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Science in China Series B: Chemistry www.scichina.


Preparation of magnetic chitosan microspheres and its

applications in wastewater treatment
YANG Hu1†, YUAN Bo1, LU YaoBo1 & CHENG RongShi1,2
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;
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-

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

serious day by day, on the other hand, the higher quality of water treatment, natural polymers have also shown
of water has been demanded with increasingly stringent excellent performances for distributing abundant free
environmental quality standards. In the view of the hydroxyl, amino and other active functional groups on
characteristics of current water pollution, the quantities the chain backbone, and natural polymer materials have
of soluble organic compounds and non-biodegradable already been believed to be one of the best substitutes
matters increased rapidly in water, but, the conventional applied in water treatment[8,9].
technologies of wastewater treatment were not efficient Chitosan, poly-β-(1→4)-2-amino-2-deoxy-D-glucose,
for removal of these impurities. Furthermore, some toxic was one of the high-performance polysaccharide materi-
residue in water may be produced by many currently als, which was prepared from deacetylation of natural
used reagents for water treatment, which were very dis- chitin, and chitin was the second most abundant natural
advantageous for the human health and environment. polymers in the world. In addition, chitosan has many
Therefore, it was one of the hottest research projects in prominent characteristics such as low toxicity and high
the field of the wastewater treatment to search the new biocompatibility, so it has been already widely applied
technologies with the characteristics of high efficiency, in many fields. Furthermore, chitosan presented abun-
low cost and nontoxicity [1,2]. dant free amino groups along the chain backbone that
Natural polymer materials, coming from animals, were cationically charged in a wide range of physio-
plants, microorganisms and so on, were a kind of re- logical pH, and showed prominent flocculating effect.
sources abundant in nature, which, after being disused, On the other hand, chitosan still bears excellent chelat-
were facile to degrade into water, carbon dioxide and so
on, and they were believed to be nontoxic and environ- Received April 8, 2008; accepted May 22, 2008; published online November 6, 2008
doi: 10.1007/s11426-008-0109-1
ment-friendly materials. Furthermore, what is most im- †
Corresponding author (email:
portant was that natural polymers were also a kind of 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

biomedicine[13 16], and only a little work has been

ing effect on the abundant free — OH and — NH2
groups, and could carry out efficiently removal of metal reported in wastewater treatment. In this article, applica-
ions, humic acids and synthetical surfactants for forma- tions of MCM in the wastewater treatment, based on
tion of complex precipitation. In addition, chitosan could different kinds of wastewater, such as metal ions, and
be also used as adsorbent to absorb impurities from the dye wastewater, have been reviewed, and the methods of
water. Therefore, it was believed that chitosan was very preparation of MCM have been also summarized care-
useful and powerful in the field of wastewater treatment fully.
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]
Figure 1 The SEM image of chitosan-Fe3O4 magnetic microspheres.
since the magnetic forces were much greater than
gravitation. In addition, MST have been applied in the
wastewater treatment, still bearing the characteristics of
2 Preparation of magnetic chitosan mi-
large-capacity, high-efficiency, small scale, and so on.
However, most materials including chitosan had no crospheres
magnetism. It was obvious that the magnetism should be As known, chitosan was a kind of natural organic poly-
endued to those nonmagnetic materials by some tech- mer materials, and usually immiscible with inorganic
niques, otherwise, MST did not work. Formation of matters. Therefore, it was difficult to disperse the inor-
the composites of the magnetic-nonmagnetic materials ganic magnetic particles into organic polymers homo-
was the usual method, having the so-called core- geneously for preparation of the high-performance inor-
shell microsphere structure: magnetic matters, such as ganic-organic composites. In addition, the structure of
Fe and Fe 3 O 4 as core, nonmagnetic materials as chitosan chain was stiff, and chitosan could dissolve in
shell [10,11] . As for chitosan, combination of chitosan very few solvents, usually only in acidic aqueous media.
and the magnetic matters, the complexes of magnetic Based on these characteristics of chitosan, two methods
chitosan microspheres (MCM) could be prepared, and a for preparation of MCM have been summarized: re-
typical SEM image of MCM: chitosan-Fe3O4 magnetic verse-phase suspension cross-linking method[17 21], and

microspheres, has been showed in Figure 1[12]. Besides

precipitation method[22 26].

the above mentioned effects, chitosan still had the func-

tion of magnetic separation. Since MCM could be sepa- 2.1 Reverse-phase suspension cross-linking method
rated and reclaimed easily by magnetic separation, after (RPSCLM)[17-21]
being desorbed, MCM could be used repeatedly. On the For RPSCLM, firstly, a stock solution of chitosan was
other hand, some of the precious impurities were recov- freshly prepared by dissolving in acidic aqueous solution.
ered also, which made MCM have much higher prac- Secondly, magnetic particles have been dispersed into
ticability in wastewater treatment. However, as for the the chitosan solution; then, the organic solvent, such as
current study of the MCM, researchers mainly focused paraffin, was added into the mixture to form a wa-
on the application in the field of biotechnology and ter-in-oil reverse-phase suspension; at last, the micro-

250 YANG Hu et al. Sci China Ser B-Chem | Mar. 2009 | vol. 52 | no. 3 | 249-256
spheres have been chemically cross-linked usually by the microspheres was not fine, so the concentration
formaldehyde and glutaraldehyde. of the chitosan should be selected in an appropriate
As previously mentioned, the bad miscibility between range.
inorganic and organic compounds made it quite difficult 2.2 Precipitation method (PM)[22-26]
to disperse the magnetic particles into the polymer solu-
Another method for preparation of MCM was precipita-
tion homogeneously. For mixing well the two immis-
tion method developed based on the special solubility
cible compounds, two popular methods have been ap-
characteristics of chitosan: dissolved in acidic aqueous
plied: one was to add the inorganic particles into the
media but precipitated in alkali one. In a definite condi-
prepared polymer solution directly, and the magnetic
tion, regular microspheres would be formed by adding
particles were dispersed by physical methods such as
chitosan solution dropwise to alkali aqueous solution.
ultrasonic treatment and mechanical stirring; the other
The detailed preparing processes of PM for MCM could
was to disperse and stabilize the magnetic particles in
be concluded in two routes: one was to disperse the
the aqueous solution by emulsification firstly, then, the
magnetic particles into the chitosan solution homogene-
above prepared magnetic fluid was added into polymer
ously by the similar methods as mentioned in previous
solution for mixing. For getting high magnetic quality
part firstly, then the mixture was added dropwise to al-
for the MCM, the magnetic particle/chitosan mass ratio
kali aqueous solution by syringe or other tools; and the
was a key parameter. Ding et al.[17] indicated that the other was to mix the pre-materials for preparation of
chitosan-Fe3O4 magnetic microspheres would have effi- magnetic particles with the chitosan solution firstly, then
cient effect of magnetic separation, when the Fe3O4/ the MCM was prepared by coprecipitation in alkali
chitosan mass ratio was higher than 9.05%. aqueous solution only in one step. For example, the
The properties of MCM prepared by RPSCLM, such mixture of ferrous and ferric compounds at an appropri-
as the size/size distribution, and magnetic quality, have ate molar ratio was usually used as pre-materials for
been greatly affected by the different experimental pa- preparation of magnetic materials of Fe3O4, and the
rameters, such as the magnetic particle/chitosan mass magnetic particles of Fe3O4 have been in-situ synthe-
ratio, concentration of chitosan, reaction time, stirring sized with the formation of chitosan microspheres by
rate, and the water/oil ratio. Denkbas et al.[18] found that coprecipitation of the aqueous mixture of chitosan and
the size of the MCM by RPSCLM decreased with ferrous/ferric compounds in alkali aqueous solution. At
increasing Fe 3 O 4 contents, implying that dispersion last, the microspheres have been chemically cross-linked
of chitosan solution into microspheres was more diffi- as usual.
cult when the Fe3O4/chitosan mass ratio increased. They Park et al.[22] dispersed the barium ferrite into chito-
also believed that the stirring rate of the suspension me- san solutions with different weight ratios by ultrasonica-
dium was another effective parameter for the properties tion, then the mixtures were added dropwise to NaOH
of the microspheres. With the stirring rate increase, the aqueous solutions with syringe respectively, and the
size of microspheres decreased, which was ascribed to MCM with different components have been prepared.
the increase of the energy transferred to the suspension They found that the sizes of the microspheres increased
medium, and made the polymer solution be dispersed with the content of chitosan increase. In addition, An et
into smaller droplets and size was reduced. In addition, al.[23] prepared the MCM using the similar method to
they found that the molecular weight of chitosan had no Park’s, they did not disperse the magnetic particles into
significant effect on the properties of MCM in their the chitosan solution, but into the NaOH solution, when
given molecular weigh range. Jiang et al.[19] indicated the chitosan solution was added dropwise into the NaOH
that the concentration of chitosan was also very impor- solution containing magnetic particles, the MCM would
tant for the formation of microspheres. If the concentra- be formed by enwrapping the dispersed magnetic parti-
tion of chitosan was high, the viscosity of polymer solu- cles in the precipitator during the conglobation of chito-
tion was increased, which made it difficult for the mag- san.
netic particles to be dispersed efficiently, and the size Yang et al.[24] prepared the MCM by coprecipitation
of the microspheres also increased. On the other hand, method. They mixed the ferrite aqueous solution con-
if the concentration of chitosan was low, the shape of taining ferrous sulfate hepta-hydrate (FeSO4·7H2O) and

YANG Hu et al. Sci China Ser B-Chem | Mar. 2009 | vol. 52 | no. 3 | 249-256 251
ferric chloride hexa-hydrate (FeCl3·6H2O) at a stoic- chain backbone, the metal ions were adsorbed and effi-
hiometric ratio of 1:2, with equal volume of chitosan ciently removed by chelating mechanism.
solution firstly, then the mixture was titrated with drops Rorrer et al.[28] prepared two kinds of multi-porous
of ammonium hydroxide to pH of around 10-11 to MCM with diameters of 1 and 3 mm respectively by PM,
formation of MCM by coprecipitation. In addition, Dong and studied the adsorption behavior of Cd2+ in aqueous
et al.[25] prepared the MCM by combination of the above solution. They indicated that both the size and the po-
mentioned two methods: RPSCLM and PM. They pre- rous structure of the MCM had a profound effect on the
pared the chitosan microspheres by RPSCLM firstly, adsorption capacity. At an initial concentration of 1690
then the microspheres were soaked in the aqueous solu- mg Cd2+/L, the smaller sized MCM with diameter of 1
tion of the ferrous and ferric aqueous mixture, after mm had both a faster adsorption rate and a larger equi-
reaching the adsorption equilibrium, the adsorbed mi- librium adsorption capacity than that with diameter of 3
crospheres have been transferred into alkali aqueous mm, due to the higher specific surface area of the
solution, and the magnetic particles would be in-situ smaller sized MCM. They also found that the metal ions
formed in the chitosan microspheres. Furthermore, Kim could not completely penetrate the microspheres and
et al.[26] tried spray-coprecipitation method for prepara- were preferentially adsorbed on the surface of the mi-
tion of the MCM. crospheres, and the behavior of adsorption isotherms
In comparison with the RPSCLM and PM for prepa- followed the monomolecular mechanism. Han et al.[29]
ration of MCM, the size of microspheres was controlled prepared the MCM by RPSCLM, and investigated the
adsorption behavior of Cu2+and Pb2+ respectively. They
more easily by RPSCLM, and in definite conditions, the
found that at lower initial concentrations of Cu2+and
microspheres, with different sizes from nanometer to
Pb2+, 98% metal ions could be both efficiently removed,
micron, could be prepared respectively. As for PM, the
and after being regenerated and used repeatedly, MCM
size of the MCM by PM was usually bigger, and the
still kept high equilibrium adsorption capacity. Li et
specific surface areas of the microspheres were usually
al.[30] further studied the adsorption behavior of MCM
lower than those prepared by RPSCLM, but, the tech-
for the rare earth metal ions such as La3+, Nd3+, Eu3+,
nology of PM was quite simple, and facile to be carried
Lu3+, and Pr3+. They found that the adsorption capacity
out especially in post-treatment. On the other hand, in
of MCM was much higher than that of chitosan particles
order to improve the performances of MCM further, re-
itself, and pH was a key parameter to the adsorption ca-
searchers began to seek new techniques to prepare the
pacity, in the weak acidic or neutral conditions, MCM
complexes microspheres of chitosan with other func-
showed a larger equilibrium adsorption capacity, the
tional materials. For example, Ding et al.[27] in-situ syn-
data of kinetic adsorption process obeyed the Langmuir
thesized the complexes magnetic microspheres of chito-
san-polyacrylicacid by self-assembly technique. Chemi-
For improvement of the adsorption capacity, and in
cal modification was also a good way to improve the
consideration of the chelation mechanism by —OH and
performances of the microspheres based on the applica-
—NH2 active groups on the chitosan chains, chemical
tions of MCM in different fields. And the chemical
modification for MCM would be introduced in detail in modification has been applied to MCM by grafting or
the next part combination of its real applications in the blending some compounds containing more or new ac-
wastewater treatment. tive functional groups to the microspheres. Chang
et al.[31] treated chitosan by carboxylation to prepare the
3 Application of MCM in wastewater tr- 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-
3.1 Treatment of wastewater containing metal boxymethyl MCM showed a faster adsorption rate, and
ions the largest equilibrium adsorption capacity appeared at
MCM have been already applied into the treatment of pH 5.5. Zhou et al.[32] applied similar method to prepare
wastewater containing metal ions. Since there are abun- the MCM by carboxymethyl chitosan with diameter of
dant free hydroxyl and amino groups distributing on the 18 nm, and found a good adsorption effect on Zn2+ from

252 YANG Hu et al. Sci China Ser B-Chem | Mar. 2009 | vol. 52 | no. 3 | 249-256
aqueous solution. showed great adsorption capacity. The experimental data
In addition, Zhou et al.[33,34] grafted ethylenediamine indicated that the MCM, after being used repeatedly 3
on the chitosan, applied the ethylenediamine-modified times, kept the efficacy with removal of 95.8% of
MCM to purifying the wastewater containing Hg2+, methyl orange. Undoubtedly, MCM exhibited a good
UO2+, Cd2+ and Ni2+ respectively. The experimental re- application foreground in treatment of dye wastewater.
sults showed that the modified MCM exhibited larger In addition, Han et al.[42] also carried out the similar ex-
adsorption capacity than original MCM. Donia et al.[35, 36] periments by Hong[41], and drew the same conclusions.
modified the chitosan resin with magnetic properties by Researchers also applied chemical modification to
the reaction between chitosan and polymeric Schiff 's improve the performances of MCM in treatment of dye
base of thiourea/glutaraldehyde. They applied it to the wastewater. Safarik [43] prepared a modified MCM,
recovery of Au3+ and Ag+ from the aqueous solution and bearing covalently immobilized copper phthalocyanine
the selective separation of Hg2 respectively.

dye on MCM, which was used selectively for removal of
3.2 Treatment of dye wastewater[41-44] polycyclic dyes from aqueous solutions and suspensions,
such as congo red, and crystal violet. These polycyclic
MCM could also be applied to the treatment of dye
dyes would be facile to form the face-to-face structures
wastewater. With the development of national economy,
with the copper phthalocyanine dye grafted on the MCM,
Department of National Environmental Protection set up
therefore, the binding of polycyclic dyes occurred be-
more rigid criterions of the treatment of dye wastewater.
cause of a chemical equilibrated and saturatable mecha-
The key problem for treatment of dye wastewater was
nism, following the Langmuir adsorption model. Chang
how to efficiently reduce the high chroma and the value
et al.[44] used carboxymethyl chitosan to prepare an ani-
of chemical oxygen demand (COD). Conventional
onic nano-sized MCM, and studied the adsorption be-
method for treatment of dye wastewater was combina-
havior of crocein orange G(AO12) and acid green
tion of physico-chemical and biochemical methods. The
25(AG25). They found that the adsorption capacity of
active adsorbents could not only remove dye matters
both AO12 and AG25 decreased with increasing pH.
from aqueous solutions efficiently, but improve maneu-
The increase in the ionic strength decreased the adsorp-
verability by further biochemical method. However, as
tion capacity of AG25 but did not affect that of AO12.
for traditional used adsorbents, such as active-carbon
From the adsorption kinetics and thermodynamics stud-
and active-diatomite, although they had good adsorption
ies, it was found that both the adsorption processes of
capacity, it was very difficult to be reclaimed for regen-
AO12 and AG25 obeyed Langmuir isotherm, and might
eration, therefore, the cost of those adsorbents was high.
be surface-reaction-controlled. In comparison with mi-
Chitosan, with abundant active functional groups on the
cro-sized MCM, nano-sized MCM exhibited a faster
chain backbone, also showed excellent adsorption ca-
adsorption rate and larger adsorption capacity for higher
pacity for dye matters. After being magnetized, MCM
specific surface area. They also indicated that both
had good effect of magnetic separation, and was facile
AO12 and AG25 could be desorbed from the MCM in
to be reclaimed and regenerated.
the aqueous mixture of NaCl and NaOH, and MCM
Hong et al.[41] investigated the application of MCM in
could be regenerated conveniently.
treatment of dye wastewater containing methyl orange.
They found that MCM exhibited excellent de-color ef- 3.3 Applications in treatment of other wastewa-
fect, especial at acidic aqueous media and at pH 3, ter[45-49]
showed largest adsorption capacity for methyl orange, Besides the metal ions and dye wastewater, people have
which was nearly three times larger than that at pH 7. also tried to apply MCM to treating other wastewater,
Furthermore, in comparison with active carbon, MCM such as phenolic, papermaking, fluoride and soy whey
had a faster adsorption rate: 99% of methyl orange could wastewater. MCM also exhibits good adsorption capac-
be removed within 30 min, but as for active carbon, it ity for those impurities.
took 8 h to remove 88% of dye matters only. After the Phenolic wastewater, usually yielding from oil refin-
adsorbed MCM being separated and collected from wa- ing, wood process, coking plant and so on, had much
ter by magnetic field, it could be regenerated by soaking more wide and harmful effects on the human health and
in NaCl aqueous solution, and the renewed MCM also environment, so it was very necessary to remove the

YANG Hu et al. Sci China Ser B-Chem | Mar. 2009 | vol. 52 | no. 3 | 249-256 253
phenolic matter from the water efficiently. Li et al.[45] In treatment of fluoride wastewater, MCM showed
prepared the MCM taking ZnFe2O4 as the magnetic core greater adsorption capacity than active-Al2O3. The major
by RPSCLM, and applied it to purifying the phenolic mechanism of fluoride adsorption onto the heterogene-
wastewater. The results indicated that 64% of phenolic ous surface of MCM was proposed by the present au-
matters could be removed by adsorption. The efficiency thors[48]. As for soy whey wastewater, MCM could ab-
was obviously better than other adsorbents. Furthermore, sorb the protein efficiently from soy whey wastewater,
MCM was facile to be reclaimed by magnetic separation, and under a definite condition, 95.6% of protein could
and regenerated. Ma et al.[46] immobilized an enzyme of be recovered[49]. In addition, the excellent separation and
HRP on the MCM. HRP was used in catalytic oxidizing regeneration effects have been exhibited in the treatment
phenolic compounds to phenol oxygen radical matters, of fluoride and soy whey wastewater.
which could be removed easily as precipitates by forma-
tion of high-molecular weight insoluble compounds. 4 Perspective
Based on the experimental results, the MCM immobi-
Above all, MCM exhibited not only the excellent char-
lizing HRP showed higher efficiency to remove phenolic
acteristics of chitosan itself, such as adsorption and che-
compounds from mixed phenolic wastewater. Further-
lating effects, low cost, and nontoxicity, but the effect of
more, the reaction activity of HRP immobilized on the
MCM was superior to that of HRP immobilized on the magnetic separation, whose peculiarities made MCM
non-magnetic chitosan microspheres and native HRP. have great application foreground in the field of waste-
Therefore, in comparison with the conventional tech- water treatment.
nologies, MCM exhibits more efficiently and exercisa- For improvement of MCM performances in waste-
bly for treatment of phenolic wastewater. water treatment, it is significative to modify the MCM
In addition, Zhu et al.[47] tried to purify the paper- further based on its applications in treatment of respec-
making wastewater by MCM. As known, the compo- tive impurities. Two mainly modifying routes are sum-
nents of papermaking wastewater were very complicated, marized: One is chemical modification to enhance the
usually containing suspension fibers, abundant organic MCM adsorption capacity by grafting more or new ac-
compounds, and so on. Meanwhile, the hydrophilic tive functional groups, especially some groups having
compounds in the papermaking wastewater would be selective adsorption to some compounds, or active en-
facile to form hydrogen bonding with water, which zyme, on the MCM. The other is to prepare nano-sized
made it very difficult to be separated from water. They and multi-porous MCM with high specific surface area
found that more than 85% of COD could be reduced by by physical chemistry method, since the adsorption of
MCM under nearly neutral condition, and the weight impurities usually took place on the surface of the mi-
ratio of used MCM to wastewater was only 1.4×10−3. crospheres, following the monomolecular adsorption
But, the capacity for removal of suspension fibers by mechanism.
MCM was not efficient, further work has to be carried In short, facing the complicated and stringent tenden-
out. cies of current water pollution, the new and environ-
Recently, researchers also applied MCM to treatment ment-friendly technologies for wastewater treatment are
of fluoride[48] and soy whey wastewater[49]. The experi- needed urgently. MCM due to the above-mentioned ex-
mental results indicated that MCM worked efficiently in cellent characteristics may be one of the useful tech-
the treatment of the fluoride and soy whey wastewater. nologies in this field.

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