loop) was continued with two stages of solid-phase crystallization in uidized beds. It is also possible to avoid using a Humid Loop, produce totally amorphous milk powder by spray drying, and then crystallize lactose in milk powder by three modules of uidized-bed dryers=crystallizers with different sets of temperature and humidities for a continuous process (Figure 3). In this case, the partial crystallization of lactose in the spray dryer will not occur and raw amorphous milk powder from the spray dryer will be crystallized in the three-stage uidized-bed crystallizer. Different numbers of processing stages with various processing conditions were tested to achieve maximum crystallinity in milk powders. It was found that the minimum number of effective processing stages to crystallize lactose in milk powder to the most crystalline state in the shortest possible processing time was three stages with the proposed temperatures and humidities shown in Table 1. The sizes of the uidized beds depend on the outlet powder ow rate from the spray dryer and the residence time needed for crystallization. At an industrial scale, these

FIG. 3. A schematic diagram of milk powder drying and crystallization in a three-stage uidized-bed system.

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TABLE 1 Process conditions in the different sections of the conventional milk powder production=crystallization with a three uidized-bed crystallizer module Process temperature ( C) Spray dryer Fluidized bed 1 Fluidized bed 2 Fluidized bed 3 Cooler Drying air 160 60 3 70 2 80 2 25 Air relative humidity (%) Inlet air 55%@25 C 50 1 40 1 40 1 55 Residence Material inlet moisture Material outlet moisture time (min) content (%,w w1) content (%,w w1) 10 5 5 5 5.6 0.2 7.9 0.2 5.2 0.1 4.0 0.1 5.6 0.2 7.9 0.2 5.2 0.1 4 0.1 3.7 0.2

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dryers are not separate, and the stages are combined into one body that is separated by internal bafes that allow zones with different operating conditions for step-wise crystallization. The nal uidized bed cooler just decreases the powders temperature and has no signicant effect on the powder moisture content and=or crystallinity. Processing Conditions Fluidization Limits Due to the hygroscopic nature of amorphous lactose, lactose-containing materials become sticky when exposed to humid environments. This sticky behavior causes problems in uidization with hot=humid air, and it is impossible to achieve smooth uidization for all temperatures and humidities.[31] The upper limit of uidization depends on the percentage of crystallinity in the powders, therefore (for a given particle size) the worst uidization corresponds to the highest amorphicity in the powders, while crystalline milk powder has very smooth uidization at high temperatures and humidities.[4] This problem is the main reason for splitting the processing time into different modules to maximize the crystallization rate by maintaining an adequately high differential temperature (TTg) in different stages corresponding to different amounts of amorphicity in the powders, which achieves a greater degree of crystallinity in less time. Different uidization ability may occur for different amounts of crystallinity in the powders, so in the uidization=crystallization process, the humidity and temperature can be increased as a function of time while the crystallinity of powders is developing. If the partial crystallization of milk powders is carried out in the spray-drying chamber, the produced powder is more easily uidized at relatively higher temperatures and humidities. Therefore the initial stage of uidized-bed processing could be performed at higher humidities or temperatures compared with raw powders from conventional spray dryers. Many researchers have studied the sticky behavior of food powders.[16,32] Hennings et al.[16] found that, at a certain relative humidity, the temperature of skim milk

powder could be 25 C more than the glass-transition temperature of lactose before the powder became sticky. These values are valid for mostly amorphous powder. The partially-crystallized powders have higher sticky-point temperatures.[33] The uidized-bed crystallizer can be fed by higher temperature= humidity air, and therefore one uidization stage can be omitted. The process complication and number of required uidized-bed dryers depend on the uidization ability and crystallinity of the powders from the spray dryer. The powders from conventional spray drying are more amorphous, and these powders need to be processed in three-stage uidized-bed dryers with a high residence time, while partiallycrystallized powders from the Humid Loop spray drying may be processed in two stages and with shorter times. The process pathways and uidization abilities of different powders are shown in Figure 4. The bold continuous line in Figure 4A (left line) presents the upper limit of uidization for the raw amorphous milk

FIG. 4. The upper limit on the relative humidity for which different types (crystallinity) of skim milk powder can be uidized and the process pathways around different stage of crystallization=drying. A) Fluidization of conventional spray-dried powders in three stages, B) Fluidization of Humid Loop spray-dried powders in two stages.

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TABLE 2 Process conditions in the different sections of the combined crystalline milk powder production with a two uidized-bed crystallizer module (Humid Loop) Process temperature ( C) Spray dryer Fluidized bed 1 Fluidized bed 2 Cooler Drying air 140 70 2 80 2 25 Air relative humidity (%) Inlet air 7580% @45 C 50 1 50 1 55 Residence time (min) 10 5 5 Material inlet moisture content (%,w w1) 8.8 0.2 6.5 0.2 4.1 0.1 Material outlet moisture content (%,w w1) 8.8 0.2 6.5 0.2 4.1 0.1 3.8 0.1

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powder at the corresponding temperatures and humidities while the bold dashed line in Figure 4A (top line) represents the upper limit of uidization of the mostly crystalline milk powder. The two dashed lines between these two upper limits are representative limits for partially crystallized powder with some percentage improved crystallinity during the process. The safe process conditions of temperature and humidity to keep the bed well uidized and avoid cake formation should be below these upper limits. The process path shows the initial conditions for processing and the changes in different stages. Figure 4B shows the partially crystallized powder in Humid Loop spray drying has higher initial upper limits of uidization due to the lower amorphous contents. Murti[34] used a similar concept to assess the stickiness of milk powder by using a particle gun. Process Set-Up Tables 1 and 2 show some typical experiments performed for this study. In this experiment, a batch-wise uidized bed was used, but the results are likely to be valid for continuous processes, especially at industrial scale, where plug-ow uidized-bed dryers are used, so that the batch time here is equivalent to the residence time in the continuous process. RESULTS Surface Morphology SEM micrographs show some morphological changes for skim milk powders after processing in the uidized beds at different humidities and temperatures. Crystallized lactose appeared to be formed on the surface and inside of the particles. Figures 5 and 6 show the different powders before and after processing (crystallizing) by hot humid air in a uidized-bed dryer. The surface of the raw milk powders (produced by conventional spray drying) appear to be untextured and amorphous (Fig. 5A), while the processed milk powders have heavily textured appearances, suggesting that the particle is crystalline. Furthermore, no crystalline lactose or lactose crystal nuclei appear on the surfaces of the raw conventional spray-dried milk powders

(Fig. 5A), while the surfaces of the spray-dried powders from a Humid Loop (Fig. 6A) contain some lactose crystal nuclei that show partial crystallization of lactose during drying with hot humid air. As Figure 5B shows, ne and uniform (approximately 200 nm) lactose crystals have appeared inside and on the surface of the processed powders from conventional spray drying after processing in a three-stage uidized-bed dryer. The processed powders from a three-stage uidized bed contain very crystalline structures throughout the particles that show deep moisture penetration into the particles and uniform crystallization of lactose in milk powder particles (Fig. 5B). On the surface of the spray-dried powders in a Humid Loop, after being processed with hot humid air in a two-stage uidized-bed dryer=crystallizer, some large lactose crystals were formed along with the smaller lactose crystals. Large lactose crystals possibly were formed from already developed lactose nuclei or from highly saturated regions of lactose due to the higher initial moisture contents of the powders from the Humid Loop. The partially crystallized powders from a Humid Loop have higher moisture contents and lower glass-transition temperature; this could cause more crystals to grow in shorter times or easier molecular movement in wet solid structures to form bigger crystals. Spray drying of powders in a Humid Loop needs to be precisely controlled to give ne and uniform

FIG. 5. A) Surface of raw skim milk powder (amorphous) produced in a conventional spray-drying process at a high magnication (scale bar 200 nm). B) Morphological structure of powder from conventional spray-dried powder after processing in a three-stage uidized bed dryer= crystallizer for 20 min (scale bar 1 mm).

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FIG. 6. A) Surface of raw skim milk powder (partially crystallized) produced in a Humid Loop (scale bar 1 mm). B) Surface of processed powder from partially crystallized particles in a Humid Loop after processing in a two-stage uidized bed dryer=crystallizer for 15 min (scale bar 1 mm).

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lactose nuclei. This technique has already demonstrated the ability to make large lactose crystals.[20] The crystal formation and crystallization control in such a highly humid drying media are under development and further approaches to control crystal formation in spray drying could help to produce uniform lactose crystals after processing in uidized beds system within the combined method. Moisture Sorption Tests It has been established[23,35,36] that the moisture adsorption peak heights (changes in moisture content, % (100 kg kg1 dry basis)) can be used to represent the extent of amorphicity in the samples. The net percentage changes in mass (dry basis) as a function of time for raw milk powder (from conventional spray drying, curve 1), CSMP (commercial reference sample, curve 2), partially crystallized powder in a Humid Loop (curve 3), and processed powders in the three (curve 4) and two-stage (curve 5) uidized bed are displayed in Figure 7. The peak height (the height between the peak and the plateau of the crystallization process) represents the amount of sorbed moisture by amorphous materials, which characterizes the degree of amorphicity for lactose in that material. There were signicant changes between different samples that were processed (crystallized) at different humidities and temperatures in the uidized bed dryer= crystallizer. The rst curve (highest peak) is the moisture sorption by raw skim milk powder from conventional laboratory spray drying, which was mostly amorphous. The highest peak shows the greatest amorphicity compared with the other samples. The second curve (Fig. 7, curve 2) shows lower moisture sorption by commercial skim milk powder (CSMP), which could possibly be due to developing the extent of crystallinity in some ingredients during drying or other deteriorative changes after drying or during the storage period (such as the Maillard reaction and aging). This situation could have occurred during largescale industrial spray drying or during post processing (belt

FIG. 7. Moisture sorption tests for different types of raw and processed skim milk powders (sorption test environment was at a temperature of 25 C and 75% relative humidity).

dryer, agglomeration, or uidized bed dryer=cooler) in a dairy plant. The peak height differences between the rst and the third curves show the benets of using a Humid Loop to develop the crystallinity of powders; the partially crystallized powders in a Humid Loop have less moisture sorption that represents less amorphous material in the powders. The moisture sorption result of the powders that were processed in a three-stage uidized bed dryer= crystallizer for 20 minutes (from conventional spray-dried powder, curve 1) is shown in curve 4. The signicant change between raw powder (curve 1) and the processed powder from three-stage crystallization shows the signicant improvement in less moisture sorption by material after crystallization due to the lower amorphous contents of the processed materials. Curve 5 shows a signicant reduction in moisture sorption by the processed powders (in a two-stage uidized bed dryer=crystallizer for 15 minutes) that had been produced (and partially crystallized) in a Humid Loop. Table 3 describes the different types of powders that were used or produced in this research. Figure 7 shows a gradual improvement in less moisture sorption that represents the degree of amorphicity in the powders. Bulk Crystallinity by X-Ray Diffraction In this study, the XRD analysis has been used to evaluate the formation of lactose crystals and the improvement in the amount of crystallinity for different skim milk powders before and after processing. The different types of

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TABLE 3 Different types of the raw and crystallized powders that were used and produced in this research Powders 1 2 3 4 5

Description From conventional spray drying Commercial type From Humid Loop spray drying Processed in three-stage uidized bed from powder 1 Processed in two-stage uidized bed from powder 3

Average particle size (micron, D50) 30 180 90 390 470

Moisture content (%, w w1) 5.6 0.2 4.1 8.8 0.2 3.7 0.2 3.8 0.1

Raw powder CSMP Partially crystallized Processed in three-stage Processed in two-stage

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Corresponding numbers to the curves in Fig. 7.

lactose crystals, which were formed in milk powders by processing at hot and high humid conditions, were identied by the location of peaks in the reference data of previous studies.[3740] The most noted representative peaks were located at 12.5 ,16.4 , 20.1 for a-lactose monohydrate; 10.5 , 21 for anhydrous b-lactose; 19.1 , 21.1 for the mixture of anhydrous a=b with a molar ratio of 5:3; and 19.5 , 21.2 for mixture of anhydrous a=b with a molar ratio of 4:1.[40,41] The progress of lactose crystallization was observed from the increasing intensities of the peaks in the XRD patterns at different angles, in the range of 19 21 , specically at 19.1 and 20 .

The mostly crystalline skim milk powder[4] that was stored at a condition of 25 C and 75% RH for two weeks was used as a reference point for nominally 100% lactose crystallinity in milk powder when the quantitative analysis of crystallization was done. Raw commercial skim milk powder was used for XRD scanning by assuming minimum (almost zero) lactose crystallinity. Figure 8 shows individual different XRD patterns for: a) mostly crystalline skim milk powder; b) powders from the humid-loop after processing in two-stage uidized bed crystallization (powder no. 5); c) CSMP that was processed in three-stage uidized bed crystallization (powder no. 4); and d) powders that

FIG. 8. X-ray diffraction patterns for: A) mostly crystalline skim milk powder; B) processed in two stages from Humid-Loop powder (powder no. 5); C) processed in three stages (powder no. 4); D) partially crystallized in Humid Loop spray drying (powder no. 3). Peaks in the X-ray diffraction patterns for different lactose crystals and crystalline polymorphs are shown as vertical lines.

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were partially crystallized in humid loop spray drying (powder no. 3). The noisy and relatively at XRD pattern for raw SMP is not shown here. The diffraction pattern for mostly crystalline SMP shows clear sharp peaks associated with a-lactose monohydrate at high intensity. There is no distinguishable peak for b-lactose at 10.5 , and the peak intensities for a=b mixtures with different molar ration at 19.1 and 19.5 are very low. The vertical line at the highest peak point (20.0 ) was considered to indicate the maximum amount of lactose crystallinity in milk powder. The patterns for processed powders in multi-stage uidized-bed crystallizers (Fig. 8B, C) include clear representative peaks for the different lactose crystals polymorphs, while the alactose monohydrate peaks have the highest intensities. The peaks at 10.5 , 21 show the formation of anhydrous b-lactose, and the peaks at 19.1 , 19.5 , 21.2 , and 21.1 show the formation of anhydrous a=b lactose polymorphs. The intensities of anhydrous a=b lactose polymorphs peaks are relatively low. The b-lactose crystals or the b-lactose containing crystals (polymorphs) were formed due to high-temperature crystallization or low-humidity conditions;[37,40] the crystallized powder from a three-stage uidized-bed crystallizer (Fig. 8C, powder No. 4) that was processed at lower humidity (initial moisture content of powder, lower humidity uidization air) contains slightly higher peaks from anhydrous b-lactose crystals. The partially crystallized powders from Humid Loop spray drying (Fig. 8C, powder No. 3) show some improvement in crystallinity but at a low intensity, while most of the lactose crystals (and nuclei) are in the a-lactose monohydrate form. DISCUSSION Yazdanpanah and Langrish[4] demonstrated the crystallization of lactose and milk powder in a uidized-bed dryer=crystallizer. The crystallinity of crystallized powder was assessed by different techniques. That process was relatively time-consuming, while the multiple-stage uidized bed systems in this research are capable of improving the crystallinity of powders in minutes. By increasing the process temperature and=or increasing the water activity by sorbing more moisture at a higher relative humidity, the temperature between the material temperature (T) and its glass-transition temperature (Tg) will be increased and the crystallization time will be decreased.[9,10,42] Therefore, as the results show for crystallized powders, by increasing the material moisture content during processing (high-humidity process air at different stages and higher initial moisture contents), the sorption peak height dramatically decreased for the processed powders. This low peak height suggests that less amorphous lactose (the most hygroscopic component) remained in the milk powder. The shorter process time and the higher degrees of crystallinity support the hypothesis of high crystallization rates

occurring at high humidity and=or hot-processing conditions.[10,43] The crystallization boost in a uidized bed is governed by the uidization upper limits of temperature and humidity that depend on the degree of amorphicity of powders. Partially crystallized powders, from humid-loop drying, may have better uidization ability with highly humid air, causing acceleration of the crystallization rate in very moist powders. This very low glass-transition temperature, and relatively low required process temperature and short residence time, avoid degradation and denaturation in the powders. Particle size distribution of the resultant processed powders has shown some particle agglomeration for the processed powders compared with the raw skim milk powder before processing in a uidized-bed system (Table 3). The agglomeration is not avoidable in this technique due to processing by high-humidity air and at temperatures above the glass-transition temperatures of the powders. Figure 5B shows that the porous conguration of the crystallized milk powders agglomerates then so that these porous agglomerated particles easily sink and disperse in solvent (water) during rehydration process.[44] The comparative peak heights (improvements) for raw and crystallized milk powders have been reported in Table 4. Moisture sorption tests have shown that there are signicant differences between the powders that were processed under different conditions and the amorphous milk powder. Amorphous skim milk powders from conventional spray drying that were processed in a three-stage uidized-bed dryer=crystallizer have 87% less moisture sorption compared with the initial state. This lower amount of moisture sorption shows the lower fraction of amorphous lactose (most hygroscopic component) in the processed powder. The 20-minute processing time at high temperature and humidity conditions was therefore sufcient to mostly crystallize the SMP from conventional spray drying. The partially crystallized powders that were produced from a Humid Loop spray drying show 36% lower moisture sorption, supporting the suggestion that the Humid Loop technique reduces the degree of amorphicity of materials by drying them under humid conditions. The moisture sorption behavior of the partially crystallized powder was considered to be the base state when the moisture sorption of other process powders from this material was calculated. Therefore the processed powder (crystallized from the Humid Loop spray-dried powder) in a two-stage uidized bed dryer=crystallizer showed 92% less moisture sorption compared with the moisture sorption level of the raw material (conventionally dried). Thus the 15-minute processing time of the partially crystallized powder in a two-stage uidized bed was adequate to complete the crystallization of lactose in the milk powder from Humid Loop spray drying. The signicant reduction (8792%) in the moisture sorption and amorphicity of the

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TABLE 4 Moisture sorption peak heights of all the experimental conditions (Figure 7) for skim milk powders with respect to the sorption peak heights of amorphous SMP from conventional spray drying (base case) Average peak height, % (in sorption) 6.32 0.83 4.07 0.34 Improvement, % (after uidized bed processing) NA 87 NA (36 ) 92

Milk powders Peak height, Mass change, % Raw powder (1 ) Processed in three-stage uidized bed (4) Partially crystallized from Humid Loop (3) Processed in two-stage uidized bed from Humid Loop (5)

Comment Used as basement for curve 4. Crystallized from powder type 1. Used as basement for curve 5. Crystallized from powder type 3.

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Corresponding numbers to the curves in Figure 7. Improvement by partial crystallization in a Humid Loop spray drying.

powders in the order of minutes has emphasized the potential of this multiple-stage processes for industrial applications. Although the sequential batch processes that were performed in this research have some dead-time between different stages, a horizontal-vibrated uidized-bed dryer with different zones of temperature and humidity could save even more process time by eliminating these dead-times and reach the same level of crystallinity in a shorter time. Table 4 summarizes the statistical analysis for the moisture sorption peak heights of all the milk powders (Table 3) and reduction in the degree of amorphicity with respect to the sorption peak heights of raw powders before crystallization in a uidized-bed system (base case). To conrm the results of the moisture-sorption tests in terms of the amount for crystallinity of different powders, an XRD analysis has been done on the various powders. The XRD patterns of processed powders show clear sharp peaks for lactose crystals in the processed milk powders with different intensities. The ratios of a- and b-lactose may change as a result of changes in temperature and water activity during the crystallization process. The different intensities of peak heights that indicate the amount of crystallinity in the powders have been used as a scale for differences in the powder crystallinities. For this comparison, the highest peak intensity of mostly crystalline SMP (Fig. 8A) at 20.0 was assumed to be 100% crystalline and the noisy XRD pattern of raw SMP with no signicant peak was taken as 0% crystallinity. The three other intensities have been rescaled accordingly. Figure 9 shows the ve XRD patterns for different powders on this scale. Like the moisture-sorption test curves, the step-wise improvements in the crystallinity of the powders could be quantied by

XRD analysis. The comparative peak points in the partially crystallized powder and the processed powders in uidized-bed crystallizers have supported the improvements in crystallinity that were assessed by moisture sorption tests. The peak intensities (crystallinity) from the XRD analysis show higher amounts of crystallinity in comparison with the moisture sorption tests. For instance, the processed powders from the two-stage uidized bed and the Humid Loop (powder No. 5, Figs. 7, 8B) show 94% crystallinity from the XRD pattern and 92% crystallinity (less moisture sorption) in the moisture sorption test. Overall, the XRD analysis shows 24% more crystallinity compared with the moisture sorption tests, which could be due to

FIG. 9. Rescaled X-ray diffraction patterns for raw, processed, and mostly crystalline skim milk powders. The peak heights from 20.0 to 20.2 have been used as references (Fig. 8). The mostly crystalline skim milk powder was assumed to be 100% crystalline (top peak) while the raw SMP was taken as being nearly zero crystallinity.

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the recrystallization of anhydrous lactose crystals (and polymorphs) in the moisture-induced crystallization process. The moisture expelled from the powders went towards the recrystallization of lactose crystals and was not used to crystallize the amorphous portion. By comparisons, the XRD shows the amount of the a-lactose monohydrate form on its own. Crystallization of amorphous powders in a uidized bed dryer=crystallizer with hot humid air is an interaction between drying and crystallization. Using high temperature processing air causes particles to desorb moisture at lower corresponding water activities. The process includes sorption, crystallization, and then desorption. Therefore, the initial moisture content, the moisture sorption rate, the drying rate, and the nal moisture content govern the particle structure and crystal conguration and the crystallization rate. Powders could have egg-shell structures with amorphous cores and crystalline surfaces,[45] mostly amorphous, mostly crystalline,[4] or with crystallized cores and amorphous surfaces. The different parameters for crystallization and drying under the upper limits of uidization could be used to give different amounts of crystallinity and particle structures. Figure 10 shows some different crystalline particle structures that could be produced using this technique. The egg-shell structure in Figure 10A that were produced by a single stage uidized-bed drying=crystallization at T 50 C, RH 60%, and t 60 min had very low initial moisture content.[45] Therefore the processing at relatively high temperature and humidity crystallized few outer layers of particles and the bulk remains amorphous. The 8.8% initial=bulk moisture content of the material from Humid Loop spray drying provides very low Tg for the materials inside the particles and processing by hot air caused crystalline core for the powders that the cross-section has been shown in Figure 10B. The large lactose crystals on the surface come from the low viscosity= high mobility of wet materials and the nucleation in the Humid Loop spray drying.

CONCLUSIONS Processed milk powders show less moisture sorption and more lactose crystals, leading to an improvement in the degree of amorphicity of spray-dried milk powder by post-processing in a two- or three-stage uidized bed dryer=crystallizer. Crystallized lactose appeared to be formed, and the processed milk powders were heavily textured (crystallized on the surface). The surface texture improvement and lower moisture sorption from the environment mean that the powders have more stability and better ow, which could potentially be a feasible solution for ow problems associated with handling, bulk transfer, and hopper design in relation to these powders. The multiple-stage uidized bed system showed distinctive potential to crystallize lactose signicantly in skim milk powder using an industrial-feasible process. This short crystallization process could be carried out in a lower processing time if the multiple-stage uidized bed crystallizer is combined with a spray dryer operating with a Humid Loop. REFERENCES
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