A Review of Maillard Reactions in Spray Dryers

Journal of Food Engineering 305 (2021) 110615
Contents lists available at ScienceDirect
Journal of Food Engineering

journal homepage: http://www.elsevier.com/locate/jfoodeng
Review
A review of Maillard reactions in spray dryers

Zelin Zhou *, Timothy Langrish
Drying and Process Technology Group, School of Chemical and Biomolecular Engineering, Building J01, The University of Sydney, Darlington, NSW, 2006, Australia
A R T I C L E I N F O A B S T R A C T
Keywords: Maillard reactions in liquid systems have been studied extensively, while those occurring during the spray-drying
Maillard reactions process have been less well studied. Current studies on Maillard reactions in spray dryers have been focussed
Spray drying heavily on empirical studies of the effects of the operating parameters. However, only modest attention has been
Wall-deposit re-entrainment
paid to the fundamental reactions or to the interactions with the fundamental spray-drying process. Studies on
Particle residence time
the spray-drying process have shown that component segregation occurs during the process. Component
segregation causes different ratios between various reacting components in different parts of particles, and this
segregation process may change the kinetics of Maillard reactions. Particle residence times and the re-
entrainment of wall deposits may also affect the extent of Maillard reaction since they determine the reaction
time in spray dryers. Improving the design of spray dryers may also help to reduce the extent of the Maillard
reactions in spray-dried products.
1. Introduction processes (Lee et al., 2017), Maillard reactions that occur during the
storage of spray-dried products, and changes in physical or sensory
Spray drying has been used since the 18th century as a method for properties in the spray-dried products that may be related to Maillard
extending the shelf life of dairy and other food products (Caric and reactions (Carter et al., 2018; Sahin et al., 2018; Park et al., 2016). A
Kalab, 1987). The quality of the spray-dried products is commonly summary of some relevant studies is shown in Table 1. Although the
assessed based on physical properties, such as moisture content, kinetics of Maillard reactions in liquid systems have been studied
wettability, and particle size. With the growing interest in the nutri extensively, little attention has been paid to the kinetics of Maillard
tional value and the integrity of components in foods, it is important to reactions inside spray dryers. Nevertheless, spray dryers of various sizes
understand the mechanism of thermal degradations in spray dryers and configurations have been used in current studies, which all have
(Lakni and Jayasinghe-Mudalige, 2010). different characteristics, making it difficult to assess the wider applica
One of the common types of thermal degradation that occurs during bility of their findings.
the spray drying processes of many food products is Maillard reactions Due to the rapid changes in the moisture content and the tempera
(Schuck, 2006). Maillard reactions are chemical reactions that occur ture of particles in most spray dryers, the mechanisms of the Maillard
between amino acids and reducing sugars (Maillard, 1912). During the reactions in spray dryers may be different to these reactions in liquid
spray drying process of milk or other dairy products, depending on the systems, and there is a need to investigate this area. The novelty of this
processing conditions, Maillard reactions may occur. Maillard reactions work is that this review discusses Maillard reactions in the context of
have many consequences, including the loss of nutritional value, the spray drying, which has not been comprehensively covered in previous
formation of nitrogen-containing brown pigments (melanoidins), the literature. The structure of this review can be summarised as follows.
formation of potential mutagenic products, and the formation of flavour The chemical reactions and kinetics of the Maillard reaction scheme
products (Nursten, 1986). have been reviewed first, then the difference between Maillard reactions
Current studies on Maillard reactions in spray dryers are mainly in liquid systems and in spray dryers have been outlined. General fac
focused on the following areas: the effect of the operating conditions (e. tors, such as the composition of the feed, and the values of the pH and
g. inlet gas temperature, feed flow rate) on the quality of spray-dried the water activity have then been discussed. Significant attention has
products (Koca et al., 2015; Park et al., 2016), using Maillard re been paid to the factors that are mainly related to the spray-drying
actions products as emulsifiers or encapsulation agents in spray-drying process. Spray-drying specific factors, including component
* Corresponding author.
E-mail address: [email protected] (Z. Zhou).
https://doi.org/10.1016/j.jfoodeng.2021.110615
Received 15 December 2020; Received in revised form 26 February 2021; Accepted 27 March 2021
Available online 31 March 2021
0260-8774/© 2021 Elsevier Ltd. All rights reserved.
Z. Zhou and T. Langrish Journal of Food Engineering 305 (2021) 110615
Table 1 Table 1 (continued )

Summary of relevant studies on Maillard reactions in spray-dryers. Authors Food systems Spray drying Degree of Maillard
Authors Food systems Spray drying Degree of Maillard conditions reactions
conditions reactions
Katekhong and Inlet/Outlet gas based on CIELab
Tomlinson et al. Model system: Bench-scale spray Structure Charoenrein temperature: colour space: ΔE: 0-
(1993) Glucose: 1 M dyer elucidation of (2018) 140◦ C–180 ◦ C/ 15
Glycine: 1 M Inlet/Outlet gas Maillard reaction 80 ◦ C
temperature: product Feed flow rate was
235 ◦ C/170 ◦ C controlled to
Flowrate: 20 ml/ maintain the same
min outlet gas
Vasbinder and de Gelatin Bench-scale spray Colour analysis temperature
Kruif (2003) hydrolysate and dyer based on CIELab (13–20 ml/min)
maltodextrin at a Inlet/outlet gas colour space: L*: Gómez-Narváez Model system: Samples were Available
ratio of 2:1 (w/ temperature: 15–20, a*: 0.38- et al. (2019) 2.91% moisture, conditioned to lysine:1.63–11.3 g/
w) 160 ◦ C–200 ◦ C/ 0.14, b*:5–16, ΔE: 5.62% ash, different moisture 100 g of protein
Solid conc:2% 92 ◦ C–112 ◦ C; 5-11 11.07% protein, contents Furosine:
w/v Flowrate: 4.0 ml/ 77.78% lactose Heated at 0.44–11.1 mg/100
min 60–90 ◦ C for 2–40 g of protein
Miao and Roos Model system: Samples were Optical density at min HMF: ND-57.7 mg/
(2004) lactose 45 wt%, conditioned to 280 nm (0–450 100 g of protein
trehalose 45 wt different moisture OD/g of dry mass) Browning index:
%, xylose 5 wt%, contents and 420 nm (0–80 0.01–0.11
and lysine wt5% Heated 40–90 ◦ C OD/g of dry mass) Colour analysis
for 5–15 min based on CIELab
Koca et al. Cheese slurry Pilot-scale spray Measured as Non- colour space: ΔL*:
(2015) Solid conc. 25 wt dryer enzymatic 10-0, Δa*:0–8,
% Inlet/outlet gas browning (NEB): Δb*:0–15, ΔE:0-18
temperature: Chroma Zhong et al. Ascorbic acid Bench-scale spray Colour analysis
160 ◦ C–230 ◦ C/ values:10–20: (2019) (vitamin C) and dyer based on CIELab
60 ◦ C–100 ◦ C Browning index: whey protein Inlet/outlet gas colour space: Red/
Atomisation 11–30. isolate (WPI) at temperature: green values (a*)
pressures: 294 Degree of different ratios 150◦ C–72 ◦ C (-5 – 30)
kPa–588 kPa NEB:0.12–0.343 (0–1:2) (10 wt% Feed flowrate:8 Fluorescence
Feed flow rate was optical density/g of WPI, and ml/min measurements with
controlled to dry mass concentration of Samples were excitation
maintain a specific Vitamin C varies aged at 20 ◦ C for wavelengths of
outlet gas based on ratios) 21 days 380/500 nm, and
temperature emission
Huang et al. Glycine and Bench-scale spray Browning pigment wavelengths 440/
(2016) sucrose at ratio dyer formation and 600 nm
of 2:1 (w/w) Inlet/outlet gas intermediate
Solid conc. 1.5% temperature: product as
w/v 160◦ C–230 ◦ C/ absorbance at 294 segregation due to the spray-drying process, wall deposition and re-
75 ◦ C–107 ◦ C nm and 420 nm, entrainment and the particle residence times in spray dryers have
Feed flow rate: 5 respectively.
been discussed in the context of Maillard reactions.
g/min - 25 g/min HMF concentration:
0–0.8 w/w%
Park et al. (2016) Skim milk Pilot-scale spray Furosine: 10–20 2. Maillard reactions
Solid conc. dryer mg/100 g of
30–50 wt% Inlet/outlet gas protein
temperature: Changes in sensory
Due to the complex nature of the Maillard reactions, Hodge devel
160 ◦ C–260 ◦ C/ properties and oped a simplified version of the Maillard reactions scheme where most
90 ◦ C volatile compounds of the reaction routes are included within that scheme (Hodge, 1953).
Feed flow rate was Nursten later included a reaction route where fission products are
controlled to
formed from Schiff’s based products to account for the more recent
maintain the same
outlet gas discoveries in the kinetics of Maillard reactions (Nursten, 2005). Hodge
temperature divided the Maillard reaction scheme into three different stages, namely
Rongsirikul and Whey protein Bench-scale spray Browning pigment the initial stage, the intermediate stage, and the final stage, as shown in
Hongsprabhas concentrates dyer formation as Fig. 1.
(2016) with/without Inlet/Outlet gas absorbance at 420
modification and temperature: nm.
trehalose at a 130 ◦ C/100 ◦ C
ratio of 3:7 Flowrate: 4.0 ml/
2.1. The early stage of Maillard reactions
Solid conc. 20% min
w/v During the early stage of Maillard reactions, reducing sugars (car
Fialho et al. Lactose- Bench-scale spray Colour analysis bohydrates) react with amino acids via Schiff’s base formation. Then
(2018) hydrolyzed dyer based on CIELab
Schiff’s base products are transformed into Amadori products via the
concentrated Inlet/outlet gas colour space: L*:
milk and temperature: 86-96 Amadori transformation, and this process can be considered to be
concentrated 160 ◦ C/53–93 ◦ C HMF concentration: effectively irreversible (Davidek et al., 2002; van Boekel, 1998). As with
milk. Feed flow rate: 5 0–130 mg/kg other reactions, the reaction rate for Amadori product formation is
Solid conc. 40% g/min - 25 g/min dependent on the reactant concentration. Both amino acids and
w/w dry mass
Egg white Pilot-scale spray Visual appearance
reducing sugars are present in two forms in aqueous systems, reactive
dryer and Colour analysis and unreactive forms (van Boekel, 2001). The open-chain form and the
unprotonated form are considered to be the reactive forms for reducing
sugars and amino acids, respectively (Figs. 2 and 3). The ratios between
2
Fig. 1. Overview of Maillard reactions scheme (reproduced based on Nursten, 2005).
Fig. 2. Open-chain form and closed-form of glucose.
Fig. 3. Amino acids in different pH environments.
3
different reactants also play an important role in the early stage of

Maillard reaction kinetics. Copado et al. (2017) created microcapsules
formulated with different concentrations of chia oil and with different
carbohydrate: protein ratios in a freeze dryer. They found that a higher
carbohydrate to protein ratio increased both the rate and the extent of Fig. 4. Kinetic model for early stage of Maillard reactions (Ge and Lee, 1997).
Maillard reactions for their system.
significantly greater than k1, which suggest that the formation of Schiff’s
2.2. The intermediate stage of Maillard reactions base is the rate-limiting step for the early stages of Maillard reactions.
The formation of Amadori product is strongly temperature-dependent
After the initial stage of the Maillard reactions, the Amadori products and favoured at higher temperatures, as suggested by the higher acti
start to break down into different small pigments, depending on the pH vation energy for step 2 compared with step 1 and the reverse of step 1.
of the environment. There are three main different breakdown routes: 1. Since there are various products that may be formed during Maillard
The 3-deoxyosone-pathway via the 1,2 enolisation route under acidic reactions, and they may interact with each other, using a multi-response
environments. 2. The 1-deoxyosone-pathway via the 2,3 enolisation modelling approach is necessary. Multi-response modelling approach is
route under neutral and alkaline environments. 3. The 4-deoxyosone- an approach that includes multiple and potentially simultaneous
pathway under slightly alkaline conditions, and it is less common than chemical reactions in a complex reaction scheme, this approach predicts
the other two pathways (van Boekel, 1998). All three different break the and changes (responses) in both reactants and products at the same
down pathways involve the formation of deoxyosones, which are reac time. This terminology has been used by Martins et al. (2000). They have
tive intermediate products. Some of the breakdown products of these explained the distinction between this concept and the concept of
reactive intermediates are known as advanced glycosylation end prod “analysing and modelling more than one component simultaneously”. Mundt
ucts (AGEs). Furfural and reductones are formed during this stage and et al. (2002) have proposed a multi-response model for the
have been found to be related to the browning outcomes in the later maltose-glycine system. The multi-response scheme gave a good fit to
stages (Hodge, 1953). the experimental results. The multi-response scheme has been further
developed and extended by including key intermediates that are pro
2.3. The final stage of Maillard reactions duced during different stages of the Maillard reactions, as shown in
Fig. 5 (Martins and van Boekel, 2002).
During the final stage of Maillard reactions, the intermediate prod The extended reaction scheme showed a good fit with experimental
ucts that are produced during previous stages react with each other via data obtained from the glucose-glycine system. Their results also sug
polymerisation, and nitrogen-containing brown pigments (melanoidins) gested that the 3-DG pathway is the main pathway for the formation of
are formed. Melanoidins have high molecular weights (up to about melanoidins. In their later study for the glucose-glycine model system,
100,000 g/mol). The exact mechanism for the formation of melanoidins glucose was found to be involved in reactions to a greater extent. Based
and their structures remains unclear. The main reactions involved in the on their results, they concluded that this phenomenon is due to (1)
formation of melanoidins are expected to include aldol condensation, glucose isomerisation; and (2) glycine is regenerated during the second
aldehyde-amine polymerisation, and the formation of heterocyclic ni stage of the Maillard reactions (Van Boekel and Martins, 2002).
trogen compounds (Hodge, 1953). The multi-response modelling approach has also been used in many
other studies (Bertrand et al., 2015; Chansataporn et al., 2019; Kocadaǧ;
2.4. Application of Maillard reactions in spray drying li and Gökmen, 2016). There are also some other kinetic models that
focus on other products that are produced due to Maillard reactions. For
Maillard reactions products are sometimes used as emulsifiers or example, the kinetics of flavour compound formation due to Maillard
encapsulation agents coupled with spray drying or other drying pro reactions have also been studied by Jousse et al. (2002). The kinetics of
cesses (Lee et al., 2017). The use of Maillard reaction products as an the formation of some other components, such as fluorescent products,
encapsulants for palm-based medium- and long-chain triacylglycerol are still unclear (Matiacevich et al., 2005).
were studied by Lee et al. (2015). They found that the Maillard reactions
can be controlled satisfactorily by choosing a suitable mixture of sodium
3.2. Kinetic studies of Maillard reactions applicable to spray drying
caseinate and soy proteins and maltodextrin, when heated as a solution
for a particular temperature and time, and that Maillard reaction
Most of the studies mentioned above are based on liquid systems,
products can act as natural emulsifiers and encapsulation agents. The
where the kinetic parameters may be different from those in solid sys
anti-oxidant properties of Maillard reaction products have been reported
tems or systems with much lower moisture content. The differences in
in many studies (Lee et al., 2017). In a study by Samborska et al. (2019),
the moisture contents may result in different component mobilities in
the effects of low-temperature spray drying with dehumidified inlet air
the systems and thus different kinetic parameters. The effect of the water
on the phenolic content, antioxidant activity and level of aroma com
activity and component mobilities will be discussed in more detail in
pounds in rapeseed honey have been investigated. Maltodextrin and
NUTRIOSE® were used as carriers, and skim milk was assessed as a
substitute for water. The authors suggested that Maillard reaction
products may contribute to the increased anti-oxidant activity in the
spray-dried powders (Samborska et al., 2019).
3. Kinetic studies of Maillard reactions
3.1. Kinetic studies of Maillard reactions in liquid systems
To understand the kinetics of the Maillard reactions in spray dryers,

kinetic modelling is necessary. Ge and Lee (1997) proposed a model for
the early stage of Maillard reactions, as shown in Fig. 4.
Here A is an amino acid; S is a reducing sugar; AS is the Schiff’s base
product, and AP is the Amadori product. In their results, k-1 and k2 are Fig. 5. Kinetic model for Maillard reactions (Van Boekel and Martins, 2002).
4
subsequent sections. used instead of a set of model systems with different ratios between the
Some studies have investigated the effect of moisture content and reactants, and thus the effects of different ratios between reactants at
temperature on Maillard reactions under conditions that are applicable various moisture contents and temperatures were not studied.
to spray drying. A freeze-dried mixture of lactose, trehalose, xylose and
lysine in a 45:45:5:5 wt ratio was used in the work of Miao and Roos 3.3. Studies on Maillard reactions in spray-dried powders during storage
(2004). Freeze-dried powders were conditioned to different moisture
contents by placing them above different saturated salt solutions. Sam There are many other studies that have addressed the problem of
ples were then heated at different temperatures (40◦ C–90 ◦ C) in sealed Maillard reactions in stored spray-dried powders (Hurrell et al., 1983;
containers for different lengths of time. The extent of Maillard reactions Nishanthi et al., 2018). Although most of the studies use lower tem
in their study was based on measuring the optical density at 280 nm and peratures and longer durations than those that could be expected in a
420 nm. However, the browning behaviours observed in Maillard re spray dryer (Chiou et al., 2008), their findings about Maillard reactions
actions do not occur until the advanced stages of the Maillard reactions, may still be applicable for Maillard reactions in spray dryers. A study by
which means that the products of the early Maillard reactions were not Hurrell et al. (1983) found that Maillard reactions in milk powder were
measured in their study. In a later study, Aalaei et al. (2019) found that, more rapid when the samples were stored at temperatures above 70 ◦ C
despite different infant formula powders having similar lysine levels than those stored at 40oC–50 ◦ C. Their results suggested that the rate of
(markers for early-stage reactions), the levels of CML (marker for Maillard reactions may increase significantly when the samples are kept
advanced-stage reactions) varied sevenfold, indicating that the above a certain temperature. Similar temperature-dependent behaviour
advanced stages of Maillard reactions vary considerably between was also reported in other studies (Miao and Roos, 2004). Nishanthi
different spray-dried samples. Their results suggested that the kinetics et al. (2018) monitored the physical properties of different types of whey
for different stages of Maillard reactions may be different from each protein powders during storage at temperatures of 4 ◦ C, 25 ◦ C, and 45 ◦ C
other. Therefore, it is necessary to monitor more than one stage of the and relative humidities of 22% and 33% for 90 days. The Maillard re
Maillard reaction scheme in a kinetic study of Maillard reactions. In action was found to be involved in changes to the surface composition
addition, Ren et al. (2015) confirmed that the early stages of Maillard and the physical properties of the powders (Huang et al., 2020; Nish
reactions are the rate-limiting steps in the overall reaction, which anthi et al., 2018).
further emphasises the importance of monitoring the early Maillard
reaction products that occur in spray dryers. Gómez-Narváez et al. 4. Factors affecting the kinetics of Maillard reactions in spray
(2019) performed a similar study when they were assessing the useful dryers
ness of different markers for Maillard reactions under conditions
applicable to the spray drying process. In their study, freeze-dried whey Studies on kinetics of Maillard reactions in liquid systems have
powders were conditioned to different moisture contents using four shown that the kinetics of Maillard reactions may be affected by various
different saturated salt solutions in a similar approach to that of Miao factors, including but not limited to temperature, pH, and reaction time.
and Roos (2004). Conditioned samples were subsequently heated at Some of the factors may be applicable to the kinetics of Maillard re
60 ◦ C, 75 ◦ C, and 90 ◦ C for up to 40 min. Then the samples were analysed actions in spray dryers, while others are not so clearly linked. In general,
using different analytical methods. Their results suggested that furosine Nunes et al. (2019) have covered general factors that affect Maillard
and bioavailable lysine are sensitive markers for Maillard reactions reactions in infant formulae. However, the connection between those
under spray drying conditions, while HMF is less useful as a marker. factors and connected to the spray-drying process was not discussed, and
Studies have shown that the formation of HMF could also be caused by spray-drying specific factors were not mentioned. Thus a more detailed
other reactions other than Maillard reactions. The conversion rate of review of Maillard reactions in spray dryers is required. A summary of
HMF from the Amadori product is low, and most of HMF come from different factors that may change the kinetics of Maillard reactions in
lactose rather than the Maillard reaction (Morales et al., 1997). As a spray dryers is shown in Fig. 6.
result, HMF could still be used as an indicator of heat-induced damage
under more severe conditions. The colour formation was also found to 4.1. Effect of feed composition
agree with the markers of furosine and bioavailable lysine, although the
sensitivity was reduced at lower temperatures. Other than the concentration of sugars and amino acids in their
Both the studies of Miao and Roos (2004) and Gómez-Narváez et al. reactive forms, other components in the feed may also play an important
(2019) showed how Maillard reactions could be affected by the moisture role in the kinetics of Maillard reactions in spray dryers. The study of
content and temperature at conditions applicable to spray drying. In Claeys et al. (2003) showed that fat present in milk promotes the for
Miao and Roos (2004), the kinetics of Maillard reactions have been mation of furosine during the thermal processing of milk when the
modelled as a zero-order reaction. A zero-order reaction model fitted the temperature is below 130 ◦ C. Furosine is an acidic degradation product
browning process in the samples well, but it did not provide insights into of the Amadori product and is often used as a marker for the early stage
the reaction mechanism for complex reaction schemes, such as the of Maillard reactions (Finot et al., 1981). Their results suggested that
overall Maillard reactions. Thus, a more comprehensive approach, such reducing the fat content in the feed may be an effective way to reduce
the as multi-response modelling approach used in studies for Maillard the extent of Maillard reactions occurring during the spray-drying pro
reactions in liquid systems (Martins and van Boekel, 2005), is required cess. Furthermore, Nijdam and Langrish’s study showed that the spray
for establishing a better understanding of the kinetics of Maillard re drying of skim milk (low fat contents) results in a higher recovery rate of
actions in spray dryers. Kocadaǧ;li and Gökmen (2016) have investi the products, by comparing the product recovery rate of spray drying
gated the kinetics of Maillard reactions in systems with low moisture skim and whole milk.
contents systems using heated glucose/wheat flour model systems (1:10 The effect of the minerals (i.e. metal ions) on the kinetics of Maillard
w/w, 7% humidity) at 160, 180 and 200 ◦ C for up to 20 min. A reaction is rather complex, as they may inhibit the formation of some
multi-response modelling approach was used in their study. Their study products, while the formation of other products is promoted. Akagawa
has shown that the multi-response modelling approach is applicable to et al. (2002) investigated the influence of metal ions, anions (e.g.
systems with low moisture contents. Although the temperatures used in phosphate, carbonate), oxygen and some other chelating agents on the
their studies were much higher than the particle temperatures that early stages of Maillard reactions. Their results suggested that metal ions
might be expected in a spray dryer (Chiou et al., 2008), some of their accelerate the degradation of Amadori products, while chelating agents
findings may still be applicable for particles that stick to the walls of reversed the effects (Gökmen and Şenyuva, 2007). They also found that
spray dryers. In the studies mentioned above, single model systems were the formation of Amadori products is accelerated by phosphate and
5
Fig. 6. Summary of factors and their main effects on Maillard reactions in spray dryers.
carbonate ions. (McSweeney and Fox, 2009). The solubility of reactive oxygen in liquids
Carrier agents (sometimes described as drying aids), such as malto decreases with higher temperatures (unlike the solubility of most solids
dextrin, gum arabic, and starches are commonly used in the spray drying in liquids), so the impact of oxygen in liquid droplets inside spray dryers
process for sugar-rich materials (Shishir and Chen, 2017). Michalska may be somewhat limited, because the droplet and particle tempera
et al. (2019) studied the effect of freeze-, vacuum- and spray-drying on tures increase towards the outlet temperature in spray dryers (as shown
the polyphenolic contents of blackcurrant juice powders. Greater in Chiou et al. (2008)). However, the role of oxygen in dry particles or
degradation of anthocyanins and a significantly higher hydrox powders inside spray dryers may be more important, because the access
ymethyl-l-furfural (HMF) content was found in powders containing to oxygen does not limit by the solubility of oxygen in the reaction
inulin than those containing maltodextrin after vacuum drying at 90 ◦ C. medium. Nunes et al. (2019) reported that, using nitrogen gas as the
This difference in the powders might be due to the fructose in the inulin drying gas is a technique that has been used to reduce the extent of
being involved in the formation of HMF via Maillard reactions or car Maillard reactions in the production of infant formulae. The situation
amelisation at high temperatures (Michalska et al., 2019). This finding may be further complicated by the possibility that Maillard reaction
regarding inulin is significant and interesting, since common carriers products may have some antioxidant activity, as pointed out in review
used in spray dryers are basically poly carbohydrates, which may also by Lee et al. (2017).
contribute to Maillard reactions in spray dryers (Shishir and Chen,
2017). Thus, more investigation about the effect of different carriers on
4.3. Effect of pH
the kinetics of Maillard reactions is required.
As mentioned in the previous sections, the pH of the system affects

4.2. Effect of oxygen the concentration of available (reactive) reactants and the degradation
pathway of Amadori products (van Boekel, 1998; Yaylayan et al., 1993).
Oxygen plays an important role in the Maillard reaction scheme, but The rate of reaction generally increases with the pH. Verardo et al.
it is not essential to the Maillard reactions. The presence of oxygen may (2017) reported that the furosine level (marker for early stage of Mail
promote the formation of the reductones, but it may also oxidise some lard reactions) in the spray-dried pasteurised egg was 55 times higher
reactants and reduce the reaction rate (Nursten, 2005). Pokorný et al. than that in the ordinary pasteurised egg. The large differences in the
(1988) found that the absence of oxygen can limit the reaction rate in furosine levels in their samples may have been due to Maillard reactions
their model systems. Their model systems were glucose and L-alanine, that were encouraged by the alkaline and high protein content envi
and the products were Amadori ones. They reported that air was ronment. The effect of the pH is also dependent on the composition of
replaced by bubbling nitrogen into the reaction system, and the reaction the systems. For systems with disaccharides, the reaction rate will be
rate was nearly halved. This result is likely to be due to the formation of more favoured at lower pH as it promotes the degradation of the di
reactive hexosulose (I) in the presence of oxygen. Oxygen may also play saccharides to form reducing sugars (Huang et al., 2016; Lea and
an important role in some systems by promoting lactose degradation Hannan, 1949). During the second stage of Maillard reactions, formic
6
acid and other organic acids are formed. The formation of these organic Roos, 2009). Other than affecting the stickiness of the particles, glass
acids may reduce the pH of spray-dried droplets and change the reaction transition also affects the mobility of the molecules. When the materials
rate or shift the degradation pathway of Amadori products. However, are in a glassy state, the molecule mobility is somewhat limited, while in
these organic acids are volatile and can be evaporated easily during the the rubbery state, greater molecular mobility is observed (Roos, 2002;
spray-drying process, and the impact of the formation of these acids on Sherrington, 1993). Different molecular mobilities may affect the reac
the kinetics of Maillard reaction in spray drying may not be so signifi tion kinetics of the Maillard reactions. An increase in the reaction rate of
cant. Nevertheless, the formation and evaporation of the organic acids Maillard reactions has been observed when the temperature is above the
may cause changes in the morphology of the spray-dried particles glass transition temperature, and the glass transition temperature of the
(Huang et al., 2016). samples (Tg) is depressed significantly due to water production via
Maillard reactions (Roos, 2002; Sherrington, 1993). In the study of Miao
4.4. The role of water and Roos (2004), a critical value of T-Tg was observed. When the T-Tg
was above this critical value, a significant increase in the rate of Maillard
Water activity (aw) is another factor that affects the kinetics of reactions was observed. A later study by Gómez-Narváez et al. (2019) on
Maillard reactions in spray dryers. At high water activity, the dilution whey powders also suggested that lactose in amorphous state promotes
effect leads to low reactant concentrations, reducing the rate of the re Maillard reactions. During the spray drying process, the moisture con
actions. At a low water activity, low mobility of the molecules also re tents of the particles change rapidly, and thus the glass transition tem
duces the rate of reactions. The water activity giving the maximum peratures of the particles also change. The results of Miao and Roos
reaction rate for Maillard reactions was found to correspond to a (2004) suggested that the change in the glass transition temperature
moisture content of approximately 50 w/w%. (Nursten, 2005). during the spray drying process is also an important factor that needs to
Spray-dried products typically contain no more than 3–4 w/w% mois be considered when studying Maillard reactions in spray dryers.
ture to prevent the growth of micro-organisms, to prolong the shelf-lives
of the products (Nursten, 2005). In practice, the feeds are usually 4.6. Segregation
dewatered before spray drying to 45-48 wt% solid content to reduce
energy consumption during drying (Písecký, 2012). The initial moisture Segregation is a process where different components in a mixture
content of the feed may have a limited impact on the kinetics of the separate from each other during processing. Many studies have reported
Maillard reactions in spray dryers, since most of the water evaporates heterogeneous distributions of components in spray-dried products,
rapidly in a short time, and the particle temperature rises slowly due to which has suggested that segregation does occur during the spray-drying
the cooling effect of the rapid evaporation. process of a multi-component system (Baklouti et al., 1998; Kim et al.,
In addition to affecting the concentration and mobility of the re 2003). These studies found that, for spray-dried protein-sugar systems,
actants, water may also play an important role in the kinetics of Maillard the surface of the particles is generally rich in protein. When fat is
reactions in spray dryers. During the formation of Amadori products, a present in the systems, the surfaces of the particles are dominated by fats
water molecule is eliminated. Thus, there are two possible degradation instead of proteins, likely due to the fact that fats are more surface active
pathways for Amadori products, hydrolysis or direct cleavage (Kocadaǧ; than proteins (Kim et al., 2003).
li and Gökmen, 2016). When the water becomes a limiting reactant, the For Maillard reactions in spray dryers, amino acids are most likely to
hydrolysis pathway is expected to be limited while the dehydration come from proteins, and reducing sugars are found in carbonyl com
pathway is preferred. As a result, certain reaction pathways, such as pounds. These two types of compounds have significantly different
direct dehydration of glucose, are expected to be favoured at high physical properties, which may cause segregation behaviour inside
temperatures and low moisture contents. This type of situation is particles during the spray-drying process, according to the hypotheses
applicable to particles near the outlet of spray dryers and those stuck to identified above (Charlesworth and Marshall, 1960; Fäldt and Bergen
the walls (Kocadaǧ;li and Gökmen, 2016). ståhl, 1994; Meerdink, 1994). For example, α-Lactalbumin, one of the
Water is produced during different stages of the Maillard reactions, main components of whey protein isolate (WPI), has a diffusion coeffi
and a substantial proportion of water is produced during the second cient of 0.12 × 10− 9 m2/s in water at 25 ◦ C (Saltzman et al., 1994), while
stage of Maillard reactions (Nursten, 2005). The production of water due lactose has a much higher diffusion coefficient under the same condi
to Maillard reactions that may occur inside a spray dryer is likely to have tions (0.566 × 10− 9 m2/s) (Killie et al., 1991). Proteins also have higher
a limited impact on the kinetics of Maillard reactions in spray dryers surface activities than sugars (Fang et al., 2013). These two components
since the amount of water produced is typically insignificant compared are found in skim milk, in significant quantities, and various studies
with the amount of water in the droplet and the drying rate of the have reported that segregation occurs during the spray-drying process of
powder. On the other hand, the production of water during the storage milk or similar systems (Fäldt and Bergenståhl, 1994; Kim et al., 2003;
of the spray-dried product may be an important factor, since the prod Nijdam and Langrish, 2006; Wang et al., 2013) (Fig. 7).
ucts typically have a low moisture content (Pereyra Gonzales et al., As a result of component segregation during the spray-drying pro
2010). In a study by Ceylan Sahin et al. (2018), different water activities cess, the ratios of each component in various layers of the particles will
were found in spray-dried samples stored using different packaging be different. The different compositions of each layer may change the
materials. Samples with higher water activity were also found to have a reaction kinetics. For example, for the outer layers of skim milk particles
greater extent of Maillard reactions. Water production in low water during the spray-drying process, the concentrations of lactose are likely
activity products (e.g. spray-dried) products may also promote the to be the rate-limiting factor for the initial stages of Maillard reactions,
growth of micro-organisms. since proteins are the dominant component. However, in the inner layer
of the particles, the concentration of protein is likely to be the rate-
4.5. Glass transition temperature (Tg) limiting factor, since lactose is the dominant component (Fäldt and
Bergenståhl, 1994).
The glass transition temperature is the temperature at which amor The impact of segregation on the overall extent of the Maillard re
phous materials transform from hard glassy to rubbery sticky states actions in spray-dried products was not considered in most of the studies
(Reid and Levine, 1991; Roos, 2016; Sherrington, 1993). As mentioned investigating Maillard reactions in spray dryers. More investigation is
in the previous section, the physical state of the reactants has a critical required to understand the segregation process and how this phenom
role in the kinetics of Maillard reactions for “dry” systems. Glass tran enon may be used for improving the quality of the final product.
sition will affect the physical properties of the material and may increase
the amount of wall deposition in spray dryers (Straatsma et al., 1999;
7
compared with the airborne residence time. Furthermore, they also

found that more than 20% of detergent particles collected from a swirl
counter-current spray dryer have been re-entrained from the wall de
posits. A similar process can be expected in other types of spray dryers.
Longer particle residence times will result in greater extents of
Maillard reactions, since Maillard reactions are clearly time-dependent
(Hodge, 1953; van Boekel, 1998). Therefore, the residence time of
particles and how they are affected by wall deposition is another
important factor that needs to be considered when studying Maillard
reactions in spray dryers.
4.8. Particle residence time distribution in spray dryers
The particle residence time in spray dryer is another important factor

that needs to be considered when studying Maillard reactions in spray
dryers (Schmitz-Schug et al., 2013; van Boekel, 1998), and it is linked to
the phenomenon of re-entrainment that has just been discussed. The
particle residence time consists of particles that travel through two
routes, creating a primary particle residence time and a secondary
particle residence time. The primary particle residence time is the
Fig. 7. Schematic diagram of dominant components in different layers of spray- amount of time for particles to move from the outlet of the nozzle to the
dried milk particle. outlet of the dryer or wall directly in the air flow. Secondary residence
time is the amount of time that a particle stays on the wall, gets
4.7. Wall deposition and re-entrainment re-entrained and then moves to the outlet of the dryer (Anandhar
amakrishnan et al., 2010).
During the spray drying process, some of the particles may deposit Kieviet investigated the particle residence time in a co-current spray
onto the inner walls of spray dryers, and this process is known as wall dryer using modelling and experimental methods. In his study, the
deposition. The main consequences of wall deposition include the loss of average primary particle residence time (estimated based on the model
products, the build-up of material within the spray dryer, the effects on developed) was found to be significantly shorter than the gas residence
the gas flow patterns, the contamination caused by re-entrainment, and time, due possibly to the initial speed of particles coming out of the
extended particle residence times (Keshani et al., 2015). Extended par nozzle (Kieviet, 1997). A similar result was also obtained in a later study
ticle residence times mean extended reaction times for the Maillard re by Anandharamakrishnan et al. (2010). Different particle residence
action. Wall deposition can be affected by the configurations of the spray times have been reported in different studies. The reported mean par
dryers. The geometry of the spray dryer is important, and inappropriate ticle residence times range from as short as 58.5 s to as long as 12 min,
geometries, sizes and shapes of spray dryers may result in an increased depending on the configuration of the spray drying system (Gian
amount of deposition (Masters, 1979; Oakley, 1994). The wall material francesco, 2009; Jeantet et al., 2008; Schmitz-Schug et al., 2013). In
may also play an important role in wall deposition (Huang et al., 2003; Kieviet’s study, some particle residence times can be up to 10 min,
Huang and Mujumdar, 2006). Experimental work by Ozmen and despite the relatively short mean particle residence time (less than a
Langrish (2003) showed that reducing the amount of swirl in the air flow minute). Extended mean particle residence times within the spray dryer
at the entrance of the spray dryer may also reduce the amount of wall may give a greater extent of thermal degradation of the product (Kieviet,
deposition. 1997). In order to understand the kinetics of Maillard reactions in spray
Other than the configuration of the spray dryer, material stickiness dryers, it is necessary to establish a good understanding of the particle
also affects the wall deposition rate in a spray dryer. The study of Ozmen residence times within the spray dryer. In previous studies, particle
and Langrish (2003) showed that less deposition is observed when the residence times have been measured by introducing tracers (e.g.
temperature of the particles is below the sticky-point value. Component maltodextrin, sodium chloride, colour dye) and collecting samples
segregation will also affect the amount of wall deposition. Migration of during the spray drying process (Gianfrancesco, 2009; Jeantet et al.,
components that have higher glass transition temperatures to the sur 2008; Kieviet, 1997; Schmitz-Schug et al., 2013). However, there are
faces of the droplet will result in a protective layer and will result in less significant limitations in the methods used in their studies; The sampling
wall deposition (Keshani et al., 2013; Kim et al., 2003; Wang and rates were limited by their sampling device. For example, in Francia
Langrish, 2009). et al.’s study (2015), samples were collected from the belt located at the
Re-entrainment of wall deposition has been reported in some studies outlet of the spray dryer, and the sampling intervals were 15 s. This
(Francia et al., 2015; Keshani et al., 2013; Kim et al., 2003; Wang and sampling frequency was sufficient for determining the residence time of
Langrish, 2009). Re-entrainment of wall deposition will cause an in re-entrained wall deposits, but insufficient for measuring the airborne
crease in the particle residence time above the time expected if particles phase residence time, as this airborne residence time is expected to be
flowed with the gas without interacting with the walls (Hanus and less than 35–45 s (Harvie et al., 2002). Furthermore, some very fine
Langrish, 2007; Kieviet and Kerkhof, 1995; Mazza et al., 2003). The particles exiting from the top of the spray dryer were not measured.
physical processes and phenomena of wall deposition, re-entrainment, Thus, a better sampling technique may be required for future studies and
agglomeration and residence time distribution are all interlinked, in need to be extended to other types of spray dryers and feeds.
the sense that the deposition of particles on the walls, and then subse In order to have a better experimental determination of the particle
quent re-entrainment, increases the effective residence time of particles, residence times, an advanced non-intrusive method is required. Intro
and also causes agglomeration of particles (Francia et al., 2015). In their ducing and activating fluorescence material during the spray drying
study, the formation of wall deposition in a swirl spray dryer was found process may be an effective method. Fluorescent tracers can be detected
to be a dynamic process. During the spray drying process, deposits on within the spray dryer (inlet, outlet, and in-between) using photo
the walls of spray dryers are constantly renewed. They also found that multipliers. This type of non-intrusive method may avoid affecting the
the age of particles in a swirl spray dryer may be extended by the for gas flow pattern within the spray dryer and thus the particle residence
mation of deposits and the re-entrainment process by 10–100 times times. Furthermore, photomultipliers may have a much faster sampling
8
rate, compared with traditional methods. However, there are still some Wang and Langrish, 2009).
potential issues, such as powder deposits on the sensors, which may Although the lumped-parameter approach (CDC) has been found by
affect the accuracy of the results and need to be addressed. Lastly, the Jaskulski et al. (2017) to be suitable for predicting the temperatures and
hazards related to the fluorescent powder produced during the experi moisture contents that affect certain types of reactions (protein dena
ment should also be taken into consideration. Other than the intro turation) during the spray-drying process, it may be less suitable for the
ducing fluorescent dye into the feed, using phase doppler anemometry predicting Maillard reactions in the spray-drying process. The main
(PDA) or other types of laser detection devices in spray dryers is also an difference between protein denaturation and Maillard reactions is that
option for estimating the particle residence times. Such approaches were more than one component is involved in Maillard reactions, while pro
used in Kohlus’s study for determining the particle size distributions tein denaturation involves a more limited range of components (Nurs
from different spray dryers (Ruprecht and Kohlus, 2019). ten, 2005). When there is more than one component involved in the
reaction, the impact of segregation during the spray drying process may
4.9. Drying kinetics in spray dryers become more significant. Due to the lumped-parameter nature of their
approach, the impact of segregation was not considered.
The drying kinetics of the particles in a spray dryer may also affect In contrast to lumped-parameter models, distributed-parameter
the kinetics of Maillard reactions in spray dryers. In a spray dryer, the models do not assume that the temperatures and moisture contents in
thermal exposure of the powder is the same as the thermal exposure of side the particles are homogenous, and thus the concentration and
the particles, so the particle temperature is very relevant to this dis temperature profiles within the particles are predicted. In theory, this
cussion. The particle temperature has been shown to be very close to type of model may be more suitable for modelling Maillard reactions
that of the outlet gas temperature in most of a co-current spray dryer by that occur in the spray dryers compared with lumped-parameter models.
Chiou et al. (2008). The only reason why a spray-drying situation might Despite the clear theoretical advantage of distributed-parameter models
be different (particle temperature close to outlet gas temperature) is that over the lumped-parameter models, the difference in estimating the
there might be a significant unhindered (constant rate) drying period, overall extent of the Maillard reactions in the spray-dried product may
when the particle temperature might be closer to the wet-bulb temper be small. Distributed-parameter models are also more computationally
ature of the air for some part of the overall drying period. However, most expensive to solve.
foods do not show a significant constant-rate period during drying
(Langrish and Kockel, 2001). Therefore the gas outlet temperature, if 5. Conclusions
measured, can normally be used as an estimate of the particle, powder
and material temperatures during spray drying, which are the reaction In this review, many factors that may affect the mechanism of
temperatures for the Maillard reactions. Maillard reactions in spray dryers have been reviewed. The mechanisms
However, the outlet gas temperature alone is not sufficient for of Maillard reactions in spray dryers may be different from those in
describing the impact of different spray drying conditions on the kinetics liquid systems due to the rapid changes in temperature and moisture
of the Maillard reactions in the spray dryer. In a later study by Park et al. content in the equipment. Although the mechanisms of Maillard re
(2016), the feed flow rate was changed during the experiments to actions in liquid systems have been studied extensively, only limited
maintain the same outlet gas temperature, where different feed solid studies have addressed this (Gómez-Narváez et al., 2019; Grigioni et al.,
contents and inlet gas temperatures were used for the experiments. In 2007; Miao and Roos, 2004; Park et al., 2016). Most of the research in
this paper, higher furosine levels were found as the inlet temperature the relevant area is mainly focused on how the operating conditions or
and the solids concentration increased. The increase in the inlet tem the storage conditions affect the extent of Maillard reactions in
perature should result in more thermal exposure for the particles, giving spray-dried products, but the mechanism of Maillard reactions occurring
a greater extent of Maillard reactions, hence increasing the furosine in spray dryers has not been investigated. Nevertheless, different spray
levels. The increase in the solids concentration is also likely to lead to a dryers were used in those studies, and they all have different charac
greater extent of Maillard reactions (greater furosine levels) due to teristics which may affect their results. However, the impact of the
changes in the atomisation behaviour, as follows. Higher solids con characteristics of the spray dryers was not considered in those studies.
centrations tend to give larger droplets, and larger droplets take longer Therefore, establishing a better understanding of the mechanisms of
to dry out and are wetter for longer, so the liquid-phase reaction times Maillard reactions in spray dryers by including the characteristics of the
are longer for larger droplets. Therefore, larger droplets (from higher spray dryers is necessary.
solids concentrations) are also likely to show more Maillard reaction
products, such as furosine, as observed in this paper. In Zbicinski et al.’s
Declaration of competing interest
(2002) study, the drying kinetics of maltodextrin and Bakers’ yeast were
investigated in situ during spray drying. In their results, different
The authors declare that they have no known competing financial
atomisation ratios were found to give different drying kinetics. There
interests or personal relationships that could have appeared to influence
fore, it is also necessary to consider the drying kinetics of particles in
the work reported in this paper.
spray dryers when investigating the Maillard reactions in this
equipment.
References
For modelling the drying kinetics of particles in spray dryers, there
are two main types of model: lumped-parameter models and distributed- Aalaei, K., Sjöholm, I., Rayner, M., Teixeira, C., Tareke, E., 2019. Early and advanced
parameter models. In lumped-parameter models, the droplet and par stages of Maillard reaction in infant formulas: analysis of available lysine and
ticle are assumed to be homogeneous, and the temperatures and con carboxymethyl-lysine. PloS One 14. https://doi.org/10.1371/journal.
pone.0220138.
centrations in different layers of the particles are assumed to be the Adhikari, B., Howes, T., Bhandari, B.R., 2007. Use of solute fixed coordinate system and
same. Examples of this approach are the concept of a characteristic method of lines for prediction of drying kinetics and surface stickiness of single
drying curve (CDC) and the reaction engineering approach (REA) (Chen droplet during convective drying. Chem. Eng. Process. Process Intensif. 46, 405–419.
https://doi.org/10.1016/j.cep.2006.06.018.
and Lin, 2005; Keey, 1978; Tran et al., 2017). However, temperature and
Akagawa, M., Miura, T., Suyama, K., 2002. Factors influencing the early stage of the
concentration profiles exist in droplets, and they may affect the drying Maillard reaction. Int. Congr. Ser. 1245, 395–396. https://doi.org/10.1016/S0531-
kinetics. Distributed parameter models have also been introduced to 5131(02)00896-8.
describe the spray-drying process. Distributed-parameter models allow Anandharamakrishnan, C., Gimbun, J., Stapley, A.G.F., Rielly, C.D., 2010. A study of
particle histories during spray drying using computational fluid dynamic
temperature and concentration profiles that exist in the particles to be simulations. Dry. Technol. 28, 566–576. https://doi.org/10.1080/
predicted (Adhikari et al., 2007; Lertsiri et al., 1995; Wang et al., 2013; 07373931003787918.
9
Baklouti, S., Chartier, T., Baumard, J.F., 1998. Binder distribution in spray-dried alumina Huang, L., Mujumdar, A.S., 2006. Numerical study of two-stage horizontal spray dryers
agglomerates. J. Eur. Ceram. Soc. 18, 2117–2121. https://doi.org/10.1016/S0955- using computational fluid dynamics. Dry. Technol. 24, 727–733. https://doi.org/
2219(98)00107-1. 10.1080/07373930600685046.
Bertrand, E., Meyer, X.M., Machado-Maturana, E., Berdagué, J.L., Kondjoyan, A., 2015. Hurrell, R.F., Finot, P.A., Ford, J.E., 1983. Storage of milk powders under adverse
Modelling the Maillard reaction during the cooking of a model cheese. Food Chem. conditions. Br. J. Nutr. 49, 343–354. https://doi.org/10.1079/bjn19830043.
184, 229–237. https://doi.org/10.1016/j.foodchem.2015.03.097. Jaskulski, M., Atuonwu, J.C., Tran, T.T.H., Stapley, A.G.F., Tsotsas, E., 2017. Predictive
Caric, M., Kalab, M., 1987. Effects of drying techniques on milk powders quality and CFD modeling of whey protein denaturation in skim milk spray drying powder
Microstructure : a review. Food Microstruct. 6, 171–180. production. Adv. Powder Technol. 14–16. https://doi.org/10.1016/j.
Carter, B., Patel, H., Barbano, D.M., Drake, M.A., 2018. The effect of spray drying on the apt.2017.09.026.
difference in flavor and functional properties of liquid and dried whey proteins, milk Jeantet, R., Ducept, F., Dolivet, A., Méjean, S., Schuck, P., 2008. Residence time
proteins, and micellar casein concentrates. J. Dairy Sci. 101, 3900–3909. https:// distribution: a tool to improve spray-drying control. Dairy Sci. Technol. 88, 31–43.
doi.org/10.3168/jds.2017-13780. https://doi.org/10.1051/dst:2007006.
Ceylan Sahin, C., Erbay, Z., Koca, N., 2018. The physical, microstructural, chemical and Jousse, F., Jongen, T., Agterof, W., Russell, S., Braat, P., 2002. Simplified kinetic scheme
sensorial properties of spray dried full-fat white cheese powders stored in different of flavor formation by the Maillard reaction. J. Food Sci. 67, 2534–2542. https://doi.
multilayer packages. J. Food Eng. 229, 57–64. https://doi.org/10.1016/j. org/10.1111/j.1365-2621.2002.tb08772.x.
jfoodeng.2017.11.022. Katekhong, W., Charoenrein, S., 2018. Influence of spray drying temperatures and
Chansataporn, W., Tangduangdee, C., Nopharatana, M., Siriwattanayotin, S., 2019. storage conditions on physical and functional properties of dried egg white. Dry.
Kinetics of Maillard Reaction in a Chicken Meat Model System Using a Technol. 36, 169–177. https://doi.org/10.1080/07373937.2017.1307218.
Multiresponses Modeling Approach. https://doi.org/10.1002/kin.21224. Keey, R.B., 1978. Introduction to Industrial Drying Operations. Pergamon.
Charlesworth, D.H., Marshall, W.R., 1960. Evaporation from drops containing dissolved Keshani, S., Daud, W.R.W., Nourouzi, M.M., Namvar, F., Ghasemi, M., 2015. Spray
solids. AIChE J. 6, 9–23. https://doi.org/10.1002/aic.690060104. drying: an overview on wall deposition, process and modeling. J. Food Eng. 146,
Chen, X.D., Lin, S.X.Q., 2005. Air drying of milk droplet under constant and time- 152–162. https://doi.org/10.1016/j.jfoodeng.2014.09.004.
dependent conditions. AIChE J. 51, 1790–1799. https://doi.org/10.1002/aic.10449. Keshani, S., Daud, W.R.W., Woo, M.W., Nourouzi, M.M., Talib, M.Z.M., Chuah, A.L.,
Chiou, D., Langrish, T.A.G., Braham, R., 2008. Partial crystallization behavior during Russly, A.R., 2013. Reducing the deposition of fat and protein covered particles with
spray drying: simulations and experiments. Dry. Technol. 26, 27–38. https://doi. low energy surfaces. J. Food Eng. 116, 737–748. https://doi.org/10.1016/j.
org/10.1080/07373930701781181. jfoodeng.2013.01.003.
Claeys, W.L., Van Loey, A.M., Hendrickx, M.E., 2003. Kinetics of hydroxymethylfurfural, Kieviet, F., Kerkhof, J.A.M., 1995. Measurements of particle residence time distributions
lactulose and furosine formation in milk with different fat content. J. Dairy Res. 70, in a co-current spray dryer. Dry. Technol. 13, 1241–1248.
85–90. https://doi.org/10.1017/S0022029902005897. Kieviet, F.G., 1997. Modelling Quality in Spray Drying. Ph.D. Dissertation. https://doi.
Copado, C.N., Diehl, B.W.K., Ixtaina, V.Y., Tomás, M.C., 2017. Application of Maillard org/10.6100/IR477431.
reaction products on chia seed oil microcapsules with different core/wall ratios. LWT Killie, S., Hafskjold, B., Borgen, O., Ratkje, S.K., Hovde, E., 1991. High-pressure diffusion
- Food Sci. Technol. (Lebensmittel-Wissenschaft -Technol.) 86, 408–417. https://doi. measurements by Mach-Zehnder interferometry. AIChE J. 37, 142–146. https://doi.
org/10.1016/j.lwt.2017.08.010. org/10.1002/aic.690370113.
Davidek, T., Clety, N., Aubin, S., Blank, I., 2002. Degradation of the Amadori compound Kim, E.H.J., Chen, X.D., Pearce, D., 2003. On the mechanisms of surface formation and
N-(1-deoxy-d-fructos-1-yl) glycine in aqueous model systems. J. Agric. Food Chem. the surface compositions of industrial milk powders. Dry. Technol. 21, 265–278.
50, 5472–5479. https://doi.org/10.1021/jf025561j. https://doi.org/10.1081/DRT-120017747.
Fäldt, P., Bergenståhl, B., 1994. The surface composition of spray-dried protein-lactose Koca, N., Erbay, Z., Kaymak-Ertekin, F., 2015. Effects of spray-drying conditions on the
powders. Colloids Surfaces A Physicochem. Eng. Asp. 90, 183–190. https://doi.org/ chemical, physical, and sensory properties of cheese powder. J. Dairy Sci. 98,
10.1016/0927-7757(94)02914-8. 2934–2943. https://doi.org/10.3168/jds.2014-9111.
Fang, Z., Wang, R., Bhandari, B., 2013. Effects of type and concentration of proteins on Kocadaǧli, T., Gökmen, V., 2016. Multiresponse kinetic modelling of Maillard reaction
the recovery of spray-dried sucrose powder. Dry. Technol. 31, 1643–1652. https:// and caramelisation in a heated glucose/wheat flour system. Food Chem. 211,
doi.org/10.1080/07373937.2013.770011. 892–902. https://doi.org/10.1016/j.foodchem.2016.05.150.
Fialho, T.L., Martins, E., Silva, C.R.D.J., Stephani, R., Tavares, G.M., Silveira, A.C.P., Lakni, W., Jayasinghe-Mudalige, U., 2010. Customer-defined quality of food: an
Perrone, Í.T., Schuck, P., De Oliveira, L.F.C., De Carvalho, A., 2018. Lactose- empirical investigation based on Kano Analytical Methods for milk powder. J. Agric.
hydrolyzed milk powder: Physicochemical and technofunctional characterization. Sci. 4 https://doi.org/10.4038/jas.v4i2.1644.
Drying Technology 36 (14), 1688–1695. https://doi.org/10.1080/ Langrish, T.A.G., Kockel, T.K., 2001. The assessment of a characteristic drying curve for
07373937.2017.1421551. milk powder for use in computational fluid dynamics modelling. Chem. Eng. J. 84,
Finot, P.A., Deutsch, R., Bujard, E., 1981. The extent of the Maillard reaction during the 69–74. https://doi.org/10.1016/S1385-8947(00)00384-3.
processing of milk. Prog. Food Nutr. Sci. 5, 345–355. Lea, C.H., Hannan, R.S., 1949. Studies of the reaction between proteins and reducing
Francia, V., Martin, L., Bayly, A.E., Simmons, M.J.H., 2015. The role of wall deposition sugars in the “dry” state. Biochim. Biophys. Acta 3, 313–325. https://doi.org/
and re-entrainment in swirl spray dryers. AIChE J. 61, 1804–1821. https://doi.org/ 10.1016/0006-3002(49)90100-6.
10.1002/aic.14767. Lee, Y.Y., Tang, T.K., Phuah, E.T., Alitheen, N.B.M., Tan, C.P., Lai, O.M., 2017. New
Ge, S.J., Lee, T.C., 1997. Kinetic significance of the Schiff base reversion in the early- functionalities of Maillard reaction products as emulsifiers and encapsulating agents,
stage maillard reaction of a phenylalanine-glucose aqueous model system. J. Agric. and the processing parameters: a brief review. J. Sci. Food Agric. 97, 1379–1385.
Food Chem. 45, 1619–1623. https://doi.org/10.1021/jf960458d. https://doi.org/10.1002/jsfa.8124.
Gianfrancesco, A., 2009. Spray drying Engineering : particle stickiness in relation with Lee, Y.Y., Tang, T.K., Tan, C.P., Alitheen, N.B.M., Phuah, E.T., Karim, N.A.A., Lai, O.M.,
agglomeration. These Times 228. 2015. Entrapment of palm-based medium- and long-chain triacylglycerol via
Gökmen, V., Şenyuva, H.Z., 2007. Effects of some cations on the formation of acrylamide maillard reaction products. Food Bioprocess Technol. 8, 1571–1582. https://doi.
and furfurals in glucose-asparagine model system. Eur. Food Res. Technol. 225, org/10.1007/s11947-015-1520-1.
815–820. https://doi.org/10.1007/s00217-006-0486-7. Lertsiri, S., Fujimoto, K., Miyazawa, T., 1995. Pyrone hydroperoxide formation during
Gómez-Narváez, F., Contreras-Calderón, J., Pérez-Martínez, L., 2019. Usefulness of some the Maillard reaction and its implication in biological systems. Biochim. Biophys.
Maillard reaction indicators for monitoring the heat damage of whey powder under Acta 1245 (3), 278–284. https://doi.org/10.1016/0304-4165(95)00129-8.
conditions applicable to spray drying. Int. Dairy J. 99 https://doi.org/10.1016/j. Maillard, L.C., 1912. Action des acides aminés sur les sucres: formation des mélanoidines
idairyj.2019.104553. par voie méthodique. Réaction de Maillard. C. R. Acad. Sci. 154, 66–68.
Grigioni, G., Biolatto, A., Irurueta, M., Sancho, A.M., Páez, R., Pensel, N., 2007. Color Martins, S.I.F.S., Jongen, W.M.F., van Boekel, M.A.J.S., 2000. A review of Maillard
changes of milk powder due to heat treatments and season of manufacture. Cienc. reaction in food and implications to kinetic modelling. Trends Food Sci. Technol. 11,
Tecnol. Aliment. 5, 335–339. https://doi.org/10.1080/11358120709487709. 364–373. https://doi.org/10.1016/S0924-2244(01)00022-X.
Hanus, M.J., Langrish, T.A.G., 2007. Re-entrainment of wall deposits from a laboratory- Martins, S.I.F.S., van Boekel, M.A.J.S., 2005. A kinetic model for the glucose/glycine
scale spray dryer. Asia Pac. J. Chem. Eng. 2, 90–107. https://doi.org/10.1002/ Maillard reaction pathways. Food Chem. 90, 257–269. https://doi.org/10.1016/j.
apj.47. foodchem.2004.04.006.
Harvie, D.J.E., Langrish, T.A.G., Fletcher, D.F., 2002. A computational fluid dynamics Martins, S.I.F.S., van Boekel, M.A.J.S., 2002. Key intermediates in early stage Maillard
study of a tall-form spray dryer. Food Bioprod. Process. Trans. Inst. Chem. Eng. Part reaction: kinetic analysis. Int. Congr. Ser. 1245, 469–470. https://doi.org/10.1016/
C 80, 163–175. https://doi.org/10.1016/S0960-3085(02)70316-7. S0531-5131(02)00904-4.
Hodge, J.E., 1953. Dehydrated foods, chemistry of browning reactions in model systems. Masters, K., 1979. Spray Drying Handbook, 3d ed. G. Godwin, London.
J. Agric. Food Chem. 1, 928–943. https://doi.org/10.1021/jf60015a004. Matiacevich, S.B., Santagapita, P.R., Buera, M.P., 2005. Fluorescence from the maillard
Huang, G.Q., Wang, H.O., Wang, F.W., Du, Y.L., Xiao, J.X., 2020. Maillard reaction in reaction and its potential applications in food science. Crit. Rev. Food Sci. Nutr. 45,
protein – polysaccharide coacervated microcapsules and its effects on microcapsule 483–495. https://doi.org/10.1080/10408390591034472.
properties. Int. J. Biol. Macromol. 155, 1194–1201. https://doi.org/10.1016/j. Mazza, M.G.G., Brandao, L.E.B., Wildhagen, G.S., 2003. Characterization of the residence
ijbiomac.2019.11.087. time distribution in spray dryers. Dry. Technol. 21, 525–538. https://doi.org/
Huang, K., Zhang, P.J., Hu, B., Yu, S.J., 2016. The effect of spray drying on sucrose- 10.1081/DRT-120018460.
glycine caramel powder preparation. J. Sci. Food Agric. 96, 2319–2327. https://doi. McSweeney, P.L.H., Fox, P.F., 2009. Advanced Dairy Chemistry, Advanced Dairy
org/10.1002/jsfa.7347. Chemistry. https://doi.org/10.1007/978-0-387-84865-5.
Huang, L., Kumar, K., Mujumdar, A.S., 2003. Use of computational fluid dynamics to Meerdink, G., 1994. Drying of liquid food droplets enzyme inactivation and
evaluate alternative spray dryer chamber configurations. Dry. Technol. 21, 385–412. multicomponent diffusion. Dry. Technol. 12 (4), 981–982. https://doi.org/10.1080/
https://doi.org/10.1081/DRT-120018454. 07373939408960007.
10
Miao, S., Roos, Y.H., 2004. Nonenzymatic browning kinetics of a carbohydrate-based Ruprecht, N.A., Kohlus, R., 2019. Determination and Modelling of the Particle Size
low-moisture food system at temperatures applicable to spray drying. J. Agric. Food Dependent Residence Time Distribution in a Pilot Plant Spray Dryer. https://doi.
Chem. 52, 5250–5257. https://doi.org/10.1021/jf049706t. org/10.4995/ids2018.2018.7740.
Michalska, A., Wojdyło, A., Brzezowska, J., Majerska, J., Ciska, E., 2019. The influence of Saltzman, W.M., Radomsky, M.L., Whaley, K.J., Cone, R.A., 1994. Antibody diffusion in
inulin on the retention of polyphenolic compounds during the drying of blackcurrant human cervical mucus. Biophys. J. 66, 508–515. https://doi.org/10.1016/S0006-
juice. Molecules 24. https://doi.org/10.3390/molecules24224167. 3495(94)80802-1.
Morales, F.J., Romero, C., Jiménez-Pérez, S., 1997. Chromatographic determination of Samborska, K., Jedlińska, A., Wiktor, A., Derewiaka, D., Wołosiak, R., Matwijczuk, A.,
bound hydroxymethylfurfural as an index of milk protein glycosylation. J. Agric. Jamróz, W., Skwarczyńska-Maj, K., Kiełczewski, D., Błażowski, Ł., Tułodziecki, M.,
Food Chem. 45, 1570–1573. https://doi.org/10.1021/jf960930v. Witrowa-Rajchert, D., 2019. The effect of low-temperature spray drying with
Mundt, S., Wedzicha, B.L., van Boekel, M.A.J.S., 2002. A kinetic model for the dehumidified air on phenolic compounds, antioxidant activity, and aroma
maltose–glycine reaction. Int. Congr. Ser. 1245, 465–467. https://doi.org/10.1016/ compounds of rapeseed honey powders. Food Bioprocess Technol. https://doi.org/
S0531-5131(02)00914-7. 10.1007/s11947-019-02260-8.
Nijdam, J.J., Langrish, T.A.G., 2006. The effect of surface composition on the functional Schmitz-Schug, I., Foerst, P., Kulozik, U., 2013. Impact of the spray drying conditions
properties of milk powders. J. Food Eng. 77, 919–925. https://doi.org/10.1016/j. and residence time distribution on lysine loss in spray dried infant formula. Dairy
jfoodeng.2005.08.020. Sci. Technol. 93, 443–462. https://doi.org/10.1007/s13594-013-0115-8.
Nijdam, J.J., Langrish, T.A.G., 2005. An investigation of milk powders produced by a Schuck, P., 2006. Spray drying of dairy products: a review. New Food 1, 14–20.
laboratory-scale spray dryer. Dry. Technol. 23, 1043–1056. https://doi.org/ Sherrington, D.C., 1993. Introduction to physical polymer science. React. Polym. 20,
10.1081/DRT-200060208. 217–218. https://doi.org/10.1016/0923-1137(93)90096-x.
Nishanthi, M., Chandrapala, J., Vasiljevic, T., 2018. Physical properties of selected spray Shishir, M.R.I., Chen, W., 2017. Trends of spray drying: a critical review on drying of
dried whey protein concentrate powders during storage. J. Food Eng. 219, 111–120. fruit and vegetable juices. Trends Food Sci. Technol. 65, 49–67. https://doi.org/
https://doi.org/10.1016/j.jfoodeng.2017.09.021. 10.1016/j.tifs.2017.05.006.
Nunes, L., Martins, E., Tuler Perrone, Í., Fernandes de Carvalho, A., 2019. The maillard Straatsma, J., Van Houwelingen, G., Steenbergen, A.E., De Jong, P., 1999. Spray drying
reaction in powdered infant formula. J. Food Nutr. Res. 7, 33–40. https://doi.org/ of food products: 1. Simulation model. J. Food Eng. 42, 67–72. https://doi.org/
10.12691/jfnr-7-1-5. 10.1016/S0260-8774(99)00107-7.
Nursten, H., 2005. The Maillard Reaction: Chemistry, Biochemistry and Implications by Tomlinson, A.J., Mlotkiewicz, J.A., Lewis, I.A.S., 1993. An investigation of the
Harry Nursten. Royal Society of Chemistry. https://doi.org/10.1071/CH0505_BR. compounds produced by spray-drying an aqueous solution of glucose and glycine.
Nursten, H.E., 1986. Maillard Browning Reaction in Dried Foods. Food Chem. 48, 373–379. https://doi.org/10.1016/0308-8146(93)90320-F.
Oakley, D.E., 1994. Scale-up of spray dryers with the aid of computational fluid Tran, T.T.H., Jaskulski, M., Tsotsas, E., 2017. Reduction of a model for single droplet
dynamics. Dry. Technol. 12, 217–233. https://doi.org/10.1080/ drying and application to CFD of skim milk spray drying. Dry. Technol. 35,
07373939408959954. 1571–1583. https://doi.org/10.1080/07373937.2016.1263204.
Ozmen, L., Langrish, T.A.G., 2003. An experimental investigation of the wall deposition van Boekel, M.A.J.S., 2001. Kinetic aspects of the Maillard reaction: a critical review.
of milk powder in a pilot-scale spray dryer. Dry. Technol. 21, 1253–1272. https:// Nahrung-Food 45, 150–159. https://doi.org/10.1002/1521-3803(20010601)45:
doi.org/10.1081/DRT-120023179. 3<150::AID-FOOD150>3.0.CO;2-9.
Park, C.W., Stout, M.A., Drake, M., 2016. The effect of spray-drying parameters on the van Boekel, M.A.J.S., 1998. Effect of heating on Maillard reactions in milk. Food Chem.
flavor of nonfat dry milk and milk protein concentrate 70%. J. Dairy Sci. 99, 62, 403–414. https://doi.org/10.1016/S0308-8146(98)00075-2.
9598–9610. https://doi.org/10.3168/jds.2016-11692. Van Boekel, M.A.J.S., Martins, S.I.F.S., 2002. Fate of glycine in the glucose–glycine
Pereyra Gonzales, A.S., Naranjo, G.B., Leiva, G.E., Malec, L.S., 2010. Maillard reaction reaction: a kinetic analysis. Int. Congr. Ser. 1245, 289–293. https://doi.org/
kinetics in milk powder: effect of water activity at mild temperatures. Int. Dairy J. 10.1016/S0531-5131(02)00893-2.
20, 40–45. https://doi.org/10.1016/j.idairyj.2009.07.007. Vasbinder, A.J., de Kruif, C.G., 2003. Casein–whey protein interactions in heated milk:
Písecký, J., 2012. Handbook of Milk Powder Manufacture. GEA Process Engineering A/S, the influence of pH. Int. Dairy J. 13, 669–677. https://doi.org/10.1016/S0958-6946
Copenhagen, Denmark, p. 124. (03)00120-1.
Pokorný, J., Pilková, L., Davídek, J., Valentová, H., 1988. Effect of Amadori Verardo, V., Riciputi, Y., Messia, M.C., Marconi, E., Caboni, M.F., 2017. Influence of
rearrangement products on the non-enzymic browning in model systems. Food drying temperatures on the quality of pasta formulated with different egg products.
Nahrung 32, 767–776. https://doi.org/10.1002/food.19880320814. Eur. Food Res. Technol. 243, 817–825. https://doi.org/10.1007/s00217-016-2795-
Reid, D.S., Levine, H., 1991. Beyond water activity: recent advances based on an 9.
alternative approach to the assessment of food quality and safety. Crit. Rev. Food Sci. Wang, S., Langrish, T., 2009. A review of process simulations and the use of additives in
Nutr. 30, 115–360. https://doi.org/10.1080/10408399109527543. spray drying. Food Res. Int. 42 (1), 13–25. https://doi.org/10.1016/j.
Ren, G.R., Zhao, L.J., Sun, Q., Xie, H.J., Lei, Q.F., Fang, W.J., 2015. Explore the reaction foodres.2008.09.006.
mechanism of the Maillard reaction: a density functional theory study. J. Mol. Wang, S., Langrish, T., Adhikari, B., 2013. A multicomponent distributed parameter
Model. 21, 1–17. https://doi.org/10.1007/s00894-015-2674-5. model for spray drying: model development and validation with experiments. Dry.
Rongsirikul, N., Hongsprabhas, P., 2016. Brown pigment formation in heated Technol. 31, 1513–1524. https://doi.org/10.1080/07373937.2013.813533.
sugar–protein mixed suspensions containing unmodified and peptically modified Yaylayan, V.A, Ismail, A.A, Mandeville, S., 1993. Quantitative determination of the effect
whey protein concentrates. J. Food Sci. Technol. 53, 800–807. https://doi.org/ of pH and temperature on the keto form of d-fructose by FT IR spectroscopy.
10.1007/s13197-015-1955-4. Carbohydr. Res. 248 (C), 355–360. https://doi.org/10.1016/0008-6215(93)84141-
Roos, Y., 2016. Phase transitions in foods. Phase Transitions in Foods. https://doi.org/ R.
10.1016/c2012-0-06577-5. Zbicinski, I., Strumillo, C., Delag, A., 2002. Drying kinetics and particle residence time in
Roos, Y.H., 2009. Solid and liquid states of lactose. Adv. Dairy Chem. 3, 1–778. https:// spray drying. Dry. Technol. 20, 1751–1768. https://doi.org/10.1081/DRT-
doi.org/10.1007/978-0-387-84865-5. 120015412.
Roos, Y.H., 2002. Importance of glass transition and water activity to spray drying and Zhong, C., Tan, S., Langrish, T., 2019. Redness generation via Maillard reactions of whey
stability of dairy powders. Lait 82, 475–484. protein isolate (WPI) and ascorbic acid (vitamin C) in spray-dried powders. J. Food
Eng. 244, 11–20. https://doi.org/10.1016/j.jfoodeng.2018.09.020.
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Journal of Food Engineering 305 (2021) 110615

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Journal of Food Engineering

A review of Maillard reactions in spray dryers

Table 1 Table 1 (continued )

Fig. 1. Overview of Maillard reactions scheme (reproduced based on Nursten, 2005).

Fig. 2. Open-chain form and closed-form of glucose.

Fig. 3. Amino acids in different pH environments.

different reactants also play an important role in the early stage of

3. Kinetic studies of Maillard reactions

3.1. Kinetic studies of Maillard reactions in liquid systems

To understand the kinetics of the Maillard reactions in spray dryers,

As mentioned in the previous sections, the pH of the system affects

compared with the airborne residence time. Furthermore, they also

4.8. Particle residence time distribution in spray dryers

The particle residence time in spray dryer is another important factor

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