Abstract
Background, aim, and scope
Dye pollutants are a major class of environmental contaminants. Over 100,000 dyes have been synthesized worldwide and more than 700,000 tons are produced annually and over 5% are discharged into aquatic environments. The adsorption or sorption is one of the most efficient methods to remove dye and heavy metal pollutants from wastewater. However, most of the present sorbents often bear some disadvantages, e.g. low sorption capacity, difficult separation of spoil, complex reproduction, or secondary pollution. Development of novel sorbents that can overcome these limitations is desirable.
Materials and methods
On the basis of the chemical coprecipitation of calcium oxalate (CaC2O4), bromopyrogallol red (BPR) was embedded during the growing of CaC2O4 particles. The ternary C2O4 2––BPR–Ca2+ sorbent was yielded by the centrifugation. Its composition was determined by spectrophotometry and AAS, and its structure and morphology were characterized by powder X-ray diffraction (XRD), laser particle-size analysis, and scanning electron microscopy (SEM). The adsorption of ethyl violet (EV) and heavy metals, e.g. Cu(II), Cd(II), Ni(II), Zn(II), and Pb(II) were carried out and their removal rate determined by spectrophotometry and ICP-OES. The adsorption performance of the sorbent was compared with powder activated carbon. The Langmuir isothermal model was applied to fit the embedment of BPR and adsorption of EV.
Results
The saturation number of BPR binding to CaC2O4 reached 0.0105 mol/mol and the adsorption constant of the complex was 4.70 × 105 M–1. Over 80% of the sorbent particles are between 0.7 and 1.02 μm, formed by the aggregation of the global CaC2O4/BPR inclusion grains of 30–50 nm size. Such a material was found to adsorb cationic dyes selectively and sensitively. Ethyl violet (EV) was used to investigate the adsorption mechanism of the material. One BPR molecule may just bind with one EV molecule. The CaC2O4/BPR inclusion material adsorbed EV over two times more efficiently than the activated carbon. The adsorption of EV on the CaC2O4/BPR inclusion sorbent was complete in only 5 min and the sedimentation complete in 1 h. However, those of EV onto activated carbon took more than 1.5 and 5 h, respectively. The treatment of methylene blue and malachite green dye wastewaters indicated that only 0.4% of the sorbent adsorbed over 80% of color substances. Besides, the material can also adsorb heavy metals by complexation with BPR. Over 90% of Pb2+, and approximately 50% of Cd2+ and Cu2+, were removed in a high Zn2+-electroplating wastewater when 3% of the material was added. Eighty-six percent of Cu2+, and 60% of Ni2+ and Cd2+, were removed in a high Cd2+-electroplating wastewater.
Discussion
The embedment of BPR into CaC2O4 particles responded to the Langmuir isothermal adsorption. As the affinity ligand of Ca2+, BPR with sulfonic groups may be adsorbed into the temporary electric double layer during the growing of CaC2O4 particles. Immediately, C2O4 2– captured the Ca2+ to form the CaC2O4 outer enclosed sphere. Thus, BPR may be released and embedded as a sandwich between CaC2O4 layers. The adsorption of EV on the sorbent obeyed the Langmuir isothermal equation and adsorption is mainly due to the ion-pair attraction between EV and BPR. Different from the inclusion sorbent, the activated carbon depended on the specific surface area to adsorb organic substances. Therefore, the adsorption capacity, equilibrium, and sedimentation time of the sorbent are much better than activated carbon. The interaction of heavy metals with the inclusion sorbent responded to their coordination.
Conclusions
By characterizing the C2O4 2––BPR–Ca2+ inclusion material using various modern instruments, the ternary in situ embedment particle, [(CaC2O4)95(BPR)] n 2n–, an electronegative, micron-sized adsorbent was synthesized. It is selective, rapid, and highly effective for adsorbing cationic dyes and heavy metals. Moreover, the adsorption is hardly subject to the impact of electrolytes.
Recommendations and perspectives
The present work provides a simple and valuable method for preparing the highly effective adsorbent. If a concentrated BPR wastewater was reused as the inclusion reactant, the sorbent will be low cost. By selecting the inclusion ligand with a special structure, we may prepare some particular functional materials to recover the valuable substances from seriously polluted wastewaters. The recommended method will play a significant role in development of advanced adsorption materials.
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Acknowledgement
We thank the National Key Technology R&D Program of China (Grant No. 2008BAJ08B13 and 2006BAJ08B10) and the State Key Laboratory Foundation of Science and Technology Ministry of China (No. PCRRK08003) for financially supporting this work.
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Wang, HY., Gao, HW. Preparation of calcium oxalate—bromopyrogallol red inclusion sorbent and application to treatment of cationic dye and heavy metal wastewaters. Environ Sci Pollut Res 16, 339–347 (2009). https://doi.org/10.1007/s11356-008-0070-8
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DOI: https://doi.org/10.1007/s11356-008-0070-8