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An International Journal
Wei Wang, Shihao Wang, Yanqiu Pan, Jing Yang, Shuo Zhang & Guohua Chen
To cite this article: Wei Wang, Shihao Wang, Yanqiu Pan, Jing Yang, Shuo Zhang & Guohua
Chen (2019) Porous frozen material approach to freeze-drying of instant coffee, Drying Technology,
37:16, 2126-2136, DOI: 10.1080/07373937.2018.1564759
GRAPHICAL ABSTRACT
Introduction
drying with hot gas. And most instant coffee produc-
Coffee is acknowledged as one of the most favorites tion comes from spray drying due to its high produc-
and widely traded agricultural merchandises in the tion capacities.[4,5] However, Spray drying as a typical
world.[1] Instant coffee refers to powder or granule thermal drying often brings possibilities of losing
obtained from fresh coffee beans through roasting, some heat-sensitive materials, such as aroma and anti-
grounding, extracting, and drying.[2] Commercially oxidant ingredients in coffee. Freeze-drying is a
used drying method is either spray drying or freeze- unique form of drying that removes moisture mainly
drying.[3] Spray drying is a well-established method of by sublimation. It can lead to the best quality of dried
producing dried powder directly from liquid by rapid products among almost all drying techniques.[6,7]
CONTACT Wei Wang dwwang@dlut.edu.cn School of Chemical Machinery and Safety, Dalian University of Technology, Dalian 116024, China.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ldrt.
ß 2019 Taylor & Francis Group, LLC
DRYING TECHNOLOGY 2127
Therefore, freeze-drying plays an important role in the during annealing.[33,34] A common characteristic of
processing of foods, pharmaceuticals, and biological these methods is that the mass transfer resistance is
products.[6,8] It has also found applications in the prep- decreased at the primary stage due to the increased size
aration of new materials.[9,10] Freeze-dried coffee yields of ice crystals, while the moisture desorption is weak-
a better quality product than spray-dried coffee.[7,11] ened at the secondary stage due to the decreased
However, freeze-drying is an energy intensive and internal surface area. The overall result depends on the
expensive process due to relatively long drying time and binding effect between the solid substrate and moisture.
poor overall energy efficiency.[12–14] Reducing freeze- If this dependency is less significant, the drying rate can
drying time so as for lowering energy consumption and be enhanced moderately.[35,36] However, those methods
raising productivity therefore become a worldwide chal- can only find limited applications in production units,
lenge during the past decades. probably due to the practical difficulties in satisfying
Freeze-drying consists of freezing and drying, and industrial-scale requirements.
the latter stage includes simultaneous sublimation- It has to be pointed out that current optimization
desorption, vacuum maintenance, and vapor conden- of the freezing stage has been implemented towards
sation. Early effort to enhance a freeze-drying process the solid frozen material through direct freezing with-
mainly focused on the drying stage itself. The simplest out initial pores. In fact, a liquid material to be
approach is the optimization of operating conditions freeze-dried can be first prepared into a frozen mater-
including heating shelf temperature and drying cham- ial with a certain initial porosity and then freeze-
ber pressure.[12,15,16] This approach can now be dried. This unconventional freezing strategy is quite
achieved in an automatic control system specially similar to the ice-cream making method.[37,38] Such a
designed although it only resulted in a limited promo- porous frozen material is expected to facilitate the
tion.[17,18] Microwave-assisted heating has been migration of sublimated vapor in prebuilt pores and
proved to facilitate the heat transfer of freeze-dry- the desorption of bound moisture due to a larger sur-
ing.[19,20] However, its application in freeze-drying face area. The main objective of the present work is
must be evaluated for each individual product. If solid to verify the effect of the initially porous frozen
substrate in a frozen material does not absorb micro- material on freeze-drying of instant coffee. The result
wave energy easily, microwave-assisted heating will be obtained can help one to clarify the mechanism of
less effective since ice crystals hardly absorb micro- process enhancement and guide the future implemen-
wave energy.[21] Dielectric material has to be used in tation of the proposed process.
this case as an internal heat source, which causes an
additional operating complexity.[22,23] Latter endeavor Materials and methods
for the process enhancement was to improve the
freezing stage. Freezing is the first and important Materials and facilities
stage of a freeze-drying process as it has impact on Soluble coffee powder (Nescafe, China) was selected
pore size, shape, and connectivity of frozen materials. as the solute in aqueous solution. De-ionized water
Subsequent process performance and product charac- was used as the solvent, which was provided by
teristics largely depend on this stage. Optimization of Dalian University of Technology (China). Liquid
the freezing stage includes freezing rate control, ice nitrogen was purchased from Dalian Institute of
nucleation regulation, and annealing.[24,25] It is recog- Chemical Physics, Chinese Academy of Sciences.
nized that fast freezing gives small and numerous ice Facilities employed here included an analytical bal-
crystals which are favorable to the secondary drying ance (ME403E/02, Mettler, Switzerland), a draught dry-
stage;[26,27] and slow freezing leads to large and less ing cabinet (DHG-9070A, Yiheng, China), a moisture
numerous crystals which are beneficial to the primary analyzer (HR83-P, Mettler, Switzerland), and a scanning
drying stage.[15,28] Ice nucleation regulation was found electronic microscope (Quanta450, FEI, America).
to produce large-size and narrowly distributed ice
crystals, and facilitate uniform freezing.[29,30]
Sample preparation
Annealing was reported to be able to reduce the freez-
ing-induced heterogeneity, simplify the amorphous The aqueous solution of coffee was prepared by dis-
structure, and increase the ice crystals size.[31,32] More solving 40 g of coffee powder with 60 g of de-ionized
recently, X-ray computed tomography was employed water. The initial moisture content was 1.5 kg/kg on a
for the determination of mass transfer resistance to dry basis. The solid frozen material without initial
vapor flow and the observation of glassy state relaxation pores was prepared by pouring the solution into a
2128 W. WANG ET AL.
Experimental apparatus
Figure 1. Schematic diagram of sample mold. Experiments were conducted in a lab-scale multifunc-
tional freeze-dryer. Flow diagram of the apparatus is
cylindrical container of 14.8 mm in diameter with a shown in Figure 2. It consists of five subunits: a vacuum
Teflon supporting pad of 5 mm in thickness at bot- unit, a temperature control unit, a data acquisition unit, a
tom, and then placed into a freezer at –48 C for 6 h. freezing unit, and a pad heating unit. The vacuum unit
The porous frozen material with a certain initial por- includes a vacuum pump (RV12, BOC Edwards, Britain),
osity was prepared with two freezing steps, initial a quartz drying chamber (2.3 L, TGP, Britain), and a
freezing and further freezing. During the initial freez- home-made cool trap. The temperature control unit con-
ing, the liquid nitrogen ice-cream making method was sists mostly of a circulator (9712, PolyScience, America), a
employed, which is described as follows. The liquid heat exchanger (0.72 m2, Yalong, China), a blower (60 m3/
nitrogen was slowly added into the solution in a heat- h, 11.8 kPa, Sensen, China), and a home-made heating
insulated barrel while mechanical stirring at about cabinet. It was designed to maintain a constant tempera-
400 rpm. The solution being processed then expanded ture on the chamber surface. The data acquisition unit is
into a mousse-like frozen material with initial pores. constitutive of a pressure sensor (APG100-XLC, BOC
It should be pointed out that no any additive like an Edwards, Britain), an infrared sensor (CI3A, Reytek,
emulsion stabilizer has been used in this step.[13,39] America), a loadcell (0.3 kg, Mavin, China), a data acqui-
Afterwards, such a premade material was molded in a sition card (PCI-6221, NI, America), and a PC (M7130,
container with a supporting pad at bottom, and Lenovo, China). It was used to digitize the analog signals
quickly placed into the freezer for further freezing at generated by the three sensors through the LabVIEW
–48 C for 6 h. The molding allowed forming the ini- source code written for display, storage, and analysis of
tially solid and porous frozen samples of equal mass. experimental data. The freezing unit is an ultralow tem-
Before freeze-drying, the contained sample mold perature freezer (DW-GW138, Meiling, China) outside
was temporarily moved out of the freezer, allowing it the drying chamber.
to stay at room temperature for a while or holding it To investigate the effect of heating mode on freeze-
in hand for a moment to remove the container. The drying, a pad heating unit was specially designed to
sample mold without the container but with the sup- implement the combined heating of radiation and
porting pad was then placed back to the freezer for at conduction, as shown in Figure 3. A thermal rod was
least 30 min to ensure a uniform initial temperature. installed between the sample mold and the loadcell so
Thus, the sample mold was well prepared and ready that the heat can be transported from the rod onto
to be freeze-dried. Schematic diagram of the sample the supporting pad of the sample mold through con-
mold is shown in Figure 1. duction. Since the loadcell was directly connected to
Two kinds of the sample molds, one for the solid the thermal rod, non-contact heat transfer had to be
frozen material without initial pores and the other for adopted to avoid loadcell signal interference. The rod
the porous one with initial pores, were prepared with was surrounded coaxially by a heating jacket within
the same initial mass of 1.6 g excluding the supporting which six electrical bars (30 W in total) were uni-
pad. The concept of saturation, S, which is the ratio formly inserted. The heat transported towards the rod
DRYING TECHNOLOGY 2129
Figure 2. Flow diagram of experimental apparatus. (1) Pad heating unit; (2) sample mold; (3) drying chamber; (4) heating cabinet;
(5) supermeter; (6) heat exchanger; (7) circulator; (8) blower; (9) regulating valve; (10) pressure sensor; (11) vacuum pump; (12)
cool trap; (13) freezer; (14) date acquisition card; (15) PC; (16) infrared sensor; (17) loadcell; (18) three-way valve; and (19)
PID controller.
Figure 6. SEM images of dried products at different magnifications. (a–c) for the initially solid frozen sample; (d–f) for the initially
porous one.
was almost three times greater than that of the solid freezing. After nucleation, ice crystals gradually grew
one. It is due to the initially prebuilt pore space that up and pushed the circumambient solute to their
sublimated/desorbed vapor can easily migrate out- interstices. Interstitial fluid became more and more
wards. For the solid frozen sample, the drying process concentrated until transforming into an amorphous
experienced a constant rate period at the early stage, solid eventually.[16] Inspection of Figure 6(b, c) shows
and then became a falling rate period gradually until that the pore shapes are irregular and the pore walls
the end of drying. For the porous frozen sample, how- are thick and closed. This would impede the subli-
ever, the drying process was always in the falling rate mated vapor to transport outside of the material
period. As a result, the primary and secondary stages being dried.
in the freeze-drying of the porous frozen material The morphology of the dried cake from the porous
were likely redistributed compared to those of the frozen sample is remarkably different from that of the
solid one as seen subsequently. solid one. Figure 6(d) exhibits a typically spherical
structure with a bidisperse porosity that is looser and
more porous. The averaged pore size for this kind of
SEM characterization of dried products
the material is much larger than that of the solid
To examine the pore size, structure, and connectivity material. This is because a certain amount of gasified
of the dried cake so as to further understand the nitrogen has been incorporated into the material dur-
freeze-drying processes of the two frozen materials, ing the initial freezing. Such a pore structure has fixed
SEM characterization was performed for the two dried before the further freezing. It is seen in Figure 6(e)
products. Figure 6 shows SEM images at different that the porous frozen material made with this new
magnifications. method has continuous pore space and pierced solid
The morphology of Figure 6(a) manifests a netlike substrate. This porous material with a certain initial
structure that is compact and dense. It has to be men- porosity would have less mass transfer resistance, and
tioned again that the solid frozen sample was obtained the sublimated vapor could escape more easily during
through direct freezing in the freezer. The coffee solu- drying, leading to a higher primary drying rate.
tion first experienced a cool supercooling during Further observation of Figure 6(f) reveals that the
2132 W. WANG ET AL.
Figure 9. Photos of two samples before and after freeze-drying. (a) solid sample before drying; (b) solid sample after drying at
35 C; (c) collapse of solid sample during drying at 50 C; (d) porous sample before drying; and (e) porous sample after drying
at 50 C.
effect of porous materials. Hence, a moderately high always maintained its original structure and geometry
chamber pressure is a favorable way to improve the throughout the process. When the temperature was
heat transfer and accordingly enhance the process for further increased from 50 C to 55 C, the freeze-dry-
this kind of the material. Compared with the chamber ing process still proceeded successfully for this kind of
surface temperature, the effect of the chamber pres- the material. Photos of the two samples before and
sure can be neglected. Similar discussion can be found after freeze-drying are shown in Figure 9. This indi-
elsewhere.[13] cated that the porous frozen sample made with this
new freezing method had higher tolerable temperature
than the solid one during freeze-drying. Since the
Effects of heating modes on freeze-drying
solid frozen sample was prepared by direct freezing
The experimental results as seen in the last section without initial pores, sublimated vapor was difficult to
have proved that the appropriate increase in chamber escape from inside out. This would increase the
surface temperature can promote the freeze-drying internal pressure of the material being dried. When
process and the change in chamber pressure had little the heat transported from outside in was more than
effect. It is necessary to further increase the tempera- that needed for the phase change of ice crystals, the
ture to improve the heat transfer of the process. This excess portion would raise the sensitive heat of the
part of the experiments was conducted with the same solid substrate and melt ice crystals. Once the solid
sample pair under the same operating conditions substrate loses its rigidity, collapse is inevitable to take
except that the temperature was increased from 45 C place during freeze-drying. In contrast with the solid
to 50 C. The result showed that the solid sample col- sample, the porous one had an intrinsic loose struc-
lapsed and the freeze-drying process failed. It was sur- ture, allowing the phase-changed vapor of easy move-
prising to find, however, that the porous sample ment in the prebuilt pore space and avoiding a vapor
2134 W. WANG ET AL.
Conclusions
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