Science in China Series B: Chemistry

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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
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 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 disadvantageous 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 resources 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 environment-friendly materials. Furthermore, what is most important was that natural polymers were also a kind of

reproducible and inexhaustible materials fully independent 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 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 materials, 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 abundant free amino groups along the chain backbone that were cationically charged in a wide range of physiological pH, and showed prominent flocculating effect. On the other hand, chitosan still bears excellent chelatReceived 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)

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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 formation 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 techniques, otherwise, MST did not work. Formation of the composites of the magnetic-nonmagnetic materials was the usual method, having the so-called coreshell 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 function of magnetic separation. Since MCM could be separated and reclaimed easily by magnetic separation, after being desorbed, MCM could be used repeatedly. On the other hand, some of the precious impurities were recovered also, which made MCM have much higher practicability in wastewater treatment. However, as for the current study of the MCM, researchers mainly focused on the application in the field of biotechnology and
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biomedicine[13 16], and only a little work has been reported in wastewater treatment. In this article, applications 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 carefully.

Figure 1

The SEM image of chitosan-Fe3O4 magnetic microspheres.

2 Preparation of magnetic chitosan microspheres
As known, chitosan was a kind of natural organic polymer materials, and usually immiscible with inorganic matters. Therefore, it was difficult to disperse the inorganic magnetic particles into organic polymers homogeneously for preparation of the high-performance inorganic-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 water-in-oil reverse-phase suspension; at last, the micro-

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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 solution homogeneously. For mixing well the two immiscible compounds, two popular methods have been applied: 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 efficient 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 parameters, 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 difficult when the Fe3O4/chitosan mass ratio increased. They also believed that the stirring rate of the suspension medium 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 important for the formation of microspheres. If the concentration of chitosan was high, the viscosity of polymer solution was increased, which made it difficult for the magnetic 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

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 precipitation method developed based on the special solubility characteristics of chitosan: dissolved in acidic aqueous media but precipitated in alkali one. In a definite condition, 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 homogeneously by the similar methods as mentioned in previous part firstly, then the mixture was added dropwise to alkali 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 appropriate 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 synthesized 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 chitosan solutions with different weight ratios by ultrasonication, 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 particles in the precipitator during the conglobation of chitosan. Yang et al.[24] prepared the MCM by coprecipitation method. They mixed the ferrite aqueous solution containing ferrous sulfate hepta-hydrate (FeSO4·7H2O) and
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ferric chloride hexa-hydrate (FeCl3·6H2O) at a stoichiometric 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 prepared the chitosan microspheres by RPSCLM firstly, then the microspheres were soaked in the aqueous solution of the ferrous and ferric aqueous mixture, after reaching the adsorption equilibrium, the adsorbed microspheres 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 preparation of the MCM. In comparison with the RPSCLM and PM for preparation 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 technology 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, researchers began to seek new techniques to prepare the complexes microspheres of chitosan with other functional materials. For example, Ding et al.[27] in-situ synthesized the complexes magnetic microspheres of chitosan-polyacrylicacid by self-assembly technique. Chemical modification was also a good way to improve the performances of the microspheres based on the applications 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.

chain backbone, the metal ions were adsorbed and efficiently 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 porous 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 equilibrium 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 microspheres, 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 capacity, 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 active 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 resulting MCM to Co2+ was studied. They found that at pH 3-7 and temperature of around 20-45℃, carboxymethyl 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

3 Application of MCM in wastewater treatment
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 abundant free hydroxyl and amino groups distributing on the
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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 results 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 combination of physico-chemical and biochemical methods. The active adsorbents could not only remove dye matters from aqueous solutions efficiently, but improve maneuverability 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 regeneration, therefore, the cost of those adsorbents was high. Chitosan, with abundant active functional groups on the chain backbone, also showed excellent adsorption capacity 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 effect, 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 water by magnetic field, it could be regenerated by soaking in NaCl aqueous solution, and the renewed MCM also

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 experiments 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 because of a chemical equilibrated and saturatable mechanism, following the Langmuir adsorption model. Chang et al.[44] used carboxymethyl chitosan to prepare an anionic nano-sized MCM, and studied the adsorption behavior 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 adsorption capacity of AG25 but did not affect that of AO12. From the adsorption kinetics and thermodynamics studies, it was found that both the adsorption processes of AO12 and AG25 obeyed Langmuir isotherm, and might be surface-reaction-controlled. In comparison with micro-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 wastewater[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 capacity for those impurities. Phenolic wastewater, usually yielding from oil refining, 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
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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 formation of high-molecular weight insoluble compounds. Based on the experimental results, the MCM immobilizing HRP showed higher efficiency to remove phenolic compounds from mixed phenolic wastewater. Furthermore, 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 technologies, MCM exhibits more efficiently and exercisably for treatment of phenolic wastewater. In addition, Zhu et al.[47] tried to purify the papermaking wastewater by MCM. As known, the components 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 experimental 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 heterogeneous surface of MCM was proposed by the present authors[48]. As for soy whey wastewater, MCM could absorb 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 characteristics of chitosan itself, such as adsorption and chelating effects, low cost, and nontoxicity, but the effect of magnetic separation, whose peculiarities made MCM have great application foreground in the field of wastewater treatment. For improvement of MCM performances in wastewater treatment, it is significative to modify the MCM further based on its applications in treatment of respective impurities. Two mainly modifying routes are summarized: One is chemical modification to enhance the MCM adsorption capacity by grafting more or new active functional groups, especially some groups having selective adsorption to some compounds, or active enzyme, 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 microspheres, following the monomolecular adsorption mechanism. In short, facing the complicated and stringent tendencies of current water pollution, the new and environment-friendly technologies for wastewater treatment are needed urgently. MCM due to the above-mentioned excellent characteristics may be one of the useful technologies in this field.
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