22 J. Agric. Food Chem.

2011, 59, 22–42

DOI:10.1021/jf1032203

Adsorption and Ion Exchange: Basic Principles and Their

Application in Food Processing
JUDITH KAMMERER, REINHOLD CARLE, AND DIETMAR R. KAMMERER*
Hohenheim University, Institute of Food Science and Biotechnology, Chair Plant Foodstuff Technology,
Garbenstrasse 25, D-70599 Stuttgart, Germany

A comprehensive overview of adsorption and ion exchange technology applied for food and nutra-
ceutical production purposes is given in the present paper. Emanating from these fields of applica-
tion, the main adsorbent and ion-exchange resin materials, their historical development, industrial
production, and the main parameters characterizing these sorbents are covered. Furthermore,
adsorption and ion exchange processes are detailed, also providing profound insights into kinetics,
thermodynamics, and equilibrium model assumptions. In addition, the most important industrial
adsorber and ion exchange processes making use of vessels and columns are summarized. Finally,
an extensive overview of selected industrial applications of these technologies is provided, which is
divided into general applications, food production applications, and the recovery of valuable bio- and
technofunctional compounds from the byproducts of plant food processing, which may be used as
natural food additives or for their potential health-beneficial effects in functional or enriched foods
and nutraceuticals.

KEYWORDS: Kinetics; equilibrium isotherms; industrial application; polyphenols; byproducts; proteins;

tocopherols

1. INTRODUCTION producers to abstain from the use of synthetic food additives and
The aim of the present review is to provide a comprehensive to apply natural “healthy” food components, which can be
and systematic overview of the application of adsorbent and ion deduced from an increasing importance of the “functional foods”
exchange technology in the food industry. This comprises not sector. The processes exemplified in the present paper are mainly
only the characterization of the main adsorbent and ion exchange based on the application of synthetic resins and were taken from
materials permitted for food application, their preparation, and a scientific publications, patents, and application brochures of resin
description of the historical development of this technology but manufacturers.
also a detailed treatise of the different kinetics, thermodynamics,
2. HISTORICAL DEVELOPMENT OF ADSORPTION AND
and equilibrium models, which are commonly used to describe
ION EXCHANGE TECHNOLOGY
adsorption and ion exchange phenomena in different systems. In
addition, the major applications of adsorption and ion exchange Adsorption phenomena were already exploited by the Egyp-
technology described in the literature are reported, and this de- tians and Sumerians, who used charcoal 3750 B.C. for reducing
scription has been restricted to solid-liquid systems. This section copper, zinc, and tin levels during bronze manufacturing. Follow-
is subdivided into “general applications”, giving an insight into ing this, the Egyptians and later Hippocrates used charcoal for
the potential use of this technology, “food production applica- first medical purposes before the first application for potable
tions”, and “recovery of valuable bio- and technofunctional water treatment was described by the Phoenicians. Such applica-
compounds from the byproducts of food processing”. The clear- tions were rather empirical, and a more systematic approach was
cut differentiation between the latter two areas of application was not developed until 1773, when the first quantitative studies of
made because of the rising accumulation of byproducts due to an adsorption phenomena were performed. Nowadays industrial
increased production quantity of industrial foods, which is asso- applications of adsorption technology reveal great diversity, and
ciated with increasing costs for the disposal of such waste streams. such techniques have become common practice for gas purifica-
On the other hand, plant-processing byproducts are of increasing tion, for example, to remove obnoxious smells from the air or in
interest because of their high contents of secondary plant metab- gas masks to protect military personnel from poisonous gas and
olites, which have been intensely discussed in the past decades further to decolorize aqueous or organic liquids, which is further
due to their health-promoting properties. This interest is associated detailed below. Numerous gas-solid and liquid-solid phase
with a growing market of natural food additives and nutraceuticals. adsorption systems using charcoal, clay, carbon of animal origin,
Additionally, consumer expectations increasingly force food zeolite, and, more recently, also activated carbon, synthetic zeolites,
and further synthetic resins based on polystyrene, polyacrylic
*Corresponding author [phone þþ49-(0) 711-459-22995; fax þþ49-(0) esters, or phenolics have been described, giving rise to very diverse
711-459-24110; e-mail [email protected]]. fields of application (1-3).

pubs.acs.org/JAFC Published on Web 12/07/2010 © 2010 American Chemical Society

Review J. Agric. Food Chem., Vol. 59, No. 1, 2011 23
The application of ion exchange phenomena can also be traced 3.3. Density. The specification of the density may be further
back to the Old Testament, in the Second Book of Moses (Ex 15, broken down into the density of individual particles and the
23 EU), where the preparation of potable water from bitter density of the particle bulk. Individual particle density may be
brackish water is described. This was probably due to the removal specified as the real density, that is, the quotient of the dry
of bitter cations through ion exchange by a piece of wood adsorbent amount and the solid volume without considering the
containing rotted cellulose; processed cellulose is known today pore volume, the apparent density, that is, the quotient of the dry
to be a very efficient ion exchange material. Around a thousand adsorbent amount and the total solid volume including the pore
years later, Aristotle (384-322 B.C.) described in his Problemata volume, or as the wet density, which means the wet adsorbent
the decrease of the salt concentration of seawater when perco- amount divided by the total solid volume including the liquid-
lating through sand. The next important observations of ion filled pore volume. In contrast, the particle bulk density is also
exchange processes were not made until 1850 when Thompson (4) referred to as the bulk density, that is, the amount of adsorbent
and Way (5), two English chemists, studied the exchange of ions needed to fill a vessel divided by the volume including the
on cultivated soils. It is assumed that the underlying physical interparticle volume, the filter bulk density, which is defined as
phenomena were not really known at that time. However, in the the bulk density measured after a single backwash step, or the
following years the development of this separation technology vibrated density, which is specified as bulk density measured
has proceeded very rapidly. At first natural mineral ion exchang- upon vibration during the filling process (9, 11).
ers were used, such as clay, glauconite, humic acid, and zeolite 3.4. Porosity or Pore Size Distribution. According to the
followed by synthetic inorganic exchanger materials, which came definition of the density, the porosity may also be further
up in 1905. Systematic investigations of ion exchange processes subdivided into particle porosity and bulk material porosity.
and of the properties of exchange materials have led to the devel- Thus, the inner porosity of individual particles is defined as the
opment of synthetic resins with well-designed characteristics proportion of the pore volume referred to the total volume of the
(1, 2, 6, 7). adsorbent particle. In contrast, the bulk porosity or outer poros-
ity is a measure of the interspaces between the adsorbent parti-
3. BASIC PRINCIPLES OF ADSORPTION AND ION EX- cles (1, 9, 11).
CHANGE 3.5. Pore Radius Distribution. Pore radius distribution is
Basically, both ion exchange and adsorption may be performed another important factor affecting adsorption and ion exchange
in solid-gas and solid-liquid systems. A strict differentiation rates. The variability of the pore radius has a major impact on the
between these two types of applications is impossible, because diffusion of the solutes into the resin material. Pore radii are
there are exchange and adsorption resins, which are used in both classified according to International Union of Pure and Applied
gas-solid and liquid-solid adsorption applications, such as acti- Chemistry (IUPAC) standards. Accordingly, pores with a diam-
vated carbon or zeolite. Additionally, the most common equilib- eter of <0.4 nm are referred to as submicropores, whereas the
rium models such as the Langmuir and Freundlich isotherms diameter of micropores ranges from 0.1 to 2.0 nm, that of
were derived by studying gas adsorption systems and subse- mesopores from 2.0 to 50 nm, and that of macropores above 50 nm.
quently applied to solid-liquid systems. In this review, only Concerning the large pore radius variability of most sorbents, the
solid-liquid adsorption and ion exchange systems were regarded, different pore classes are assumed to exert particular functions.
although there are some solid-gas applications in food processing, The macro- and mesopores allow the transport of the solute
such as waste air purification, removal of fat, and gas purifica- molecules, whereas inside the micropores adsorption and ion
tion, especially of oxygen and nitrogen, prior to their use in food exchange occur (9, 11).
processing (8, 9).
Adsorbent and ion exchange materials are categorized not only 4. ADSORBENT AND ION EXCHANGE MATERIALS
on the basis of their matrix composition, polarity, and chemical Adsorbent and ion exchange materials, which are allowed for
and physical resistance but also by their particle size distribution, food use, are regulated by the respective national legislation as
their inner and specific surface areas, density, and porosity as well well as the U.S. Food and Drug Administration (FDA) and the
as their pore radius distribution (10). Council of Europe. The most commonly applied and most im-
3.1. Particle Size Distribution. The resin particle size distribu- portant materials, which conform to these regulations, are further
tion is important not only because of its influence on the pressure specified below.
loss upon passing the solvent through the adsorbent and ion 4.1. Activated Carbon. Activated carbon is probably the best-
exchange columns but also because of its effect on mass known adsorbent material. It can be manufactured from animal
transfer rates. Naturally, pressure loss increases with decreas- and plant carbonaceous materials, such as bones, coals, petro-
ing particle size, at the same time mass exchange rates increase leum coke, nutshells, peat, wood, and lignite. Its manufacturing
with decreasing particle size because of shorter diffusion paths. process may be partitioned into two phases. The first phase is
For characterizing the particle size distribution the average characterized by carbonization, during which undesirable byprod-
particle diameter, the most frequently occurring particle diam- ucts are removed from the raw materials at 400-600 °C in an
eter, and the particle size range (“mesh”) are usually speci- oxygen-depleted atmosphere. In the second phase the material is
fied (9). activated, which may be achieved through gas or by chemical
3.2. Inner or Specific Surface Area. The inner or specific surface activation. Gas activation is performed at temperatures of 750-
area usually is a multiple of the outer surface of an adsorbent and 1100 °C for the partial gasification of carbon with water vapor,
is the site where adsorption occurs. Consequently, this parameter carbon dioxide, and oxygen, respectively. In contrast, chemical
deserves particular attention upon decision-making when choos- activation is achieved using dehydrating chemical agents, such as
ing a particular resin, and maximal inner surface areas should be potassium sulfide, sulfuric acid, zinc chloride, and phosphoric
aimed at. Due to the fact that the inner surface area is inversely acid at temperatures of 350-600 °C. Under these conditions
proportional to the pore diameter, the molecular size of the carbonization, gasification, and activation occur simultaneously
adsorbent constitutes a major limitation of its application, because (1, 11, 12). Through the selection of the raw material and by
if the pore diameter is too small, the adsorptive may not diffuse controlling the carbonization and activation conditions the tailoring
into the adsorbent (9, 11). of pore size distribution is possible, and activated carbon for
24 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Kammerer et al.
particular applications may be manufactured. Thus, activated
carbon is available with surface areas ranging from 300 to 3000 m2/g
and pore volumes from 0.7 to 1.8 cm3/g, in the form of powder
(PAC), granules (GAC), pellets, or tissues derived from different
raw materials. This great diversity of different types of activated Figure 1. Hydrolytic formation of silicic acid.
carbon is associated with an immense variability of different appli-
cations. It is used to remove unwanted substances from gases,
vapors, and liquids in the chemical industry, in medicine, for
water and wastewater treatment, in ventilation and air-condition-
ing technology, and for the adsorptive removal of compounds
that may cause contaminations and discoloration or that may
negatively affect taste and odor (1, 8).
4.2. Zeolites. Zeolites may be subdivided into 40 natural and
more than 150 synthetic crystalline aluminosilicates of alkali or
earth alkali elements, such as sodium, potassium, and calcium. Figure 2. Polymerization of silicic acids.
Their primary structure is based on the tetrahedra of silicon
(SiO4) and aluminum (AlO4), which build up secondary poly- acid, upon stirring at high temperatures, thus yielding silicic acid
hedral units of cubes, hexagonal prisms, octahedral, or truncated precipitates. Upon further neutralization the polycondensation of
octahedral systems, respectively, and which are linked via oxygen low molecular silicic acids leads to colloidal SiO2 particles, which
atoms. Furthermore, the three-dimensional crystalline network further grow to a certain size. The redundant electrolyte together
of zeolites consists of secondary units, with these secondary struc- with van der Waals forces enhances coagulation of these particles
tures building up cages, which are connected through channels to agglomerates, with the agglomerate structures forming aggre-
crossing the three-dimensional structure. The size of the channels gates that subsequently precipitate.
is determined by the number of silicon and aluminum atoms, The second route is governed by gel-sol conversion, a poly-
which are linked with each other, and also by the counterion of merization reaction obtained by mixing a sodium silicate solution
the negatively charged aluminum, which may partially obstruct with a mineral acid, such as sulfuric or hydrochloric acids. The
the channel and reduce its size. Thus, differences may be observed reaction products form a dispersion of finely divided particles of
when Ca2þ is substituted by Naþ. Furthermore, not only does the hydrated SiO2, which are also referred to as silica hydrosol or
number of silicon and aluminum atoms have an effect on the silicic acid (eq 1) and which build up at a particular pH value.
channel size but also the Si/Al ratio. With increasing Si propor-
tions, the affinity of water and other polar molecules toward Na2 SiO3 þ 2HCl þ nH2 O f 2NaCl þ SiO2 3 nH2 O þ H2 O ð1Þ
zeolites is lowered, bringing about a more hydrophobic character.
Silicic acid (Si(OH)4), with its strong tendency to polymerization,
Accordingly, numerous different zeolites can be manufactured,
forms a white jelly-like precipitate network of siloxanes, which
with each of them having tailor-made properties and being
need to be washed, dried, and activated prior to further use. The
characterized by its unique surface chemistry and structure, which
variable properties of silica gels with respect to pore volume and
allows a highly selective application based on ion exchange
surface area may be achieved through varying the silica concen-
phenomena and depending on the size and polarity of the
tration, pH value, and temperature during polymerization or the
adsorptive. The three most frequently used zeolites are types A,
temperature during activation.
X, and Y. Their common basic structure is made up of a truncated
A further process to prepare silica gels is based on the reaction
octahedron called sodalite cage. Type A is built up of two linked
of silicon alkoxides with water in the presence of an alcohol (eq 2),
four-member rings of sodalite and a Si/Al ratio of 1. Types X and
whereas silicic acids can also be formed through hydrolysis
Y consist of an octahedron with six-member rings of sodalite as
(Figure 1). Accordingly, the polymerization of silicic acids may
base structure, which differ in their Si/Al ratios (type X, 1-1.5;
be described as illustrated in Figure 2.
type Y, 1.5-3) (8, 12). Additionally, the substitution of Si or Al
through other elements expands the number of zeolite structures, ROH
which are then formally not classified as zeolites. The synthesis of f SiO2 þ 4ROH
SiðORÞ4 þ 2H2 O s ð2Þ
zeolites is a two-step process, consisting of gel formation at 25 °C A pyrotechnic process is the third option to obtain silicon gels,
from aqueous NaOH, NaAl(OH)4, and Na2SiO3, probably due where silane tetrachloride is continuously passed over into the gas
to copolymerization of silicate and aluminate, followed by crys- phase at a temperature of around 1000-1200 °C and reacts
tallization in a closed hydrothermal system. This process may within an oxyhydrogen flame with water to form fine particles of
need a few hours up to several days at temperatures up to 175 °C. silicon oxides (eq 3).
Furthermore, the use of organic additives, such as organic amines,
1000- 1200 o C
mainly quaternary amines, is an interesting tool to influence 2H2 þ O2 þ SiCl4 sf SiO2 þ 4HCl ð3Þ
zeolite formation during crystallization. On the bases of their
different structures, zeolites are used for separation and purifica- These hydrophilic synthetic silicas are usually modified in sub-
tion and as molecular sieves, for example, for the drying and sequent treatment procedures to expand their technological
dehydrating of gases or organic solvents (12, 13). properties. In this way, different silanes carrying various func-
4.3. Silica Gels. With regard to the increasing use of modified tional groups are obtained, which may be used, for example, as
silica gels for column chromatographic purposes and various grafting agents, where temperatures of around 70 °C are applied
other applications, this sorbent material shall be considered here for treating the silica surface. Accordingly, surfaces with im-
as well. In general, there are different routes to obtain this widely proved separation efficiency exhibiting polar or apolar properties
used amorphous desiccant with its large water-binding capacity may be created by selective modification (12, 14, 15).
and its easy regeneration. The first synthesis route, which is most Because of their very high adsorption capacity and straightfor-
commonly used, is characterized by chemical precipitation of ward regeneration, silica gels are also used for analytical purposes
alkali silicate, such as sodium silicate, with acids, mostly sulfuric as filter material, column material, and fining agent. Depending
Review J. Agric. Food Chem., Vol. 59, No. 1, 2011 25

Figure 3. Polycondensation of phenol with formaldehyde via acidic or basic catalysis.

Figure 4. Polymerization of styrene (A) and methacrylic acid (B) with divinylbenzene as cross-linking agent.

on their properties and manufacturing processes, silica is also from step-growth polymerizations, such as polyaddition or poly-
applicable in food production, such as to adjust the pourability of condensation reactions.
vegetable, fruit, and sauce powders, to produce flavors in powder Polycondensation products are obtained through electrophilic
form, in the cosmetics industry as carriers of active compounds, aromatic substitution of phenolic compounds with formaldehyde
as raw material for powders, as dispersing agent, as fining agent, under acidic or basic catalysis (Figure 3) and, as for polyaddition
and in the paint industry for adjusting viscosity and thixotropy products, are formed in stepwise reactions. The type of phenolic
(12, 14, 15). compound and the ratio of the precursor materials used for
4.4. Synthetic Resins. Synthetic resins are polymeric adsor- synthesis define their properties.
bents with large internal surface areas and a much more consistent Polymerization belongs to the poly reactions, which proceed
structure compared to activated carbon. They are manufactured through chain propagation reactions and may be realized in tech-
by polycondensation or polymerization, with the products of the nical processes such as bulk polymerization, solution polymeri-
polymerization reaction being more consistent with respect to zation, emulsion polymerization, suspension polymerization, pre-
temperature or chemical influences than the polycondensation cipitation polymerization, and gas phase polymerization. Upon
products. In this context it is important to note that there are polymerization, styrene (Figure 4A), acrylic acid, or methacrylic
major differences in the literature with regard to the classification acid (Figure 4B), respectively, may polymerize with divinylben-
of polyreactions and their definitions. In the English literature zene or other divinyl monomers as cross-linking agents, whereas
polymerization may generally be perceived as a transformation of polyacrylamide (Figure 5A), polyvinylpyrrolidone (PVP) (Figure 5B),
low molecular weight to high molecular weight compounds. On and polyvinylpolypyrrolidone (PVPP) are also manufactured by
the other hand, the term polymerization is often specifically used radical polymerization but without cross-linking agents. Styrene
to describe chain-growth reactions, thus differentiating such reactions molecules as well as styrene and divinylbenzene are polymerized
26 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Kammerer et al.
through radical polymerization with benzoyl peroxide as an initiator 4.4.1. Gel Type Adsorbents and Ion Exchangers. For the
of the radical chain reaction. Additionally, there are further ways to production of gel type resins, styrene and relatively low amounts
obtain cross-links between styrene chains after their formation, if the of divinylbenzene (2-12%) are blended with approximately the
aromatic bodies have been chloromethylated, which is commonly same amount of water devoid of any organic solvent in a chemical
performed in the course of functionalization to produce ion exchange reactor. Subsequently, the mixture is dispersed through stirring to
resins. Thus, methylene bridge formation may occur between produce small globules with a size of about 1 mm. At this stage the
a chloromethylated styrene chain and a neighbor chain (Figure 6); addition of benzoyl peroxide initiates the radical chain reaction
however, such bridges may negatively affect the positive character- and therewith the polymerization, which leads to the formation of
istics of an existing pore system (16, 17). A second way of cross- small plastic beads of the polystyrene/divinylbenzene molecules.
linking is given via the Friedel-Crafts reaction. p-Xylylene dichloride Such resin types are commonly used especially for water treat-
(XDC), 1,4-bis(chloromethyl)diphenyl (CMDP), monochlorodi- ment (18, 19, 21).
methyl ether (MCDE), dimethylformal, tris(chloromethyl)mesitylene 4.4.2. Macroreticular Resins. Macroreticular resins are
(CMM), and p,p0 -bis(chloromethyl)-1,4-diphenylbutane (DPB) are characterized by high porosity, which can be achieved using an
cross-linking agents used for this purpose (18); however, these chem- inert material or porogen, which is miscible with the monomeric
icals are not commonly used for manufacturing resins applied in the compounds but which does not influence the chain propagation
food sector. and is easy to extract or to vaporize, thus forming pores. Inert
In addition, cationic and anionic copolymerization are two materials used for this purpose are swelling agents, which are
further possible reaction mechanisms for producing polymeric good solvents for the monomers as well as the polymer products
resins, with the initiator being a cation, which reacts via an elec- or precipitating agents, in which the polymeric products are
trophilic addition, or an anion, which starts the reaction via a hardly soluble. The variability of adsorbent resins can be achieved
nucleophilic addition to a carbon-carbon double bond, respec- through choosing different types and concentrations of the inert
tively (19). material or porogen and by varying the amount of divinylbenzene
There are also literature reports on the so-called living poly- and the type and concentrations of other monomers as well as the
merization, allowing one to specially control the preparation and reaction conditions during polymerization. The large-pored
the uniformity of the polymer architecture of resins, for example, structures produced under such conditions are characterized by
by retaining the termination step. This means that after complete a huge inner area and a more homogeneous appearance com-
reaction of all monomeric units and further addition of educts, the pared to the gel type. To increase their mechanical stability,
chains may still continue to grow (19). For this purpose anionic higher amounts of cross-linking components are needed as
living polymerization (20), reversible addition-fragmentation compared to the production of gel-type resins. This coincides
chain transfer (RAFT), or radical living polymerization, such with a number of interesting properties, such as a larger free inner
as free stable radical mediated polymerization (SFRP), is commonly volume, lower swelling differences between polar and unpolar
applied. solvents, lower volume decrease during resin drying, and higher
The polymers formed according to these different mechanisms oxidation stability, and such resins are also suitable for catalytic
may be obtained either in gel type form, in macroreticular form or purposes. Besides the recovery of low molecular weight com-
as hypercrosslinked resins, which significantly affects their prop- pounds as described for hyper-cross-linked polystyrenes (4.4.3),
erties and areas of application. macroreticular resins with their large inner volumes provide the
opportunity to recover large molecules due to the accessibility of
the inner surface areas (6, 11, 18, 19).
4.4.3. Hyper-cross-linked Polystyrenes or Styrosorbs.
Hyper-cross-linked resins are extremely rigid networks with a
cross-linking degree above 40% showing much greater sorption
capacities than that of other known organic and inorganic
sorbents. Due to the high inner volume of the network not only
the surface of macropores is accessible for the target compounds,
which may explain the high capacity of such resins. According to
Davankov and Tsyurupa (18) the hyper-cross-linked polymers are
able to swell in any liquid and also in gaseous media, whereas harsh
treatments such as drying may lead to a decrease of the volume.
Synthetic adsorbent resins are appropriate to and commonly
used for the removal and recovery of aromatic components such
Figure 5. Structural features of polyacrylamide (A) and polyvinylpyrroli- as polyphenols, naphthalenes, hydrocarbons, pesticides, alcohols,
done (PVP) (B) and of their corresponding monomers. and ketones (11).

Figure 6. Methylene bridge formation between a chloromethylated polystyrene chain and a neighbor chain.
Review J. Agric. Food Chem., Vol. 59, No. 1, 2011 27
1
Table 1. Ion Exchange Resins Applied in the Food Industry

1a
SDVB, styrene-divinylbenzene; b DVB, divinylbenzene (6, 69, 99, 100)

Respective national legislatures as well as the FDA (22,23) and that is, an electrophilic substitution of the aromatic backbone of
the Council of Europe (24) regulate the types of resins, mono- the resins occurring upon treatment with concentrated sulfuric
mers, starting components, chemical modifiers, and polymeriza- acid at elevated temperatures, or by chloromethylation via the
tion aids to be used as well as food production processes, where Friedel-Crafts/Blanc reaction followed by amination of the
such resins may be applied. intermediate reaction products (Figure 7). Additionally, specific
4.5. Synthetic Ion Exchanger Materials. Ion exchangers are ion exchangers may be obtained by the insertion of functional
by definition firm and insoluble high molecular weight polyelec- groups with well-desired properties. Among such ion exchangers,
trolytes, which may exchange their loosely bound ions against chelating, imprinted exchangers, or ligand exchangers, may be
ions of the same charge from the surrounding media. Ion found (2, 25).
exchange is a reversible and stoichiometric process. As mentioned for adsorbent resins, the types of ion exchangers,
Synthetic ion exchangers are composed of a matrix, a three- monomers, starting substances, chemical modifiers, and poly-
dimensional high molecular network, with charged functional merizations aids, respectively, permitted for the production of
groups attached to it by chemical bonds. According to the afore- resins for food applications are regulated by national legislation,
mentioned variability of synthetic adsorbent resins, the structural the FDA, and the Council of Europe (22-24).
diversity of ion exchangers is even more pronounced, because a
number of different functional groups may be attached to the 5. PRINCIPLES OF ADSORPTION AND ION EXCHANGE
apolar networks. The choice of matrix material depends on the 5.1. Adsorption. Adsorption may be described as an enrich-
type of ion exchange to be applied. As an example, the resins ment of compounds, for example, from fluids on surfaces of solid
produced by cross-linking acrylic and methacrylic acids with state bodies. During this accumulation, interactions between the
divinylbenzene, respectively, carry carboxylic groups, which act atoms and molecules of the fluid phase (adsorptive) and the solid
as weak cation exchangers without further modification of the (adsorbent) occur. The solid surface may be regarded as a site
resins. The charge of the groups attached to the resin matrix with certain electronic and sterical properties characteristic of the
determines the kind of ion exchanger. Cation exchangers carry adsorbent matrix structure, which induce energetically hetero-
bound anions, and anion exchangers reveal the presence of cationic geneous energy levels based on the degree of the interaction with
groups with the respective reversely charged counterions attached the adsorptive. Furthermore, most adsorbents are not only
by electrostatic interactions. In addition, there are amphoteric ion characterized by their exterior surface but are also significantly
exchangers, containing both ion types at the same time. affected by their inner porous surface, which also contributes to
The aforementioned main types of ion exchangers may be adsorption. However, there are major differences in the interac-
differentiated into strong basic, weak basic, or acidic ion ex- tion forces and the kinetics of adsorption onto the exterior or
changers on the basis of their functional groups. Table 1 provides inner surface (26). Adsorption processes are generally distin-
an overview of the most popular ion exchange types used in the guished in three different sorption types depending on the nature
food industry (6, 7). of the interactions between the adsorbent matrix and the adsorp-
4.5.1. Functionalization of Synthetic Resins. Cross-linked tive. Physisorption commonly is a reversible and rapid sorption
resins may be functionalized by treatments such as sulfonation, process, which is mainly based on van der Waals forces, dipole
28 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Kammerer et al.

Figure 7. Functionalization of cross-linked resins via sulfonation with concentrated sulfuric acid or by chloromethylation via the Friedel-Crafts/Blanc reaction
followed by amination to obtain cation and anion exchange resins.

forces, dipole-dipole forces, and dispersion forces as well as resin particles, whereas the heat transfer through the liquid phase
induction forces, which are usually below 50 kJ/mol. In contrast, may be disregarded because of its high heat capacity.
chemisorption relates to a chemical bonding between the adsor- The mathematical description of adsorption kinetics can be
bent and adsorptive. Accordingly, the interaction forces are much realized in two ways, either by considering the global mass and
higher and are reported to be in the range of 60-450 kJ/mol. heat transfers separately or by taking into consideration combi-
Furthermore, in the course of ionosorption an ion transfer nations of various processes running in parallel and sequentially.
occurs (11, 26). These approaches are called the heterogeneous and homogeneous
5.1.1. Kinetics and Thermodynamics of Adsorption Pro- models, respectively (9, 11), and are further detailed below.
cesses. Adsorption kinetics describes the time-dependent evolu- Heterogeneous Model. According to this model both the mass
tion of the sorption process until equilibrium is reached. The and heat transfer of the film diffusion process are separately
sorption process is divided into mass transport and heat trans- predictable (9). In contrast to particle diffusion the mass transfer
port, with the first being subdivided into four consecutive steps: in the subsurface has a nondominant role, because the pore
(1) transport of the adsorptive from the fluid phase to the resistance is the dominating step of mass transfer. The subsurface
subsurface, which is built up around the adsorbent; (2) transport effect may be further limited through higher flow rates, whereas a
through the subsurface, which is also called film diffusion; (3) sufficient contact time of the adsorptive with the adsorbent needs
simultaneous transport into the pores of the adsorbent through to be warranted, thus limiting maximal flow rates. In contrast,
diffusion by the pore fluid, also referred to as pore diffusion and heat transfer through the subsurface is the dominating step of
diffusion along the inner surface upon adsorption (surface energy transfer.
diffusion); (4) interaction with the active sites of the adsorbent. The overall mass transfer kinetics is dominated by the mass
The first step is not directly related to adsorption. The heat transport in the pores. The diffusion processes within the particles
transport is divided into energy transfer inside the sorbent mate- occurring in the liquid phase are subdivided into free pore
rial and energy transfer through the subsurface surrounding the diffusion, surface diffusion, and intercrystalline diffusion, all of
Review J. Agric. Food Chem., Vol. 59, No. 1, 2011 29
which may also occur simultaneously. Due to these different determined according to eq 8 (28, 29):
diffusion mechanisms occurring in parallel, the diffusion types
cannot clearly be differentiated and, accordingly, the determina- ΔG ¼ ΔH  - TΔS ð8Þ
tion of the dominating step is difficult. In liquid phases, both
Furthermore, the half-adsorption time t1/2, that is, the time
relevant mechanisms, that is, pore diffusion and surface diffusion,
needed to bind half of the equilibrium amounts onto the resin
are superimposed, because both mechanisms proceed simulta-
surface, may be determined according to eq 9:
neously in the same pore. In this context, the diffusion differs
depending on whether the gradient of particle loading or the ln 2
concentration gradient is the driving force of the overall pro- t1=2 ¼ ð9Þ
k
cess (9).
Homogeneous Model. The homogeneous model is applied 5.1.1.2. Pseudo-First-Order Kinetic Model (Lagergren’s
when the underlying dominating mechanisms of a system are Rate Equation). According to Rudzinski and Plazinski (30, 31)
unknown. In this case, the linear driving forces (LDF) approach Lagergren adsorption kinetics (eq 10) is a limiting form of the
describes the overall mass transfer between the adsorbent and Langmuir model, if the system is not far from equilibrium
the fluid phase. This approach assumes a homogeneous loading conditions:
of the sorbent surface, which is independent of the particle
dqt
radius, and the resistance of the mass transfer due to the subsur- ¼ kðqe - qt Þ ð10Þ
face (9). dt
According to Bathen and Breitbach (9), the kinetics of multi- k is the rate constant (1/s), and qe and qt are the amounts adsorbed
compound systems has been less thoroughly studied because of per mass of adsorbent (mg/g) at equilibrium and after time t,
the difficult assessment of the interactions of different compounds respectively. By plotting ln(qe - qt) against the time t according to
simultaneously diffusing in the pores. the linearized Lagergren equation (eq 11), the rate constant k and
Adsorption processes are commonly exothermic. Normally, β may be determined from the slope and intercept of the linear
adsorption phenomena are characterized by energies ranging up graph. Following this, the intercept β can be used to determine the
to approximately 100 kcal/mol. Under these conditions, sorption nature of the rate-determining step (31, 32):
processes may be observed even at temperatures below 100 K,
and both adsorption and desorption occur spontaneously. In lnðqe - qt Þ ¼ β - kt ð11Þ
contrast, desorption may not occur without chemical modifica-
tion of the target compounds for sorption processes with adsorp- Furthermore, according to the first-order kinetics model, the half-
tion energies of g100 kcal/mol (26). adsorption time can be deduced according to eq 12.
5.1.1.1. First-Order Kinetic Adsorption Model. First-order
ln 2
sorption phenomena are unimolecular processes based on a t1=2 ¼ ð12Þ
reversible equilibrium reaction, which may be characterized as k

dðqe - qt Þ 5.1.1.3. Pseudo-Second-Order Kinetic Model. The pseudo-

¼ - kðqe - qt Þ ð4Þ second-order reaction is a two-site-occupancy adsorption. Thus,
dt according to this model a solute molecule reacts with two adsorp-
where qe (mg/g) and qt (mg/g) are the maximum amount that can tion sites, with the reaction rate being defined as
be adsorbed per mass of adsorbent and the amount adsorbed
dqt
after time t, respectively (27). t (s) is the time and k the rate ¼ kðqe - qt Þ2 ð13Þ
constant (1/s) (1). By integration of the differential form of eq 4 dt
the following equation (eq 5) results: where k is the rate constant (g/mg 3 s) and qe and qt are the
lnðqe - qt Þ ¼ - kt þ C ð5Þ amounts adsorbed per mass of adsorbent (mg/g) at equilibrium
and after time t, respectively (1, 27). Most commonly, this model
C is an integration constant (mg/g), which is defined as ln(qe) at is represented in its linearized form (eq 14), which produces a
t = 0, because qt = 0 at t = 0 (28). Furthermore, it is possible to linear graph if t/qt is plotted versus time t. The rate constant k and
deduce the energy of activation by applying the linearized qe may be determined from the slope and intercept of the graph:
Arrhenius equation, if the rate constant k is calculated for
different temperatures (eq 6). t 1 1
¼ þ t ð14Þ
qt kqe 2 qe
Ea
ln k ¼ ln A - ð6Þ
RT Summarizing these common kinetic models, the thorough con-
siderations of Rudzinski and Plazinski (27,30,31,33-36) deserve
R is the gas constant, T the absolute temperature (K), and Ea the particular attention. The main conclusion of these authors is that
activation energy of the sorption process, which can be calculated adsorption kinetics is better described with different models,
together with the pre-exponential factor A from the slope and which ideally fit to the respective stages of the adsorption process,
intercept of a linear plot of ln k versus 1/T (28,29). On the basis of rather than relying on one kinetic assumption to describe the
this relationship and using the Eyring equation (eq 7) the enthalpy entire sorption process from the initial stages until equilibrium
of activation ΔH* and the entropy of activation ΔS* may be calcu- conditions. These authors based their assumptions on the appli-
lated from the intercept and slope of the linear plot of ln(k/T) cation of the pseudo-first- and pseudo-second-order kinetic models.
versus 1/T (28, 29): 5.1.2. Adsorption Equilibrium. The adjustment and the



k kb ΔS ΔH  general parameters of adsorption equilibria depend on the inter-
ln ¼ ln þ - ð7Þ actions of the adsorptive and adsorbent as well as the properties
T h R RT
of the solutions brought into contact with the sorbent material
kb and h are the Boltzmann and Plank constants, respectively. and of the adsorptive. Furthermore, if several compounds coexist
Following this, the free energy of activation (ΔG*) may be in one solution, they will inevitably compete for sorption sites of
30 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Kammerer et al.
the sorbent. Accordingly, equilibrium concentrations of individ- the adsorbent surface when it is completely covered by an
ual compounds in complex mixtures depend on such mutual adsorbate monolayer. This value may be calculated by dividing
interactions. the Langmuir constants KL (L/g) and aL (L/mg). qe (mg/g) is
Experimental data obtained under equilibrium conditions defined as the amount of adsorbate per gram of sorbent at
may be used for deducing adsorption isotherms by varying equilibrium, whereas Ce (mg/L) is the equilibrium solute con-
experimental conditions, such as pH value, adsorbent amounts, centration.
or adsorptive concentrations. Furthermore, it needs to be At low concentrations (aLCe , 1), the Langmuir isotherm can
considered that there are no generally applicable adsorption be approximated by the Henry isotherm (11, 37)
isotherms, which allow one to describe the experimental results
obtained under any condition. Thus, the most familiar iso- qe ¼ QmL aL Ce ¼ kH Ce ð18Þ
therms, which are based on theoretical model concepts or
whereas at high concentrations (aLCe . 1) a constant saturation
which have been deduced empirically, are presented below.
value (maximal coverage) results, which equates to the irreversi-
These approaches may be classified first into parameter-
ble isotherm (11):
dependent isotherms and second into isotherms depending
on the number of compounds to be considered in the respective qe ¼ QmL ¼ const ð19Þ
adsorption system.
5.1.2.1. Isotherm Equations Describing Single-Compound On the basis of the linearized form of the Langmuir isotherm
Systems. Most isotherms dealing with single-compound adsorp- (eq 20), the Langmuir constant KL and adsorbent capacity QmL
tion are derived from gas phase adsorption systems. However, may be obtained from the slope and the intercept of the linear plot
these models have also been successfully applied to liquid-solid of 1/qe values of experimental data against 1/Ce (38).
phase adsorption in numerous cases.
5.1.2.1.1. Irreversible Isotherm/Single Parameter Isotherm 1 1 1
¼ þ ð20Þ
5.1.2.1.1.1. Irreversible Isotherms. The irreversible iso- qe KL Ce QmL
therm (eq 15) describes a concentration-independent loading of
5.1.2.1.2.2. Freundlich Isotherm. In contrast to the Langmuir
the adsorbent, which is of relevance in certain limiting cases
equation, the Freundlich isotherm, which is also very fre-
such as the application of high solute concentrations, when the
quently applied, assumes monolayer adsorption onto sorbent
system is described by the Langmuir isotherm (cf. eq 19) (11):
surfaces, which are characterized by heterogeneous sorption
qe ¼ const ð15Þ sites (eq 21):

qe (mg/g) is the amount of adsorbate per gram of sorbent at qe ¼ KF CebF ð21Þ

equilibrium.
5.1.2.1.1.2. Henry Isotherm. This one-parameter equation qe (mg/g) is the amount of adsorbate per gram of sorbent at
(eq 16) is based on the assumption that all sorption sites are equilibrium, and Ce (mg/L) is the solute concentration under
identical and may be occupied. Furthermore, interactions be- equilibrium conditions. Furthermore, the Freundlich constant
tween the compounds bound onto the resin surface are ex- KF (L/g) describes the adsorption capacity, and the dimensionless
cluded (9). parameter bF is a measure of the adsorption intensity (38). In
contrast to the Langmuir isotherm, eq 21 cannot be approxi-
qe ¼ kH Ce ð16Þ mated by the Henry isotherm at low concentrations and does not
result in a saturation value at very high solute concentrations (11).
qe (mg/g) is the amount of adsorbate per gram of sorbent at On the basis of the linearized form of the Freundlich equation
equilibrium, Ce (mg/L) is the equilibrium solute concentration, (eq 22), the adsorption capacity KF and dimensionless parameter
and kH is a proportionality factor, also known as the Henry bF may be obtained from the slope and intercept of the linear plot
constant, which is equivalent to the slope of an isotherm, when the of log qe against log Ce (38):
resin loading approximates zero. This isotherm equation cannot
be thermodynamically deduced and, therefore, caution must be log qe ¼ log KF þ bF log Ce ð22Þ
exercised when it is applied. However, due to its good linear
adjustment for small concentrations, the Henry isotherm is 5.1.2.1.2.3. Brunauer-Emmett-Teller Isotherm (BET).
frequently used. The BET isotherm (eq 23) extends Langmuir’s idea of a mono-
5.1.2.1.2. Two-Parameter Isotherms layer adsorption system to a multilayer model, where the sorption
5.1.2.1.2.1. Langmuir Isotherm. The Langmuir adsorption sites are energetically homogeneous and where interactions
model is one of the best known and most frequently applied between individual molecules of one layer do not exist. In
isotherms. It describes the physisorption of neutral particles, that contrast, the BET model assumes such interactions between
is, molecules or atoms, by the sorbent surface, which is char- molecules of different layers. This adsorption isotherm correlates
acterized by energetically homogeneous sorption sites. Further- the binding of target compounds in a monolayer with a decrease
more, only a monomolecular coverage of the adsorbent surface is of binding enthalpy and in addition with a decrease of vaporiza-
assumed, and the desorption rate from a particular sorption site is tion enthalpy because of multilayer formation. The sum of the
thought to be independent of the occupancy of the neighboring changes of binding and vaporization enthalpy can be measured as
sorption sites. adsorption enthalpy. The BET isotherm is specified in eq 23 (39):

Q mL a L C e KL Ce Kp
qe ¼ ¼ ð17Þ c ¼ cm
 ð23Þ
1 þ aL C e 1 þ aL Ce p
ðp0 þ ðK - 1ÞpÞ  1 -
p0
The Langmuir isotherm is illustrated in eq 17 with QmL (mg/g)
being the monolayer adsorbent capacity under equilibrium con- c (mol/g) is the amount adsorbed under equilibrium conditions,
ditions, which indicates the maximum concentration retained by cm (mol/g) is the amount adsorbed in a monomolecular layer, and
Review J. Agric. Food Chem., Vol. 59, No. 1, 2011 31
K is a constant. Furthermore, p0 constitutes the saturation vapor is given through Ce (mg/L). Furthermore, AR (L/g) and BR (L/
pressure and p the adsorptive partial pressure. mg) are the Redlich-Peterson isotherm constants, and Qm (mg/g)
The BET equation can hardly be applied to describe solid- is the monolayer adsorbent capacity. βR is defined as the Redlich-
liquid adsorption systems. Nevertheless, it deserves particular Petersen exponent with values ranging from 0 to 1. The equation
attention because it is commonly used to determine the specific may be approximated by the Henry equation if BR 3 Ce , 1. In
inner surface of microporous adsorbents (9, 11). contrast, saturation cannot be explained with this model (BRCe .
5.1.2.1.2.4. Tempkin Isotherm. The Tempkin model as- 1), but there is an approximation to the Freundlich type (9,11,37).
sumes the existence of indirect adsorbate/adsorbate interactions, This approximation is given in eq 29:
which have a significant effect on the adsorption isotherm. These
AR
interactions are suggested to cause a linear decrease of the heat of qe ¼  Ce 1- β ð29Þ
adsorption of all molecules with increasing surface coverage (37). BR

RT where AR/BR represents KF of the Freundlich model and (1 - β) is

qe ¼  ðln ACe Þ ð24Þ equivalent to 1/bF (41).
bT
The linearized form of this equation can be expressed as follows
The Tempkin isotherm is given in eq 24, where qe (mg/g) is the (eq 30) (42):
equilibrium solid phase concentration and Ce (mg/L) the equi-  
librium liquid phase concentration of the target compounds. AR Ce
ln - 1 ¼ ln BR þ βR ln Ce ð30Þ
Furthermore, A is defined as the isotherm constant (L/mg) and qe
bT (J/mol) as the Tempkin isotherm energy constant. On the basis
5.1.2.1.3.3. Tóth Isotherm. The Tóth isotherm equation
of the linearized form of the Tempkin equation experimental data
(eq 31) relies on a combination of the Langmuir and Freundlich
are used to obtain the isotherm constants A and B by plotting qe
isotherms by forming a differential equation through multiplying
against ln Ce (eq 25)
both differential equations with each other.
qe ¼ B ln A þ B ln Ce ð25Þ
Ce AT
qe ¼
AT =BT ð31Þ
with B as the isotherm energy constant, which is equivalent to the 1
product of the gas constant R (J/mol 3 K) and the absolute þ Ce BT
KT
temperature T (K) divided by the Tempkin isotherm energy
constant bT (J/mol) (eq 26). In solid-liquid phase systems qe (mg/g) expresses the amount of
RT adsorbate per gram of sorbent at equilibrium and Ce (mg/L) the
B ¼ ð26Þ solute concentration under equilibrium conditions, whereas KT,
bT
AT, and BT are temperature-dependent constants. In the follow-
5.1.2.1.3. Three-Parameter Isotherms. Some of the three- ing edge cases the three-parameter equation is simplified, yielding
parameter equations reported in the literature are further devel- the Langmuir isotherm (AT = BT = 1), Henry isotherm (AT =
opments of the Langmuir isotherm. The most common of these BT = 1, and Ce ,1/KT) or Freundlich isotherm (BT = 1 and Ce ,
isotherms are specified below. 1/KT), respectively (9, 37).
5.1.2.1.3.1. Langmuir-Freundlich Isotherm. The Langmuir- 5.1.2.1.4. Isotherm Equations for Models Considering
Freundlich isotherm, which has been developed by Sips, also More than Three Parameters. Isotherm equations considering
takes the energetic heterogeneity of many sorbent surfaces into more than three parameters are rarely used because of the
account by introducing the heterogeneity parameter nLF increasing complexity of their determination with an increasing
(eq 27) (11 , 40 ): number of parameters. Furthermore, the adjustment of experi-
mental data to such models is limited because of measuring
QmLF aLF Ce nLF errors. In this context, the Fritz-Sch€ulner isotherm and the
qe ¼ ð27Þ
1 þ aLF Ce nLF vacancy solution theory (VS theory), which has been modified
by Fukuchi (43) to adjust this model to liquid systems, need to be
QmLF (mg/g) is the monolayer adsorbent capacity under
mentioned. This work has been reported in the literature, but is of
equilibrium conditions, and aLF (L/mg) is the Langmuir
minor importance as compared to the aforementioned the-
constant. qe (mg/g) is defined as the amount of adsorbate
ories (8, 9, 11).
per gram of sorbent at equilibrium, whereas Ce (mg/L) is the
5.1.2.2. Adsorption from Mixture Solutions. The afore-
solute concentration under equilibrium conditions.
mentioned isotherms are commonly applied to describe the
At low concentrations (aLFCenLF , 1) this equation is approxi-
adsorption in single-compound systems. Models for the determi-
mated by the Freundlich isotherm and not the Henry isotherm,
nation of adsorption equilibrium isotherms using mixture solu-
whereas this model predicts saturation at high solute concentra-
tions are divided into two groups. In the first, mixture isotherms
tions (aLFCenLF . 1).
merely rely on the expansion of common single-isotherm equa-
5.1.2.1.3.2. Redlich-Petersen Isotherm. In contrast to the
tions, whereas the second comprises thermodynamic determina-
previous model, the Redlich-Peterson equation exhibits an
tion methods to describe the more complex systems. Both groups
exponent only in the denominator. The isotherm (eq 28) repre-
have thoroughly been reviewed by K€ummel and Worch (11).
sents an empirical three-parameter equation, which allows the
5.2. Ion Exchange. Ion exchange phenomena exhibit numer-
description of adsorption equilibria over a wide concentration
ous similarities with adsorption processes, but there are also some
range.
significant differences. The compound species considered in this
Qm BR Ce AR Ce type of process are ions that are not removed from the solutions
qe ¼ βR
¼ ð28Þ but are replaced by ions bound by the solid phase via electrostatic
1 þ BR Ce 1 þ BR Ce βR
interactions to achieve electroneutrality. Accordingly, there are
The equilibrium concentration in the solid phase is described by qe two ionic fluxes, one into the ion exchange particles and the other
(mg/g), whereas the equilibrium concentration in the liquid phase in the opposite direction out of the resin particles.
32 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Kammerer et al.
In most cases, adsorption and ion exchange phenomena are not temperature. This results from differences in the exchange of ions
differentiated in practical applications, and most theories and with different valences due to concentration-valence effects (1).
models have been approached by using adsorbent resins. This is Thus, the expression isotherm-isonormal should rather be used
due to the fact that the situation is less complex if the resins are for such equilibrium curves when ion exchange phenomena are
devoid of functional groups. In numerous cases, these findings characterized. In theory, one isotherm can be obtained for the
have been translated into ion exchange processes (1). exchange of ions with the same charge. In the case of different
One aspect, which has attracted little interest so far, is the fact valences, it is necessary to use the same normality for ion ex-
that upon the exchange of ionic organic compounds adsorption change experiments.
also occurs onto the resin matrix due to hydrophobic interactions. Using normalized ion exchange isotherms, the interdepen-
This makes the evaluation of ion exchange data much more dence between the ionic composition of the liquid and solid phase
complex. Accordingly, calculations specific to ion exchange pro- in ion exchange systems can be shown. For this purpose, the
cesses based on experimental results obtained from studies with equivalent ion fraction of one counterion on the ion exchanger
charged organic compounds may only be a rough assessment. surface (X) (eq 32) is plotted versus the equivalent ion fraction of
This is attributed to the fact that the differentiation between ion the same ion in the solution (X) (eq 33).
exchange and sorption processes is impossible without further
analytical investigations, such as the quantification of counter- Zi ½ioni  Zi ½ioni 
X ¼ ¼ ð32Þ
ions released during the process. P
n
Q
Zj ½ionj 
5.2.1. Kinetics and Thermodynamics of Ion Exchange j¼i
Processes. The kinetics of ion exchange is much more compli-
cated than that of sorption processes, because there is not only a Zi ½ioni 
mass flow directed toward the exchanger material as in the case of X ¼ 0eXe1 ð33Þ
P
n
adsorbent resins but also a countercurrent of two opposite Zj ½ionj 
electrical charges: first, of the target compounds to be bound j¼i
by the exchange material and, second, of the counterions, which
are released during the exchange process and migrate into the where Zi and [ioni] or [ioni] are the charge and molar concentra-
surrounding solution. The electroneutrality needs to be preserved tion of the respective ion in the solution (mol/L) or in the solid
throughout the exchange process. This not only depends on these phase (mol/g), respectively, whereas Q is the ion exchange
two ion species migrating in opposite direction but also depends capacity of the resin. The deviation of this plot from a diagonal
on the co-ion transport through the exchange matrix, whereas the isotherm, which indicates no preference for any of the ions, allows
latter may be restricted by the Donnan exclusion in many cases. selective enrichment of one ion and thus enables selective extract
The rate-determining step may also depend on the film or purification. An S-shaped isotherm indicates a two-step process,
particle diffusion, which are also affected by the different diffu- with one process dominating at lower and the other at higher
sion rates of the replaced ions and target compounds. Such loading degrees (2, 7).
unequal ion fluxes cause deviation from electroneutrality and With regard to the appropriateness of individual isotherms for
induce an electric potential (diffusion potential), which affects the particular ion exchange systems, there are no general rules or
diffusion of both ions types, that is, the potential accelerates established isotherms, and commonly the isotherm that best fits
slower and decelerates faster ions. the analytical data is used (cf. 1.4.1.2).
Most models established so far describe the kinetics based on 5.2.2.1. Selectivity Characteristics. Ion exchange processes
diffusion processes as can be deduced from the decrease of the can generally be expressed as follows:
target compound contents in the solution and not on ion ex-
AþB h AþB ð34Þ
change rates. Furthermore, theoretical kinetic models are simpli-
fications of the highly complex ion exchange processes. Accord- where A and B illustrate the ions present in the solution brought
ingly, most models are based on major restrictions, such as the into contact with the resin and A and B are the counterions bound
assumption of homogeneous matrices with regard to surface area by the functional groups of the exchanger. Accordingly, ion B is
and pore structure and of constant diffusion coefficients over the exchanged against A.
whole process and for all ionic compounds. Furthermore, most The separation parameters described below give a first over-
models consider only one counterion species or assume that view of the most common characteristics, which have been
significant changes in swelling or in the swelling pressure do not described in the literature but which can only partially be used
occur, which leads to the assumption that such models may not be for the comparison of different exchanger systems. In general, the
applicable to more complex ion exchange systems. Real systems comparison of equivalent proportions of one ion between the two
usually comprise several ions, which compete for the functional phases is the simplest method to obtain information on the
groups of the resins. This means that they have different affinities selectivity of ion exchange processes.
for the functional groups and that they interact with each other or 5.2.2.1.1. Separation Factor. On the basis of eq 35 it is
with the backbone of the exchange material. Thus, on the basis of possible to determine the separation factor R of the ion exchange
these assumptions the kinetics of ion exchange may be specified process at equilibrium.
on the basis of diffusion, applying one of the model assumptions
described by Helfferich (7), which are based on Fick’s first law mA mB X A XB CA CB λA
taking into consideration the aforementioned restrictions, or RA- B ¼ ¼ ¼ ¼ ð35Þ
mB mA X B XA CB CA λB
utilizing one of the rate laws, that is, the first-, pseudo-first- or
pseudo-second-order kinetics (1, 2, 7). In this expression mi and mi are the molalities and Ci and Ci the
5.2.2. Ion Exchange Equilibrium. Comparable to adsorp- molarities of the respective ions, whereas X and X represent the
tion processes, equilibrium isotherms of ion exchange phenomena proportions of the ion in the solid phase and liquid phase at
describe the distribution of the target components between the equilibrium, respectively. Separation factor values above 1 in-
solid and liquid phase at equilibrium. In contrast to adsorption, dicate a preference of ion A, whereas ion B is preferably bound at
ion exchange may show more than one isotherm at a particular R values of <1. The numerical value of the separation factor R
Review J. Agric. Food Chem., Vol. 59, No. 1, 2011 33
and its independence from the concentration scale is a great 6.1. Bed Processes with Fixed Bed Reactors. The bed process
advantage with regard to the application as parameter for is the most commonly used and simplest technology for fluid
comparison (2, 7). adsorption and ion exchange processes. In this type of process,
5.2.2.1.2. Distribution Coefficient. The molal or molar resin loading is performed until the concentration of the solution
distribution coefficient λi and λi0 , of the ion i, respectively, is leaving the bed exceeds a certain threshold level. This stage of the
another parameter helpful for describing the equilibrium distri- process indicates exhaustion of the resin capacity and is referred
bution of ions between the liquid phase and the solid phase of the to as breakthrough. In bed sorption processes breakthrough
ion exchanger (1, 2, 7). These parameters are defined as follows loading is commonly performed instead of equilibrium loading,
(eqs 36 and 37): which is characterized by much higher compound leakage.
mi Subsequently, the resin needs to be regenerated or substituted.
λi ¼ ð36Þ For a better utilization of the resin in bed processes, adsorber and
mi
ion exchange columns are commonly connected in series using
0 Ci either several columns in different loading states or one adsorber
λi ¼ ð37Þ with several adsorption layers. Alternatively, adsorbent or ion
Ci
exchange columns in different loading states may be connected in
5.2.2.1.3. Selectivity Coefficient. The selectivity coefficient parallel to obtain a mixed concentration of the column eluates.
can also be used instead of the separation factor to describe ion Bed processes may be further differentiated on the basis of the
exchange equilibriums. This may apply if the ion exchange method of regeneration. In cocurrent regeneration procedures
reaction (eq 34) obeys the mass action law and is described by both the loading and regeneration of the resin are performed in
its term, because the ion exchange process can be regarded as a the same flow direction. In contrast, countercurrent regeneration
physical redistribution of ions without chemical reaction. means that the solutions used for regeneration are applied to the
column in the opposite direction as compared to sample applica-
0 mA ZB mB ZA
kA - B ¼ ð38Þ tion. This procedure yields higher concentrations upon desorp-
mB ZA mA ZB tion, because the resin particles at the end of the sorbent column
ZB are not brought into contact with highly concentrated eluates.
00 C A CB ZA
kA- B ¼ Z
ð39Þ Consequently, countercurrent processes require less desorbent
C B A CA ZB and afford higher eluate concentrations. Besides some disadvan-
tages, bed processes have crucial advantages with regard to marginal
Equation 38 describes the selectivity coefficient kA-B0 using the instrument and metrological equipment requirements (1,2,9,11).
molality of the ions, whereas kA-B00 (eq 39) is calculated using 6.2. Batch Processes in Agitated Reactors. Batch processes
molarities. ZA and ZB are the electrochemical valences of the may be operated in continuous and discontinuous modes. Agitat-
species A and B. ing a fixed amount of adsorbent in a defined fluid volume is the
If the selectivity coefficient is used for comparing different simplest application of such a discontinuous batch process. After
systems, it should be kept in mind that this parameter strongly reaching equilibrium conditions, the adsorbent needs to be
depends on the operation conditions. Consequently, selectivity removed from the fluid, for example, by filtration or sedimenta-
coefficients obtained through applying different experimental tion, after which the adsorbent can be reused or disposed of.
conditions may not be compared (2, 7). However, in industrial applications equilibrium is normally not
However, it has also been noted that eq 39 may only be reached, because the recovery of the target compounds per time is
calculated using the equilibrium concentrations CiZj and CiZj if optimized. In contrast, continuous processes are based on multi-
complex formation in the solution does not occur and if interac- stage purification or separation steps, with an economic evalua-
tions between the counterions are not observed (2). tion being required to deduce optimum conditions for each
The selectivity coefficient may also be calculated using equiva- application. The sorbent amount needed can be lowered through
lent ionic fractions and is then equated with the rational selectivity optimized utilization. For this purpose, the adsorbent and the
coefficient fluid, which is to be purified or contains the target compounds to
Z be recovered, may be brought in contact in countercurrent pro-
X A B XB ZA
KA- B ¼ Z
ð40Þ cesses. Furthermore, an increase in the number of process stages
X B A XA ZB also contributes to the need for lower resin amounts. Addition-
ally, the wide variation of residence time of the adsorbent in the
where only in the case of identical valences of the counterions
reactor gives rise to uneven loading of the resin particles. Due to
(ZA = ZB) is the selectivity coefficient predicted by the molality
the lower exploitation of adsorbent capacity in batch processes as
(eq 38) or the molarity (eq 39), respectively, identical to the
compared to bed process technology as well as higher acquisition
selectivity coefficient determined according to eq 40.
and operating costs, bed processes are commonly preferred.
As mentioned by Helfferich (7), unfortunately the notation of
Nevertheless, the comparatively expensive batch adsorption pro-
the aforementioned equations in the literature strongly differs,
cess using agitated reactors is mainly applied for producing high-
which also aggravates direct comparison. As an example, Zagor-
quality biotechnological and pharmaceutical products, such as
odni (2) differentiates between the selectivity coefficient and
antibiotics or proteins. Furthermore, batch processes are also
equilibrium coefficient, whereas the latter is consistent with the
commonly applied in the beverage industry and for potable water
expression given as eq 40.
preparation using powdered activated carbon (1, 2, 8, 9, 11).
6.3. Moving Bed Processes Performed in Reactors with Moving
6. TECHNIQUES OF ADSORPTION AND ION EXCHANGE Solid Phase. This technology consists of continuous sorption
As described further below, the applications of adsorbent and processes applicable to sorbent materials, which are not delivered
ion exchange technology and the industrial equipment, which is in powder form. Here the sorbent material crosses the system
used for different requirements, are highly variable. Consequently, from top to bottom without being kept in suspension and is
it is only possible to provide a brief overview of the currently used removed from the system from time to time. The solution
adsorbent and ion exchange processes. containing the adsorptive is applied in countercurrent direction,
34 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Kammerer et al.
thus introduced at the bottom end and removed at the top end of Moreover, biotechnological processes make use of not only
the reactor. Another moving bed process variant is characterized adsorbent technology but also ion exchange techniques. In this
by the periodic application of a solvent flow through the adsorber context, in the production and application of microbial transglu-
from bottom to top that leads to a pulsative rise of the adsorbent taminase, extracellular transglutaminase was separated from the
(expanded bed, semifluidized bed, or suspended bed). The flow fermentation broth in a downstream process inter alia by a
rate of the adsorbent is controlled via the continuous quantifica- strongly acidic ion exchanger (55). The production of microbial
tion of the target compounds in the feed stream and by the transglutaminase instead of its isolation from animal and plant
maximum tolerable level of these components in the fluid stream tissues allowed for the first time mass production of this techno-
after adsorption or ion exchange. Even though circumventing logically important enzyme from relatively cheap substrates.
major disadvantages of bed processes, moving bed technology Consequently, such novel production strategies enable the appli-
also has some significant disadvantages, such as high investment cation of enzymes, such as transglutaminase, on a large scale in
costs and the complexity of resin dosage and suspension and the food processing and the cosmetics and pharmaceutical industries
control of the fluid and solid phase transport. Fluidized bed as well as for medical treatments. The very diverse applications of
adsorbers have a further advantage common to all moving bed this particular enzyme comprise the modification of the func-
processes, because these technologies may be applied even if the tional properties of food proteins, such as whey and soy proteins,
solutions to be purified contain solid particles. However, such gluten, myosin, and actomyosin by catalyzing the cross-linking of
processes are currently still limited to research applications (1,2,8,9). proteins (56). These modifications may bring about textured
products and yield food proteins of higher nutritive values by
7. APPLICATIONS OF ADSORPTION AND ION EXCHANGE cross-linking proteins, which complement each other with regard
TECHNOLOGY to their limiting amino acids. Such cross-linking reactions also
7.1. General Applications. Together with the development of significantly affect the technofunctional properties; they may
more sophisticated synthetic ion exchange and adsorbent resins, improve the elasticity and water-holding capacity and modify
the number of potential applications on industrial scale rose as the solubility and further functional properties of the proteins,
well. In recent decades, profound knowledge has been accumu- and they help to avoid the heat treatment necessary for gelation.
lated concerning the structure and properties of ion exchange and Furthermore, transglutaminase-catalyzed reactions contribute to
adsorbent resins. Concomitantly, the bonding types and interac- the protection of lysine against a number of chemical reactions
tions between the adsorptive and adsorbent as well as between the involving food proteins or can be used to encapsulate lipids and
counterion and the ion exchanger were studied, resulting in more lipid-soluble materials or to produce heat- and water-resistant
detailed information, which is useful for process optimization and films.
further investigations (1-3, 8, 32, 44-49). The purification of lactic acid produced through fermentation
7.1.1. Adsorbent Resins. Water purification is one of the processes is a further application of ion exchange on an industrial
most important applications of adsorbent technology in solid- scale. Inhibitory effects due to product accumulation usually
liquid systems, providing water in high quality, which is required characterize the microbial production of lactic acid using differ-
for industrial purposes, for example, for the production of paper, ent natural feedstocks. Because this inhibition is already induced
synthetic fibers, electrical power, or electronic components as well by relatively low amounts of lactic acid in the fermentation
as for pharmaceutical and food production and for laboratory broths, Ataei and Vasheghani-Farahani (57) proposed an in situ
purposes (1,2,50). Furthermore, there are many biotechnological separation of lactic acid from the fermentation media using a
processes making use of sorbent recovery to enrich and purify strongly basic ion exchanger. On the other hand, the purification
components used in foods, beverages, cosmetics, and pharmaceu- of lactic acid following fermentative production has also been
ticals. As an example, Hua et al. (51) reported enhanced vanillin reported using weak anionic (58) and strong anionic ion exchange
production from ferulic acid through a biotransformation strat- materials (59), respectively. Furthermore, combinations of cation
egy by selectively adsorbing vanillin throughout the process. and anion exchange resins, which are applicable either to recover
Consequently, increased vanillin yields may be reached by avoid- lactic acid (60, 61) or to remove all other compounds from the
ing toxic effects on the Streptomyces sp. strain V-1 used in this fermentation broth except lactic acid (62) have been described as
study for converting ferulic acid. In addition, inhibition of the well. Lactic acid is widely applied in the food industry, in
microorganisms due to product accumulation can be prevented medicine, chemical, and pharmaceutical fields, and as educt for
by sorptive recovery of the target compound. the production of biodegradable and biocompatible polymers in
In another process, adsorbent resins were applied to purify the packaging industry and in medicine (63, 64). In this case, ion
rosmarinic acid from Lavandula vera DC. biomass, which was exchange technology proves to be a suitable and relatively simple
cultivated in bioreactors (52). Rosmarinic acid is used for pharma- and inexpensive alternative to other tedious purification methods
cological purposes due to its antibacterial, antiviral, anti-inflam- used so far (57, 62, 64).
matory, antioxidant properties, and concomitant low toxicity. Further applications of ion exchangers comprise the purifica-
From a pharmacological and cosmetics point of view, oregonin tion of blood, vitamins (65), and enzymes as well as of pharma-
is another interesting compound, and its recovery from alder cologically active compounds (2, 44, 54), such as antibiotics
species such as Alnus glutinosa L. and Alnus incana L. has been (66-68). Sometimes ion exchange resins themselves are used as
described (53). For this purpose, oregonin was extracted from the active pharmaceutical ingredients or as excipients (69).
bark with hot water, subsequently concentrated by binding onto 7.2. Food Production. In food production, ion exchange and
an adsorbent resin based on acrylic esters, and finally eluted with adsorption technology is applied for numerous purposes, not
alcoholic solutions. only during food production itself but also for wastewater
7.1.2. Ion Exchange Resins. In accordance with adsorbent treatment. With respect to holistic and sustainable agricultural
resins, water softening and purification are by far the economi- production, the residues of food production are of increasing
cally most important applications of ion exchange, thus providing interest to processing companies, because these byproducts are
water in high quality required for industrial purposes, for example, normally still rich in a number of valuable compounds. Accord-
for pharmaceutical, food, and textile production as well as power ingly, they can be used to obtain, for example, proteins or pectins
generation (2, 44, 50, 54). and to recover non-nutritive plant secondary metabolites, such as
Review J. Agric. Food Chem., Vol. 59, No. 1, 2011 35
polyphenols, which are used as supplements of functional or However, off-tastes and off-flavors developed during storage are
enriched foods. The most important applications for these purposes unaffected by such a treatment. These off-tastes and off-flavors
are summarized below. are formed from precursors, which themselves do not negatively
7.2.1. Adsorbent Resins in Food Production. As mentioned affect the sensory properties of the fresh juice, if they are degraded
before, adsorbent technology is not only implemented into or react with other juice components. Precursor components,
existing food production lines but also commonly applied to which contribute to off-flavor formation, may result from the
treat the huge amounts of wastewater originating from such heating process in the course of thermal preservation of the juices,
processes. In this context, adsorbent technology may form a from degradation processes such as the Strecker reaction or from
substantial part of the respective concept of water treatment for other nonenzymatic browning reactions. Ferulic acid is an
removing organic compounds (1, 70). For example, olive oil mill example of such a precursor compound, because it may lead
effluents are decolorized prior to their anaerobic digestion (71). to the formation of p-vinylguaiacol, which contributes to an
Fruit juice technology is one of the most important application “old fruit” or “rotten” flavor (84, 85). Processes to cope with
areas of adsorbent resins in the food industry. As an example, off-tastes and off-flavors arising during storage by removing
Vivekanand et al. (72) have described a process for the quality such precursor components from juices using adsorbent resins
improvement of UF-clarified pear juice by successively using an have been described with the changes being immediately
adsorbent resin and a weak ion exchanger at different operating noticeable. Such a process enhances the sensory quality of
temperatures. The adsorbent resin brings about the removal of the juices without affecting their nutritional values and at the
most colored organic compounds from the preconcentrated pear same time extending shelf life over a long period even if stored
juice, whereas the ion exchanger significantly lowers color in- at ambient temperature, provided that microbiological stabil-
tensity and titratable acidity, thus leading to desirable clear, light- ity is given (84, 85).
colored, and weakly flavored juices. Such products have been The selective removal of unwanted compounds from olive oil
designed to retain their nutritional values and extended their shelf miscella is a completely different application of adsorbent res-
life. They are used as a substitute for sugar syrup in canned fruits ins (86). In this process, n-hexane extracts from crushed olives,
or as a source of natural sugar when mixed with other juices, containing pigments, such as carotenoids, chlorophylls, and
because they are devoid of precursor compounds, which may pheophytins, and also free fatty acids, phospholipids, and various
cause haze formation and discoloration upon storage (72). oxidation products, need to be refined by using adsorbent
Adsorbent resins may not only be used for the aforementioned materials in single-step or multistep processes after oil extraction.
juice and syrup production for the fruit canning industry but also After sorptive removal of these compounds, the oil can be used
for the stabilization and decoloration of fruit juices as well as for for edible purposes. A systematic comparison revealed the
reducing the bitterness of citrus juices. In this context, adsorbent efficiency of activated carbon and activated earth to be much
technology appears to be an appropriate alternative to common higher compared to synthetic resins with regard to the removal of
fining methods using bentonite, gelatin, and silica sol, respec- the aforementioned components. Furthermore, the selectivity of
tively. The combination of adsorbent technology with an up- the recovery of these different compound classes significantly
stream ultrafiltration step reveals synergistic effects by removing depended on the type of adsorbent material and the adsorbent/
compounds above a particular molecular size and additionally by oil ratio. In addition, due to the different selectivities of the
exploiting hydrophobic interactions of juice components with the sorbents the sequential application of different materials might be
adsorbent resin. In general, adsorption processes provide the useful (86).
opportunity to standardize juices and even to produce light- 7.2.2. Ion Exchangers in Food Production. As mentioned
colored almost water-clear juices (73-75). On the other hand, for adsorbent resins, ion exchangers also play a dominant role in
fruit juices such as apple juice have been applied as model wastewater treatment as well as in water softening, desalination,
solutions in laboratory-scale experiments for studying the selec- and purification to provide water in sufficient purity for the
tive recovery and fractionation of phenolic compounds using respective applications (1, 2, 50, 87).
adsorbent resins. These efforts aim at the systematic optimization The decolorization of sugar beet and sugar cane extracts during
of purification and separation processes by adaptation of process sugar production is another very important application of ion
parameters to obtain polyphenol preparations with well-defined exchange technology. The spoiling pigments result from Maillard
functional properties, which may be applied in functional or reactions and alkaline degradation of hexoses (88, 89), but may
enriched foods (76). Furthermore, the recovery of phenolic also be of phenolic nature (90). To produce colorless sucrose
compounds with adsorbent resins using apple polyphenol model crystals sugar syrups may be decolorized by highly cross-linked,
solutions has also been performed at pilot scale. The leakage rates macroporous styrenic copolymers functionalized with weakly
during column loading as well as the elution of individual basic as well as weakly acidic functional groups, respectively (90),
compounds with hydroalcoholic and NaOH solutions were or by styrene divinylbenzene copolymer based adsorbent re-
demonstrated to be structure-dependent, which allows selective sins (88). Furthermore, a macroporous copolymeric resin, made
enrichment of certain polyphenol classes (77). up of a monovinyl aromatic monomer, which was post-cross-linked
Off-tastes and off-flavors are another issue associated with in the swollen state and additionally functionalized with hydro-
juice production. Such problems may arise immediately after philic groups, has also been reported to be applicable for the
processing or during storage. The bitterness of grapefruits and decolorization of aqueous sugar solutions. This also allows the
navel oranges caused by naringin and limonin and by hesperidin subsequent recovery of the colorants and of their precursors (91).
and limonin, respectively, are examples of such off-tastes occur- It is well-known that the nature of colorants is quite different in
ring prestorage (78-83). Furthermore, consumers may reject sugar beet and sugar cane extracts, which also has an impact on
highly acidic juices (79, 80). According to literature reports, such the requirements of the resin materials used for decoloriza-
off-tastes and off-flavors can be removed by treating the juices tion (89). Furthermore, the evolution of colorants in sugar beet
with adsorbents as a final step of juice production. With regard to juices during decolorization using a strong anionic styrene resin
the reduction of juice acidity, it has been demonstrated that in has been studied in detail, revealing that operating conditions and
comparison to adsorbent resins organic acids may be more the type of solvent have significant impacts on the binding and
effectively removed by using weak anion exchangers (79, 80). elution of the colorants and also showing that different affinities
36 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Kammerer et al.
of the colorants depend on the differences in their molecular milk preparation was below 0.25 g/L. Finally, the juice and milk
weights (89). components were blended, homogenized, and subsequently pas-
The decaffeination of liquid extracts such as of coffee, tea, and teurized or sterilized, respectively, and/or carbonated. The bev-
cocoa is another very interesting application of ion exchangers. erages obtained did not show any precipitation or curdling,
Using a gel copolymer composed of monovinyl aromatic mono- although the pH of the beverages was below the isoelectric point
mer units, cross-linked after polymerization in swollen state and of casein.
functionalized with hydrophilic groups, has been shown to be Processes for the selective removal of sugars from beverages,
efficient in binding caffeine without removing substantial such as citrus juice, cranberry juice, apple juice, or pineapple juice,
amounts of chlorogenic acid from coffee extracts. The subsequent alcoholic beverages, and dairy products are a completely different
elution of bound caffeine may be performed with organic application of ion exchange technology (98). The resin used for
solvents. Compared to other decaffeination processes, this pro- that particular purpose is composed of a cation exchanger, which
cedure affords a very aromatic, dark colored, and very flavorful builds up a complex with the sugars via its counterions Ca2þ,
product (92). By applying ion exchange and adsorption technol- Naþ, and Kþ. This process helps to reduce energy costs signifi-
ogy the disadvantages of other processes, such as the extraction of cantly during juice concentration, to bring down costs of storage
caffeine with organic solvents, supercritical extraction requiring and transport, and to produce low-calorie juices and alcoholic
cost-intensive equipment and high pressures, or the Swiss extrac- beverages sweetened with synthetic additives without affecting
tion using carbon beds that act abrasively, thus causing costly the natural contents of minerals, vitamins, and other beneficial
maintenance, may be avoided (92). compounds as well as flavor, aroma, and color. Accordingly, ion
Ion exchange technology has a wide area of application in the exchangers also allow reducing the lactose contents in milk and
beverage industry, where it is used to resolve a number of other dairy products.
problems. In this context, haze formation in beer, wine, and fruit Furthermore, ion exchange technology and combinations with
juices upon storage is a major problem. To prevent haze forma- adsorbent resins may be applied in a wide range of other fields as
tion in these beverages, the precursors, that is, proteins and can be deduced from the product descriptions of resin manufac-
polyphenols, need to be lowered in their contents, whereas the turers (99, 100). As an example, the desalination of inulin from
removal of phenolic compounds also causes undesirable color chicory and Jerusalem artichoke and the desalination and prep-
losses. A procedure used so far, which also brings about partial aration of syrups from corn, wheat, potatoes, and cassava have
color loss, implies the application of bentonite in combination been described. Ion exchange is also applicable for the selective
with diatomaceous earth filters to remove the bentonite after its purification of sugar alcohols, obtained from mono- and di-
use. This process is characterized by the disadvantage of causing saccharides by nickel catalysis. For this purpose, the catalysts are
negative taste in wines and being responsible for decreased recovered and the solution decolorized and desalted. Finally,
product recovery rates (73, 93). Due to these drawbacks the resins are available for the softening of gelatin and the desalting of
application of an anion exchange resin in sulfonated form has pectins.
been suggested to selectively remove haze-forming proteins in 7.3. Recovery of Bio- and Technofunctional Compounds from
beer and wine without markedly affecting color (93). Another ion Byproducts of Food Processing. Food production is commonly
exchange- and reverse osmosis-based process to remove divalent associated with large amounts of byproducts, which are still very
ions from tea beverages has been reported to obtain a product rich in valuable compounds. This provides the opportunity to
containing tea polyphenols from black and/or green tea leaves, recover such components as added value and to contribute to
which is stable in color and devoid of any turbidity (94). sustainable agricultural production (101, 102). Ion exchangers
Furthermore, ion exchange technology is commonly used for and adsorbent resins may be applied to enrich and purify such
the reduction of organic acid contents of fruit juices, mostly of products from food-processing byproducts, and some of these
citrus juices (79, 80). In addition, the production of fruit syrups applications are further described below. However, not all of
from apples, pears, plums, damsons, cherries, figs, dates, grapes, these processes are applied on an industrial scale so far.
pineapples, bananas, and carobs using anion and cation exchange 7.3.1. Protein and Peptide Recovery. Among other meth-
resins for the demineralization, deionization, and decolorization ods ion exchangers are used for the purification and isolation of
has been described (95). proteins and amino acids, for example, of whey proteins originat-
There are also studies describing the improvement of white and ing in huge amounts as byproducts of cheese production. Whey
rosé wine decoloration by applying continuous ion exchange proteins are mainly composed of R-lactalbumin and β-lacto-
processes instead of the common discontinuous decoloration globulin as well as lower amounts of immunoglobulin, bovine serum
with activated carbon, which is a time-consuming process due albumin, glycomacropeptides, lactoferrin, and lactoperoxidase.
to the settling and filtration process, respectively, which is These different proteins may be separated by exploiting the
associated with considerable losses regarding production quan- selective binding onto or desorption from exchanger resins under
tity and a considerable amount of solid wastes (96). optimized operating conditions (103). Thus, a number of methods
Additionally, the application of ion exchangers has been for whey protein isolation using cation exchangers have been
suggested to produce low-acid fruit juice/vegetable-milk bev- patented, preventing protein denaturation during purification (104).
erages (97). For this purpose, the juices were decationized using a These purified proteins of high nutritional value can be applied as
strong cation exchange resin, causing a pH decrease to 2.5-3.0. a mixture in food products, for example, as thickening or stabi-
Subsequently, a strong anion exchanger was applied to increase lizing agents in clear beverages and as infant or enteral formula or
the pH value to 8.0-11.5 and deanionize the vegetable or fruit pharmaceutical formulations, respectively. The purification of
juices. As a further step, the juices were once more treated with a individual whey proteins has been studied in detail. As an example,
strong cation exchange resin, resulting in a pH value of 3.5-4.5. the dependency of the purification of glycomacropeptide, a
The milk component of the beverage was obtained by contacting decomposition product formed because of enzymatic cleavage
the milk with a strong cation exchange resin, thus, decreasing the of κ-casein during cheese production, from conductivity, pH
pH value to 1.5-3.2. Following this, the milk was treated with a value, and elution buffer salinity when using an anion exchanger
strong anion exchanger to remove anions and increase the pH was assessed (105). Great importance has been attached in this
value to 3.5-4.5. The resulting mineral content of the obtained study to the use of food-grade resins, food-grade eluent buffers,
Review J. Agric. Food Chem., Vol. 59, No. 1, 2011 37
and operating conditions relevant to industrial procedures, show- demonstrate another application area of ion exchange and
ing that highest recovery may be reached at decreasing conduc- adsorbent technology (114). Tocopherols and tocotrienols, com-
tivity and increasing pH value of the mozzarella whey feed stream monly referred to as vitamin E, are the most important natural
used in this study. Glycomacropeptides have attracted much fat-soluble antioxidants, which are able to donate their phenolic
interest because they are devoid of aromatic amino acids, such hydrogen to free radicals, thus acting as radical scavengers.
as phenylalanine, tryptophan, and tyrosine, thus making them Tocopherols and tocotrienols can be recovered using strongly
an interesting protein source for people suffering from phenyl- basic anion exchangers or nonionic adsorbent resins. The selec-
ketonuria. tivity of the recovery process when using nonionic adsorbent
Furthermore, the purification of whey permeate using benton- resins is mainly determined by the elution step. For this purpose,
ite and ion exchangers yields syrups containing hydrolyzed tocopherol mixtures are dissolved in a long-chain alkane and
lactose, which may be used as potential sweetener or as energy applied to the adsorbent column. During the fractionated de-
source in nutrient solutions applied for fermentation purposes sorption of the tocopherols, the polarity of the eluent is constantly
(106). Gonzales et al. (107) described the production of a modified increased. The desorption starts with a long-chain alkane to elute
whey powder characterized by low mineral contents, low hygro- R-tocopherol, followed by a mixture of long-chain alkane sol-
scopicity, and beneficial organoleptic properties using ion ex- vents containing ketones to elute γ-tocopherol and finally by a
change resins. This product may be applied in dry form, for monohydric alcohol or mixtures thereof to recover all other
example, in biscuits, confectionery, or powdered soft drinks. tocopherols. In contrast, when strongly basic anion exchangers
Additionally, adsorbent technology is useful for desalting and are used, the sample containing the tocopherol mixture is dis-
debittering whey, soy, defatted sesame, and fish skin protein solved in a polar solvent mixture, containing, for example,
hydrolysates (108-111). For this purpose, protein hydrolysates methanol and acetone. In this case, fractionation may be obtained
are adsorbed onto a macroporous resin. Subsequently, the resin is due to the weaker interaction of nonpolar tocopherols with the
washed with deionized water to remove salts, and the adsorbed ion exchanger as compared to more polar ones (114). Khare (115)
peptides may be desorbed fractionwise by using different alcohol used organic solvents such as methanol for the elution of
concentrations (110, 111). Accordingly, bitter peptides can be γ-tocopherol, whereas R-tocopherol was also eluted with this
selectively removed from the hydrolysates. With regard to fish solvent. In contrast, δ-tocopherol was eluted by using an acidified
skin hydrolysates it was noted that the washing step causes a organic solvent. According to another process the isolation of
significant reduction of fish flavor and of the bitter taste of the tocopherol isomers from crude palm oil, palm oil products, or palm
final product (110). These hydrolysates may find application in oil byproducts as well as vegetable oils or vitamin E-comprising
pharmaceutical products, in functional foods, and in infant preparations can be achieved. For this purpose, free fatty acids
formula, as well as in clinical nutrition (111). and triacylglycerols were esterified or transesterified and, subse-
The recovery of grass carp fish scale peptides using nonpolar quently, the esters were removed by distillation before the
macroporous resins is another quite different approach demon- obtained vitamin E concentrate was selectively bound onto an
strating the broad applicability of this technique (112). Protein adsorbent resin. The fractionated elution of the tocopherols was
hydrolysates are of particular interest to both the food and realized using a supercritical fluid, such as CO2, in combination
pharmaceutical industries due to their biofunctional properties. with a modifier or other solvent such as propane, propene, or
In the case of grass carp peptides the inhibition of the angiotensin-I ethylene (116). Using this technology, tocopherols can also
converting enzyme (ACE), resulting in a decrease of blood directly be isolated from plant oils. Thus, such a recovery process
pressure, is the bioactive principle rendering their recovery is not restricted to the byproducts of plant oil production.
worthwhile. On the other hand, increasing costs for the disposal 7.3.3. Polyphenol Recovery from Food Processing Byprod-
of the filleting residues in the growing grass carp fish production, ucts. Byproducts originating from plant food processing are
and the fact that they are underutilized so far, spark interest in usually particularly rich in plant secondary metabolites, especially
their exploitation to recover novel value-added products. In polyphenols. Due to the technofunctional properties of phenolic
summary, such grass carp peptide preparations were obtained compounds, such as their antioxidant and antimicrobial potential
by dissolving freeze-dried powders of the scale hydrolysates in or their protective and stabilizing effects on food color and aroma
water and applying them to adsorbent resins, followed by the as well as their biofunctional characteristics, including anti-
desalting with distilled water and the fractionwise elution of the carcinogenic, antithrombotic, anti-inflammatory, antimicrobial,
peptides with aqueous ethanol solutions of increasing alcohol and antioxidant properties, they are highly interesting for the
proportions. food, pharmaceutical, and cosmetics industries. The character-
In addition, resin adsorption and ion exchange were demon- istics and fields of application of extracts obtained from food-
strated to be valuable tools for the recovery of protein isolates of processing byproducts may significantly differ depending on the
high nutritional and sensory quality from the byproducts of type of fruit or vegetable residue used for polyphenol recovery.
sunflower oil processing. These proteins have not been utilized 7.3.3.1. Fruit Phenolics. The byproducts of citrus juice pro-
for human consumption so far because of major drawbacks due duction, that is, peels as well as core, cell, and membrane residues,
to coextracted phenolic compounds, which may covalently bind are commonly used as cattle feed, but may also be exploited for
to the proteins bringing about discoloration and impaired tech- pectin recovery. Furthermore, citrus byproducts might serve as
nofunctional characteristics of the protein isolates. For this sources of cold-pressed oils, D-limonene, natural flavors, aroma,
purpose, adsorbent and ion exchange resins, which show minimal ethanol, molasses, pulp wash, and flavonoids (102, 117). Citrus
interactions with the proteins, are instrumental to selectively bind fruits and products derived therefrom are known to be particu-
the phenolic compounds from crude protein extracts, thus yield- larly rich in flavanones and flavanone glycosides.
ing proteins devoid of polyphenols with improved functional and Accordingly, Di Mauro et al. (118) developed and optimized a
sensory properties (113). process for the recovery of hesperidin from orange peels through
7.3.2. Tocopherol Recovery from Food Processing Byprod- concentration on a styrene-divinylbenzene copolymerisate. For
ucts. The separation and purification of tocopherols and toco- this purpose, extraction was carried out with an aqueous calcium
trienols from natural sources, especially the byproducts of plant hydroxide solution, causing the precipitation of colloidal pectins
oil refining, synthetic and semisynthetic tocopherol products, as calcium pectate, which otherwise may interfere with the subsequent
38 J. Agric. Food Chem., Vol. 59, No. 1, 2011 Kammerer et al.
separation and concentration of hesperidin by adsorbent resins. the phenolic compounds are desorbed with methanol, which
The neutralized crude extract was loaded onto the adsorbent resin allows gentle concentration by evaporating the alcohol. The
and subsequently eluted with a 0.5 N sodium hydroxide solution almost colorless pectins were recovered through precipitation
containing 10% ethanol, prior to crystallizing hesperidin upon with alcohols from the eluates, which were collected during
acidification of the solution. Hesperidin was obtained in high column loading with the crude apple pomace extract.
purity and concentrated form with the pectins being removed. Besides apple pomace, the byproducts of pomegranate process-
Furthermore, adsorbent resins may also be used for the recov- ing have also been identified as rich sources of phenolic com-
ery of anthocyanins from the pulp wash of pigmented oranges, pounds. To exploit the potential, a recovery process for rapid
for example, from water-extractable orange solids obtained large-scale purification of ellagitannins from pomegranate husks
through several washing and refinishing steps by sorptive binding has been described (127). For this purpose, pomegranate husks,
and subsequent desorption with ethanol. Besides great amounts the byproducts of juice preparation, were extracted, and the
of anthocyanins, eluates obtained under these conditions contain aqueous polyphenol extract was purified using an evacuated
hesperidin and hydroxycinnamic acid derivatives, which may column filled with Amberlite XAD-16. This procedure yielded
further stabilize anthocyanins through intermolecular copigmen- pomegranate tannins, punicalagin, ellagic acid, punicalin, and
tation (119). This valorization process has been further expanded ellagic acid-glycosides, that is, a pentoside, hexoside, and rham-
by deacidification of the adsorbent column eluates, which are noside, in substantial yields. This low-cost recovery method is
devoid of polyphenols, using ion exchange resins followed by also applicable on an industrial scale to exploit a currently
ultrafiltration and reverse osmosis steps to remove enzymes, underutilized food-processing byproduct for the recovery of food
microorganisms, and 80% of the water, respectively. According and cosmetic additives acting as biopreservatives or phytoceuti-
to this process, a brilliant and almost colorless natural sweetener cals based on the potential health benefits of these components.
can be obtained (120). Not only are solid plant residues a source The discovery of sources for the recovery of colored plant
of polyphenols such as hesperidin but also wastewater originating secondary metabolites, such as anthocyanins, betalains, and carot-
from citrus processing. Such wastewaters arise from the essential enoids, has attracted even more interest, which is due to the so-
oil recovery process and still contain considerable amounts of called Southampton study revealing a correlation between the
hesperidin. In this case hesperidin may be separated through consumption of beverages colored with synthetic additives and
solubilization by adding calcium hydroxide to reach a pH value of the occurrence of attention-deficit hyperactivity disorder in 3- and
12 followed by filtration and neutralization of the solution (pH 6) 8/9-year-old children (128). Consequently, foods colored with
prior to adsorptive binding of hesperidin onto an adsorbent resin. synthetic pigments need to be labeled with a warning according to
Desorption can be realized using a 10% aqueous ethanol solution the newest European Food Safety Authority (EFSA) regulations.
containing 0.46 M sodium hydroxide as eluent and subsequent This study significantly enhanced consumer rejection of artificial
precipitation at pH 5, yielding high purities of the flavanone (121). colorants and resulted in an increased demand for natural food
Furthermore, the treatment of citrus peel juice and molasses by colorants and coloring foodstuffs.
macroporous adsorbent resins has been thoroughly studied, One of the potential sources for the recovery of natural color-
aiming at the removal of bitter limonoids and phenolic com- ants and coloring foodstuffs is red grape pomace. Together with
pounds, whereas other polyphenols not significantly affecting white grape pomace, it represents a valuable source of phenolic
sensory properties, organic and inorganic acids, may be removed compounds, which are present in high amounts in grape skins and
by activated carbon or anion exchange resins, respectively (122). seeds and which are only poorly extracted upon vinification. Even
Styrene-divinylbenzene copolymerisates are also applicable for though grape pomace is a valuable source of ethanol, organic
the recovery of cold-pressed grapefruit oil constituents, such as acids, and grape seed oil, it is still largely used for compost
D-limonene, R-terpineol, nootkatone, linalool, octanal, and decanal, production and as soil conditioner (102, 129). Besides that, the
from wastewater of citrus fruit processing. The bound essential oil extraction of phenolic compounds from grape pomace becomes
was recovered from the resin using 95% ethanol (123). increasingly important, and numerous studies have been per-
Apple juice production is also associated with great amounts of formed concerning this matter (130). The reports include the
wet pomace, increasingly posing environmental problems and optimization of pigment extraction (131), the isolation of indivi-
causing high disposal costs for the juice-producing companies. So dual hydroxycinnamoyltartaric acids by high-speed countercur-
far, these byproducts are mostly used as forage, as game feed, and rent chromatography (HSCCC) from grape pomace (132), and
for biogas or fertilizer production. Apple pomace is also often the recovery of polyphenols from the byproducts of grape seed oil
incinerated or used for land filling, even though the press residues production (133). Among these studies, processes for the recovery
are particularly rich in pectins and plant secondary metabolites, of anthocyanins using adsorbent resins have been described (134).
mainly polyphenols. Having this in mind, the utilization of the For this purpose, grape pomace extracts were produced by sulfite-
apple pomace for pectin recovery is profitable (124) and thus free aqueous enzyme-assisted extraction of the grape skins,
performed on an industrial scale. On the other hand, polyphenol followed by solid-liquid separation using a decanter centrifuge.
recovery from apple pomace has only become increasingly To optimize operating conditions systematically, the aqueous
attractive in recent years due to increased knowledge of biofunc- extracts were loaded onto a laboratory-scale column filled with
tional properties of polyphenols. Amberlite XAD 16 HP and washed with water; fractionated
For this purpose, and to improve the visual appearance of elution was performed with acidified ethanol, methanol, and
apple pectin, a process for the simultaneous recovery of phenolic 2-propanol, respectively, at 25 and 50 °C, revealing that the
compounds and pectins from apple pomace has been developed, pigments bound by the resin may be recovered almost quantita-
which is applicable on an industrial scale (125, 126). This process tively under optimal conditions. To demonstrate the applicability
requires extraction of the dried apple pomace with diluted mineral of this process, the optimized process was scaled up to pilot scale.
acid, thereby recovering both pectins and phenolic compounds. Furthermore, a patent has been filed describing a novel process
Subsequently, the polyphenols are bound using a hydrophobic for the extraction, purification, and concentration of polyphenols
styrene divinylbenzene copolymerisate by applying the apple from whole grapes, seeds, and grape pomace. This process
pomace crude extract onto the adsorber column. After washing consists of hot water extraction mostly comprising the acidifica-
the column with deionized water to remove pectins quantitatively, tion of the extracts followed by neutralization to precipitate
Review J. Agric. Food Chem., Vol. 59, No. 1, 2011 39
polymers, such as proteins, polysaccharides, and other macro- soy protein extracts, soy molasses, or soy whey feed stream has
molecules. Subsequently, the clear extracts are concentrated and been developed (140). For this purpose, the respective tempera-
purified using trimethylolpropane trimethacrylate adsorbent res- ture was selected on the basis of the solubility of the isoflavones in
ins, such as Amberlite XAD-7HP, eluting the target compounds the soy feed stream. Subsequently, the heated solution was
with aqueous ethanol, methanol, or acetone (135). Numerous ultrafiltered or subjected to reverse osmosis to further concentrate
processes have also been reported combining sulfite-assisted extrac- the solutes. Finally, the permeate was used for further selective
tion of anthocyanins from food-processing byproducts with their enrichment of the isoflavones using an adsorbent resin, with the
selective purification using adsorbent resins. However, due to column being washed with water prior to the elution of isofla-
potential pseudoallergenic reactions after consumption caused by vones with aqueous alcohols and the drying of the eluates. Thus,
trace amounts of sulfite inevitably associated with such antho- the resulting dried product is obtained in a comparatively
cyanin preparations, the use of sulfite is increasingly avoided. straightforward and rapid process. This procedure allows one
Furthermore, anthocyanins of purple-fleshed potatoes are also to obtain storable products and to enrich certain isoflavone
highly interesting with regard to their potential application as fractions or individual isoflavones selectively, thus yielding prep-
natural colorants or coloring foodstuff (38), and early studies arations with neutral color and flavor. Accordingly, this approach
demonstrated the potential to recover these pigments by different helps to produce pharmacologically active preparations from soy
adsorbent resins. Anthocyanins can also be recovered from other whey, which are so far affected by unpleasant color and taste.
sources, such as mulberries, and the optimization of process Soybeans are not only interesting because of their isoflavones,
parameters for their industrial recovery using macroporous resins but also because of their carbohydrates, such as D-pinitol (D-3-O-
is reported in the literature (136). methyl-chiro-inositol) and the cyclitol D-chiro-inositol, showing
7.3.3.2. Vegetable Polyphenols. Vegetables may also serve efficacy in lowering blood glucose levels. Consequently, there is an
as a rich source of valuable plant phenolics, which can be increasing industrial demand for the recovery preferably of pure
recovered by adsorbent resins. As an example, various macro- pinitol by applying simple methods for the use as insulin substitutes
porous resins have been applied for optimizing the isolation of and food supplements. Thus, a simple two-step extraction proce-
luteolin, one of the main phenolic compounds of pigeon pea dure has been suggested comprising the maceration of soybean
(Cajanus cajan (L.) Millsp.) (137). Pigeon pea is cultivated not leaves with ethanol solutions and chloroform followed by an ion
only to produce animal feed and as valuable source of proteins exchange step applying the aqueous supernatants after centrifuga-
and vitamin B in Africa and India but also for medical purposes, tion to two columns filled with a strong cation and strong anion
such as the stabilization of menstruation or to treat dysentery. exchanger resin, respectively, which are connected in series. The
The leaves find application in Chinese folk medicine as an cyclitols may be finally eluted using water devoid of CO2. After
anthelminthic drug, to ease pain or arrest blood, which is due freeze-drying, a white, crystalline product was obtained, which can
to their antibiotic and anti-inflammatory properties, abirritation be rehydrated with deionized water. However, prior to its produc-
effects, and their potential to lower capillary permeability. Luteolin tion on industrial scale, the safety of the product with respect to
has been associated, for example, with antiallergenic, antioxidant, human consumption still needs to be demonstrated (141).
antiproliferative and anti-inflammatory properties as well as
cytotoxicity toward certain cancer cells, thus rendering its recov- 8. CONCLUSIONS
ery, for example, from pigeon pea highly interesting. In summary, the broad range of applications of ion exchange
A further application of adsorbent technology was reported by and adsorbent resins in food production and for the cost-efficient
Aehle et al. (138), who developed a natural antioxidant prepara- valorization of food processing byproducts demonstrates the high
tion enriched in phenolic compounds from aqueous spinach potential of these technologies for the food, pharmaceutical, and
extracts because of the increasing commercial value of spinach cosmetics industries. Ion exchange and adsorber technology have
wastes. The results revealed higher antioxidant recovery rates been significantly improved in recent years and decades, not only
with synthetic adsorbent resins as compared to charcoal, and in with regard to process optimization during the sorption and
this regard, macroporous polystyrene cross-linked polymers desorption step but also with regard to the development of highly
appeared to be better suited than macroreticular aliphatic acrylic sophisticated resin materials allowing novel applications. In
cross-linked polymers for the selective enrichment of spinach contrast to many other extraction methods, adsorption and ion
antioxidants. exchange technology offers higher selectivity and improved cost
Also, the cell wall matrix of fruit and vegetable byproducts may efficiency and can be realized with relatively simple technical
also still be exploited to recover phenolic antioxidants. Ferulic equipment. However, the prediction of sorption and ion exchange
acid can be obtained upon alkaline hydrolysis of polysaccharides, behavior, when multicompound solute systems are considered, is
such as arabinogalactans and xyloglucans, which are covalently highly complex and should not be underestimated upon optimi-
bound to the hydroxycinnamate. The subsequent purification of zation of such processes. Nevertheless, with a steady increase in
the alkaline hydrolysate to yield the phenolic acid is possible by knowledge of the underlying theory, processes will increasingly be
using a combination of activated charcoal and a strongly basic tailored, thus yielding products with well-desired compositions
anion exchanger (139). Feedstocks such as sugar cane bagasse, and functional properties, which will certainly expand the appli-
sugar beet pulp, and wheat or grain bran could be used for that cation of these technologies to further areas in the future.
particular purpose.
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