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Preparation of magnetic chitosan microspheres and its

applications in wastewater treatment
YANG Hu1†, YUAN Bo1, LU YaoBo1 & CHENG RongShi1,2
1
Key Laboratory for Mesoscopic Chemistry of Ministry of Education, Department of Polymer Science and Technology, School of
Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China;
2
College of Material Science and Engineering, Polymer Institute, South China University of Technology, Guangzhou 510640, China

The methods of preparation of magnetic chitosan microspheres have been introduced. In addition, their
applications in the wastewater treatment, based on different kinds of wastewater, have been reviewed,
and their mechanisms have been discussed.

magnetic chitosan microspheres, preparation, applications in wastewater treatment

1 Introduction reproducible and inexhaustible materials fully inde-

Water is one of the most basic requirements for human
daily life. However, with rapid development of modern
industries, the problem of water pollution turned more
pendent of petroleum resources. Those peculiarities of
natural polymer materials have been already applied
widely into different fields such as biotechnology, bio-
medicine, food, and cosmetics[3 7]. However, in the field
－

serious day by day, on the other hand, the higher quality
of water has been demanded with increasingly stringent
environmental quality standards. In the view of the
characteristics of current water pollution, the quantities
of soluble organic compounds and non-biodegradable
matters increased rapidly in water, but, the conventional
technologies of wastewater treatment were not efficient
for removal of these impurities. Furthermore, some toxic
residue in water may be produced by many currently
used reagents for water treatment, which were very dis-
advantageous for the human health and environment.
Therefore, it was one of the hottest research projects in
the field of the wastewater treatment to search the new
technologies with the characteristics of high efficiency,
low cost and nontoxicity [1,2].
Natural polymer materials, coming from animals,
plants, microorganisms and so on, were a kind of re-
sources abundant in nature, which, after being disused,
were facile to degrade into water, carbon dioxide and so
on, and they were believed to be nontoxic and environ-
ment-friendly materials. Furthermore, what is most im-
portant was that natural polymers were also a kind of
of water treatment, natural polymers have also shown
excellent performances for distributing abundant free
hydroxyl, amino and other active functional groups on
the chain backbone, and natural polymer materials have
already been believed to be one of the best substitutes
applied in water treatment[8,9].
Chitosan, poly-β-(1→4)-2-amino-2-deoxy-D-glucose,
was one of the high-performance polysaccharide materi-
als, which was prepared from deacetylation of natural
chitin, and chitin was the second most abundant natural
polymers in the world. In addition, chitosan has many
prominent characteristics such as low toxicity and high
biocompatibility, so it has been already widely applied
in many fields. Furthermore, chitosan presented abun-
dant free amino groups along the chain backbone that
were cationically charged in a wide range of physio-
logical pH, and showed prominent flocculating effect.
On the other hand, chitosan still bears excellent chelat-
Received April 8, 2008; accepted May 22, 2008; published online November 6, 2008
doi: 10.1007/s11426-008-0109-1
†
Corresponding author (email: yanghu@nju.edu.cn)
Supported by the Key Natural Science Foundation of China (Grant No. 50633030)

Sci China Ser B-Chem | Mar. 2009 | vol. 52 | no. 3 | 249-256


ing effect on the abundant free — OH and — NH2
groups, and could carry out efficiently removal of metal
ions, humic acids and synthetical surfactants for forma-
tion of complex precipitation. In addition, chitosan could
be also used as adsorbent to absorb impurities from the
water. Therefore, it was believed that chitosan was very
useful and powerful in the field of wastewater treatment
because of its multifunction: flocculating, chelating and
adsorption effects[8,9].
However, in the real applications in the wastwater
treatment, chitosan itself also had some problems. When
used as adsorbents, sometimes it was quite difficult to be
separated from the water rapidly after adsorption of the
impurities. On the other hand, some of these impurities
were very precious, and need to be recovered. So it was
a great interesting work to seek techniques for
separation of the adsorbents from the water efficiently.
Recently, magnetic separation technologies (MST) have
been applied into the field of wastewater treatment, and
the magnetic matters could be separated from the water
rapidly and efficiently with the aid of magnetic force[1]
since the magnetic forces were much greater than
gravitation. In addition, MST have been applied in the
wastewater treatment, still bearing the characteristics of
large-capacity, high-efficiency, small scale, and so on.
However, most materials including chitosan had no
magnetism. It was obvious that the magnetism should be
endued to those nonmagnetic materials by some tech-
niques, otherwise, MST did not work. Formation of
the composites of the magnetic-nonmagnetic materials
was the usual method, having the so-called core-
shell microsphere structure: magnetic matters, such as
Fe and Fe 3 O 4 as core, nonmagnetic materials as
shell [10,11] . As for chitosan, combination of chitosan
and the magnetic matters, the complexes of magnetic
chitosan microspheres (MCM) could be prepared, and a
typical SEM image of MCM: chitosan-Fe3O4 magnetic
microspheres, has been showed in Figure 1[12]. Besides
the above mentioned effects, chitosan still had the func-
tion of magnetic separation. Since MCM could be sepa-
rated and reclaimed easily by magnetic separation, after
being desorbed, MCM could be used repeatedly. On the
other hand, some of the precious impurities were recov-
ered also, which made MCM have much higher prac-
ticability in wastewater treatment. However, as for the
current study of the MCM, researchers mainly focused
on the application in the field of biotechnology and
250 YANG Hu et al. Sci China Ser B-Chem | Mar. 2009 | vol. 52 | no. 3 | 249-256
biomedicine[13 16], and only a little work has been
－
reported in wastewater treatment. In this article, applica-
tions of MCM in the wastewater treatment, based on
different kinds of wastewater, such as metal ions, and
dye wastewater, have been reviewed, and the methods of
preparation of MCM have been also summarized care-
fully.
Figure 1 The SEM image of chitosan-Fe3O4 magnetic microspheres.
2 Preparation of magnetic chitosan mi-
crospheres
As known, chitosan was a kind of natural organic poly-
mer materials, and usually immiscible with inorganic
matters. Therefore, it was difficult to disperse the inor-
ganic magnetic particles into organic polymers homo-
geneously for preparation of the high-performance inor-
ganic-organic composites. In addition, the structure of
chitosan chain was stiff, and chitosan could dissolve in
very few solvents, usually only in acidic aqueous media.
Based on these characteristics of chitosan, two methods
for preparation of MCM have been summarized: re-
verse-phase suspension cross-linking method[17 21], and
－
precipitation method[22 26].
－
2.1 Reverse-phase suspension cross-linking method
(RPSCLM)[17－21]
For RPSCLM, firstly, a stock solution of chitosan was
freshly prepared by dissolving in acidic aqueous solution.
Secondly, magnetic particles have been dispersed into
the chitosan solution; then, the organic solvent, such as
paraffin, was added into the mixture to form a wa-
ter-in-oil reverse-phase suspension; at last, the micro-
spheres have been chemically cross-linked usually by
formaldehyde and glutaraldehyde.
As previously mentioned, the bad miscibility between
inorganic and organic compounds made it quite difficult
to disperse the magnetic particles into the polymer solu-
tion homogeneously. For mixing well the two immis-
cible compounds, two popular methods have been ap-
plied: one was to add the inorganic particles into the
prepared polymer solution directly, and the magnetic
particles were dispersed by physical methods such as
ultrasonic treatment and mechanical stirring; the other
was to disperse and stabilize the magnetic particles in
the aqueous solution by emulsification firstly, then, the
above prepared magnetic fluid was added into polymer
solution for mixing. For getting high magnetic quality
for the MCM, the magnetic particle/chitosan mass ratio
was a key parameter. Ding et al.[17] indicated that the
chitosan-Fe3O4 magnetic microspheres would have effi-
cient effect of magnetic separation, when the Fe3O4/
chitosan mass ratio was higher than 9.05%.
The properties of MCM prepared by RPSCLM, such
as the size/size distribution, and magnetic quality, have
been greatly affected by the different experimental pa-
rameters, such as the magnetic particle/chitosan mass
ratio, concentration of chitosan, reaction time, stirring
rate, and the water/oil ratio. Denkbas et al.[18] found that
the size of the MCM by RPSCLM decreased with
increasing Fe 3 O 4 contents, implying that dispersion
of chitosan solution into microspheres was more diffi-
cult when the Fe3O4/chitosan mass ratio increased. They
also believed that the stirring rate of the suspension me-
dium was another effective parameter for the properties
of the microspheres. With the stirring rate increase, the
size of microspheres decreased, which was ascribed to
the increase of the energy transferred to the suspension
medium, and made the polymer solution be dispersed
into smaller droplets and size was reduced. In addition,
they found that the molecular weight of chitosan had no
significant effect on the properties of MCM in their
given molecular weigh range. Jiang et al.[19] indicated
that the concentration of chitosan was also very impor-
tant for the formation of microspheres. If the concentra-
tion of chitosan was high, the viscosity of polymer solu-
tion was increased, which made it difficult for the mag-
netic particles to be dispersed efficiently, and the size
of the microspheres also increased. On the other hand,
if the concentration of chitosan was low, the shape of
YANG Hu et al. Sci China Ser B-Chem | Mar. 2009 | vol. 52 | no. 3 | 249-256
the microspheres was not fine, so the concentration
of the chitosan should be selected in an appropriate
range.
2.2 Precipitation method (PM)[22－26]
Another method for preparation of MCM was precipita-
tion method developed based on the special solubility
characteristics of chitosan: dissolved in acidic aqueous
media but precipitated in alkali one. In a definite condi-
tion, regular microspheres would be formed by adding
chitosan solution dropwise to alkali aqueous solution.
The detailed preparing processes of PM for MCM could
be concluded in two routes: one was to disperse the
magnetic particles into the chitosan solution homogene-
ously by the similar methods as mentioned in previous
part firstly, then the mixture was added dropwise to al-
kali aqueous solution by syringe or other tools; and the
other was to mix the pre-materials for preparation of
magnetic particles with the chitosan solution firstly, then
the MCM was prepared by coprecipitation in alkali
aqueous solution only in one step. For example, the
mixture of ferrous and ferric compounds at an appropri-
ate molar ratio was usually used as pre-materials for
preparation of magnetic materials of Fe3O4, and the
magnetic particles of Fe3O4 have been in-situ synthe-
sized with the formation of chitosan microspheres by
coprecipitation of the aqueous mixture of chitosan and
ferrous/ferric compounds in alkali aqueous solution. At
last, the microspheres have been chemically cross-linked
as usual.
Park et al.[22] dispersed the barium ferrite into chito-
san solutions with different weight ratios by ultrasonica-
tion, then the mixtures were added dropwise to NaOH
aqueous solutions with syringe respectively, and the
MCM with different components have been prepared.
They found that the sizes of the microspheres increased
with the content of chitosan increase. In addition, An et
al.[23] prepared the MCM using the similar method to
Park’s, they did not disperse the magnetic particles into
the chitosan solution, but into the NaOH solution, when
the chitosan solution was added dropwise into the NaOH
solution containing magnetic particles, the MCM would
be formed by enwrapping the dispersed magnetic parti-
cles in the precipitator during the conglobation of chito-
san.
Yang et al.[24] prepared the MCM by coprecipitation
method. They mixed the ferrite aqueous solution con-
taining ferrous sulfate hepta-hydrate (FeSO4·7H2O) and
251
ferric chloride hexa-hydrate (FeCl3·6H2O) at a stoic-
hiometric ratio of 1:2, with equal volume of chitosan
solution firstly, then the mixture was titrated with drops
of ammonium hydroxide to pH of around 10－11 to
formation of MCM by coprecipitation. In addition, Dong
et al.[25] prepared the MCM by combination of the above
mentioned two methods: RPSCLM and PM. They pre-
pared the chitosan microspheres by RPSCLM firstly,
then the microspheres were soaked in the aqueous solu-
tion of the ferrous and ferric aqueous mixture, after
reaching the adsorption equilibrium, the adsorbed mi-
crospheres have been transferred into alkali aqueous
solution, and the magnetic particles would be in-situ
formed in the chitosan microspheres. Furthermore, Kim
et al.[26] tried spray-coprecipitation method for prepara-
tion of the MCM.
In comparison with the RPSCLM and PM for prepa-
ration of MCM, the size of microspheres was controlled
more easily by RPSCLM, and in definite conditions, the
microspheres, with different sizes from nanometer to
micron, could be prepared respectively. As for PM, the
size of the MCM by PM was usually bigger, and the
specific surface areas of the microspheres were usually
lower than those prepared by RPSCLM, but, the tech-
nology of PM was quite simple, and facile to be carried
out especially in post-treatment. On the other hand, in
order to improve the performances of MCM further, re-
searchers began to seek new techniques to prepare the
complexes microspheres of chitosan with other func-
tional materials. For example, Ding et al.[27] in-situ syn-
thesized the complexes magnetic microspheres of chito-
san-polyacrylicacid by self-assembly technique. Chemi-
cal modification was also a good way to improve the
performances of the microspheres based on the applica-
tions of MCM in different fields. And the chemical
modification for MCM would be introduced in detail in
the next part combination of its real applications in the
wastewater treatment.
3 Application of MCM in wastewater tr-
eatment
3.1 Treatment of wastewater containing metal
[28－40]
ions
MCM have been already applied into the treatment of
wastewater containing metal ions. Since there are abun-
dant free hydroxyl and amino groups distributing on the
252 YANG Hu et al. Sci China Ser B-Chem | Mar. 2009 | vol. 52 | no. 3 | 249-256
chain backbone, the metal ions were adsorbed and effi-
ciently removed by chelating mechanism.
Rorrer et al.[28] prepared two kinds of multi-porous
MCM with diameters of 1 and 3 mm respectively by PM,
and studied the adsorption behavior of Cd2+ in aqueous
solution. They indicated that both the size and the po-
rous structure of the MCM had a profound effect on the
adsorption capacity. At an initial concentration of 1690
mg Cd2+/L, the smaller sized MCM with diameter of 1
mm had both a faster adsorption rate and a larger equi-
librium adsorption capacity than that with diameter of 3
mm, due to the higher specific surface area of the
smaller sized MCM. They also found that the metal ions
could not completely penetrate the microspheres and
were preferentially adsorbed on the surface of the mi-
crospheres, and the behavior of adsorption isotherms
followed the monomolecular mechanism. Han et al.[29]
prepared the MCM by RPSCLM, and investigated the
adsorption behavior of Cu2+and Pb2+ respectively. They
found that at lower initial concentrations of Cu2+and
Pb2+, 98% metal ions could be both efficiently removed,
and after being regenerated and used repeatedly, MCM
still kept high equilibrium adsorption capacity. Li et
al.[30] further studied the adsorption behavior of MCM
for the rare earth metal ions such as La3+, Nd3+, Eu3+,
Lu3+, and Pr3+. They found that the adsorption capacity
of MCM was much higher than that of chitosan particles
itself, and pH was a key parameter to the adsorption ca-
pacity, in the weak acidic or neutral conditions, MCM
showed a larger equilibrium adsorption capacity, the
data of kinetic adsorption process obeyed the Langmuir
equation.
For improvement of the adsorption capacity, and in
consideration of the chelation mechanism by —OH and
—NH2 active groups on the chitosan chains, chemical
modification has been applied to MCM by grafting or
blending some compounds containing more or new ac-
tive functional groups to the microspheres. Chang
et al.[31] treated chitosan by carboxylation to prepare the
MCM of 13.5 nm. The adsorption behavior of the re-
sulting MCM to Co2+ was studied. They found that at
pH 3－7 and temperature of around 20－45℃, car-
boxymethyl MCM showed a faster adsorption rate, and
the largest equilibrium adsorption capacity appeared at
pH 5.5. Zhou et al.[32] applied similar method to prepare
the MCM by carboxymethyl chitosan with diameter of
18 nm, and found a good adsorption effect on Zn2+ from
aqueous solution.
In addition, Zhou et al.[33,34] grafted ethylenediamine
on the chitosan, applied the ethylenediamine-modified
MCM to purifying the wastewater containing Hg2+,
UO2+, Cd2+ and Ni2+ respectively. The experimental re-
sults showed that the modified MCM exhibited larger
adsorption capacity than original MCM. Donia et al.[35, 36]
modified the chitosan resin with magnetic properties by
the reaction between chitosan and polymeric Schiff 's
base of thiourea/glutaraldehyde. They applied it to the
recovery of Au3+ and Ag+ from the aqueous solution and
the selective separation of Hg2 respectively.
＋
3.2 Treatment of dye wastewater[41－44]
MCM could also be applied to the treatment of dye
wastewater. With the development of national economy,
Department of National Environmental Protection set up
more rigid criterions of the treatment of dye wastewater.
The key problem for treatment of dye wastewater was
how to efficiently reduce the high chroma and the value
of chemical oxygen demand (COD). Conventional
method for treatment of dye wastewater was combina-
tion of physico-chemical and biochemical methods. The
active adsorbents could not only remove dye matters
from aqueous solutions efficiently, but improve maneu-
verability by further biochemical method. However, as
for traditional used adsorbents, such as active-carbon
and active-diatomite, although they had good adsorption
capacity, it was very difficult to be reclaimed for regen-
eration, therefore, the cost of those adsorbents was high.
Chitosan, with abundant active functional groups on the
chain backbone, also showed excellent adsorption ca-
pacity for dye matters. After being magnetized, MCM
had good effect of magnetic separation, and was facile
to be reclaimed and regenerated.
Hong et al.[41] investigated the application of MCM in
treatment of dye wastewater containing methyl orange.
They found that MCM exhibited excellent de-color ef-
fect, especial at acidic aqueous media and at pH 3,
showed largest adsorption capacity for methyl orange,
which was nearly three times larger than that at pH 7.
Furthermore, in comparison with active carbon, MCM
had a faster adsorption rate: 99% of methyl orange could
be removed within 30 min, but as for active carbon, it
took 8 h to remove 88% of dye matters only. After the
adsorbed MCM being separated and collected from wa-
ter by magnetic field, it could be regenerated by soaking
in NaCl aqueous solution, and the renewed MCM also
YANG Hu et al. Sci China Ser B-Chem | Mar. 2009 | vol. 52 | no. 3 | 249-256
showed great adsorption capacity. The experimental data
indicated that the MCM, after being used repeatedly 3
times, kept the efficacy with removal of 95.8% of
methyl orange. Undoubtedly, MCM exhibited a good
application foreground in treatment of dye wastewater.
In addition, Han et al.[42] also carried out the similar ex-
periments by Hong[41], and drew the same conclusions.
Researchers also applied chemical modification to
improve the performances of MCM in treatment of dye
wastewater. Safarik [43] prepared a modified MCM,
bearing covalently immobilized copper phthalocyanine
dye on MCM, which was used selectively for removal of
polycyclic dyes from aqueous solutions and suspensions,
such as congo red, and crystal violet. These polycyclic
dyes would be facile to form the face-to-face structures
with the copper phthalocyanine dye grafted on the MCM,
therefore, the binding of polycyclic dyes occurred be-
cause of a chemical equilibrated and saturatable mecha-
nism, following the Langmuir adsorption model. Chang
et al.[44] used carboxymethyl chitosan to prepare an ani-
onic nano-sized MCM, and studied the adsorption be-
havior of crocein orange G(AO12) and acid green
25(AG25). They found that the adsorption capacity of
both AO12 and AG25 decreased with increasing pH.
The increase in the ionic strength decreased the adsorp-
tion capacity of AG25 but did not affect that of AO12.
From the adsorption kinetics and thermodynamics stud-
ies, it was found that both the adsorption processes of
AO12 and AG25 obeyed Langmuir isotherm, and might
be surface-reaction-controlled. In comparison with mi-
cro-sized MCM, nano-sized MCM exhibited a faster
adsorption rate and larger adsorption capacity for higher
specific surface area. They also indicated that both
AO12 and AG25 could be desorbed from the MCM in
the aqueous mixture of NaCl and NaOH, and MCM
could be regenerated conveniently.
3.3 Applications in treatment of other wastewa-
ter[45－49]
Besides the metal ions and dye wastewater, people have
also tried to apply MCM to treating other wastewater,
such as phenolic, papermaking, fluoride and soy whey
wastewater. MCM also exhibits good adsorption capac-
ity for those impurities.
Phenolic wastewater, usually yielding from oil refin-
ing, wood process, coking plant and so on, had much
more wide and harmful effects on the human health and
environment, so it was very necessary to remove the
253
phenolic matter from the water efficiently. Li et al.[45]
prepared the MCM taking ZnFe2O4 as the magnetic core
by RPSCLM, and applied it to purifying the phenolic
wastewater. The results indicated that 64% of phenolic
matters could be removed by adsorption. The efficiency
was obviously better than other adsorbents. Furthermore,
MCM was facile to be reclaimed by magnetic separation,
and regenerated. Ma et al.[46] immobilized an enzyme of
HRP on the MCM. HRP was used in catalytic oxidizing
phenolic compounds to phenol oxygen radical matters,
which could be removed easily as precipitates by forma-
tion of high-molecular weight insoluble compounds.
Based on the experimental results, the MCM immobi-
lizing HRP showed higher efficiency to remove phenolic
compounds from mixed phenolic wastewater. Further-
more, the reaction activity of HRP immobilized on the
MCM was superior to that of HRP immobilized on the
non-magnetic chitosan microspheres and native HRP.
Therefore, in comparison with the conventional tech-
nologies, MCM exhibits more efficiently and exercisa-
bly for treatment of phenolic wastewater.
In addition, Zhu et al.[47] tried to purify the paper-
making wastewater by MCM. As known, the compo-
nents of papermaking wastewater were very complicated,
usually containing suspension fibers, abundant organic
compounds, and so on. Meanwhile, the hydrophilic
compounds in the papermaking wastewater would be
facile to form hydrogen bonding with water, which
made it very difficult to be separated from water. They
found that more than 85% of COD could be reduced by
MCM under nearly neutral condition, and the weight
ratio of used MCM to wastewater was only 1.4×10−3.
But, the capacity for removal of suspension fibers by
MCM was not efficient, further work has to be carried
out.
Recently, researchers also applied MCM to treatment
of fluoride[48] and soy whey wastewater[49]. The experi-
mental results indicated that MCM worked efficiently in
the treatment of the fluoride and soy whey wastewater.
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In treatment of fluoride wastewater, MCM showed
greater adsorption capacity than active-Al2O3. The major
mechanism of fluoride adsorption onto the heterogene-
ous surface of MCM was proposed by the present au-
thors[48]. As for soy whey wastewater, MCM could ab-
sorb the protein efficiently from soy whey wastewater,
and under a definite condition, 95.6% of protein could
be recovered[49]. In addition, the excellent separation and
regeneration effects have been exhibited in the treatment
of fluoride and soy whey wastewater.
4 Perspective
Above all, MCM exhibited not only the excellent char-
acteristics of chitosan itself, such as adsorption and che-
lating effects, low cost, and nontoxicity, but the effect of
magnetic separation, whose peculiarities made MCM
have great application foreground in the field of waste-
water treatment.
For improvement of MCM performances in waste-
water treatment, it is significative to modify the MCM
further based on its applications in treatment of respec-
tive impurities. Two mainly modifying routes are sum-
marized: One is chemical modification to enhance the
MCM adsorption capacity by grafting more or new ac-
tive functional groups, especially some groups having
selective adsorption to some compounds, or active en-
zyme, on the MCM. The other is to prepare nano-sized
and multi-porous MCM with high specific surface area
by physical chemistry method, since the adsorption of
impurities usually took place on the surface of the mi-
crospheres, following the monomolecular adsorption
mechanism.
In short, facing the complicated and stringent tenden-
cies of current water pollution, the new and environ-
ment-friendly technologies for wastewater treatment are
needed urgently. MCM due to the above-mentioned ex-
cellent characteristics may be one of the useful tech-
nologies in this field.
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