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cn Journal of Environmental Management

Characterization and coagulation of a polyaluminum chloride (PAC) coagulant with high Al13 content
Bao-Yu GAO *, Yong-Bao CHU, Qin-Yan YUE, Bing-Jian WANG, Shu-Guang WANG
School of Environmental Science and Engineering, Shandong University, No.27 Shanda South Road, Jinan 250100, Shandong, P.R.China

Abstract
A polyaluminum chloride (PAC) coagulant was prepared from AlCl36H2O and Na2CO3. The Al13 species in PAC was separated and purified by the SO42-/Ba2+ deposition-replacement method, and characterized by 27 Al-NMR and XRD. From 27Al-NMR spectroscopy, it was found that PAC obtained after separation and purification contained more Al13 (PAC-Al13, for short) than original PAC before separation and purification. In XRD spectra, a strong Al13 signal appeared in the range of 2from 5to 25. Jar tests were performed to test the coagulation efficiency of AlCl3, PAC and PAC-Al13 in treating synthetic or actual water samples. Compared with PAC and AlCl3, PAC-Al13 gives the best results for turbidity, humic acid and color removal, and achieves the highest charge-neutralizing ability. Under the study conditions, PAC-Al13 gave about 90 % humic acid removal and almost 100% dye reactive blue removal when its dosages were 4.0 mg/L and 15 mg/L as Al, respectively. Al13 species is a higher positive-charged and most effective polymeric Al species in water and wastewater treatment. Keywords: Al13 species; coagulation; polyaluminum chloride; separation and purification

1. INTRODUCTION Polyaluminum chloride (PAC) coagulant has been developed and used in water and wastewater treatment since 1980s throughout the world (Jiang, 2001). PAC is made by partial hydrolysis of acid aluminum chloride solution using a specific reactor. Many species have been proposed to form during hydrolysis; more commonly accepted species include the monomers Al3+, Al(OH)2+, Al(OH)2+ , Al(OH)3(am) and Al(OH)4-, as well as a dimmer (Al2(OH)24+), a trimer (Al3(OH)45+) and the tridecamer (Al13O4(OH)247+, often denoted by Al13) (Bertsch, 1989). The nature of the species formed depends on various factors such as the concentration of Al(); the basic ratio (r), defined as the molar ratio of the Al ions to hydroxide ions; base concentration; base addition rate; and the hydrolysis duration of Al() solution (aging time) and aging temperature. The most important parameters that govern the nature of the species are value and the aging temperature and time (Gray, 1995). Among the species, it seems that Al13 species is the most effective and stable polymeric Al species in water and wastewater treatment (Jiang, 1998; Tang, 1995). Thus, production of PAC with a high Al13 concentration seems to be main aim of the PAC research and production industry (Tang, 1995). The structure of Al13 species has been detected by NMR spectroscopy method(Parthasarathy, 1985), with the central Al atom in tetrahedral coordination, and 12 other aluminum atoms are in octahedral coordination. This type of structure is known as Al13-Keggin structure and with a radius of about 2.5 nm (Peng, 2001; Tang, 1998). The Al13-Keggin structure is stable in aqueous solution, but less stable in solutions with higher pH where it hydrolyzes to bayerite -Al(OH)3 (Wang, 1999). The Al13 species easily aggregate together to form aggregates with
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a size ranging from decades to hundreds nanometer (Tang, 1998). Since 1960s, a lot of research on the preparation, properties and aluminum species of PAC has been done (Jiang, 2001), however, little information is available regards the separation and purification of Al13 species and the coagulation/flocculation performance of Al13 species in water and wastewater treatment. In this study, experiments were carried out to prepare PAC coagulants with r value of 2.0 and 2.2, respectively, then, to separate and purify Al13 species from PAC to obtain high Al13 concentration of PAC (denoted by PAC-Al13) by the SO42-/Ba2+ replacement method, and then, to characterize the Al13 species by NMR and XRD, and finally, to investigate the coagulation performance of PAC-Al13 in comparison with PAC, and/or AlCl3.
2. Materials and Methods PAC was prepared in our laboratory using AlCl3 and Na2CO3 as raw materials. Briefly, a Na2CO3 solution (~25.0% Na2CO3) was slowly added to a solution of AlCl3 (~5.0 % Al) with stirring at room temperature to obtain the desired r (between 2.0 and 2.2) of PAC. After addition of Na2CO3 solution, the mixture was stirred until no bubbles formed and the solution became transparent, then it was diluted with deionized water to a concentration of 0.3 M of Al, and then it was allowed to rest for more than 24 h before the Al13 species in PAC was separated and purified and the properties of the coagulant were examined. A 25 ml of 0.3 M PAC solution was placed in a beaker, and reacted with 25 ml of 0.3 M Na2SO4 solution for 24 hours at room temperature. After reaction, the Al13 polyoxocations in the PAC solution were precipitated from the solution as a sulfate salt. Then the solution was filtered through filter paper and the deposit was collected and washed 56 times with denionized water. And then, the deposit, 5 ml denionized water and 25 ml 0.3 M Ba(NO3)2 solution were added in a 25 ml tube and the mixture was sonicated for 4 hours. Finally, the mixture was centrifugalized in a centrifuge for 15 min at a speed of 1500 rpm, and the supernatant liquid with high content Al13 species, or PAC-Al13, was obtained. The concentration of Al and the percentage of Al13 species in PAC-Al13 are about 0.15 M and 90%, respectively. During experiment, all chemicals utilized were analytical regent grade. The Al species in PAC-Al13, PAC , AlCl3 and Al2(SO4)3 was analyzed using a JEOL FX-90 Q NMR spectrometer with a sample tube of 10 mm diameter. At the center of the sample tube, a capillary of 1 mm diameter was inserted. The 0.20 M NaAl(OH)4 aqueous solution and the same volume of heavy water (D2O) as that of the NaAl(OH)4 aqueous solution, which was used as the internal standard of the deuterium lock and aluminum content, were added into the capillary. The scanning frequency is 23.31 MHz, observation offset 38.68 KHz, the angle of pulse 90, pulse delay time 0.1 s, 8 K data point, and the spectrum width 200 ppm. The number of samplings depends on aluminum content in the sample. The powder samples of PAC and PAC-Al13, dried in a vacuum oven at 65 , were used to analyze using a D/max-A model Diffraction Meter with a Cu-K source ( =1.54184 ) and random packed powder diffraction mounts. Samples were scanned from 5-70 2 using a step size of 0.02 2, and a step speed of 0.5 sec/step. Coagulation tests were performed by using either synthetic water samples or actual surface water. All coagulation experiments were conducted in 1.0 L plexiglass beakers using a DC-506 laboratory stirrer (Huashui New Technological Development Co., Shanghai, China). The 800 mL water sample solutions were dosed with different coagulants. The solution was stirred rapidly at 200 rpm for 2 min during coagulant addition. Directly after the rapid mixing, 2.0 mL of the suspension was taken by a 2.0 mL syringe for zeta potential measurement using a Zetasizer (3000 HSA, Malvern Corporation). There then followed a 15 min slow stirring (40 rpm) and 10 min sedimentation. The coagulation pH was maintained by addition of the pre-determined volume of NaHCO3 solution (3.5 mM) simultaneously with the coagulant. After sedimentation, a supernatant sample was withdrawn from a point 3 cm below the surface of the test water sample for turbidity
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measurement using YZD-1 turbidimeter (Yinchuan Instrument Co., China ) and color measurements using a Lambda 5 UV/VIS spectrophotometer (Perkia-Elmer Corporation).

3. Results and discussion 3.1. Characterization of PAC and PAC-Al13 by 27Al-NMR spectrum and XRD spectrum The 27Al-NMR spectra of the Al2(SO4)3 , AlCl3, PAC and PAC-Al13 samples are shown in Figure 1. Three signals are observed for PAC-Al13and PAC: the signal near 0.0 ppm represents the monomeric and dimeric aluminum species; the signal at 62.5 ppm denotes Al13 species; and the signal at 80.0ppm indicates the formation of Al(OH)4- (the internal standard)( Akitt, 1981). It can be seen from Fig.1, there are only two signals at 0.0 ppm and 80.0 ppm in the Al2(SO4)3 and AlCl3 27Al-NMR spectrum, which indicates that only monomeric and dimeric aluminum species are present, but no Al13 species. The 27Al-NMR spectra of PAC show three signal peaks, but the signal near 62.5ppm is very low, which indicates the content of Al13 is very low. It was also found that the intensity of the signal at 62.5ppm in PAC increases with increasing r value, which means that PAC with higher value has a higher content of Al13 species. When the r value is the same, PAC-Al13 shows a much stronger signal at 62.5ppm, while the signal near 0.0 ppm is much lower than in PAC, which indicates PAC-Al13 has a much higher content of Al13 species and much lower content of monomeric and dimeric aluminum species than PAC. For PAC-Al13, the content of Al13 species increases but the content of monomeric and dimeric aluminum species decreases with increasing value. The results above show that Al13 is the predominant species in PAC-Al13. Calculated according to Gao (2002), the Al13 content in PAC-Al13 can reach about 90%.

Fig.1 27Al-NMR spectra A: Al2(SO4)3 B: AlCl3 C: PAC( r=2.0) D: PAC(r =2.2) E: PAC-Al13 (r =2.0) F: PAC-Al13 (r =2.2)

The Al13 signals appeared in the range of 2 from 5 to 25 in XRD spectrum (Wang,1999). Fig.2 shows the XRD spectra of PAC and PAC-Al13. It can be seen from Fig.2 that there is a distinct difference between PAC-Al13 and PAC in the XRD spectra. No any peak appears in the range of 2from 5to 25in PAC XRD spectrum. However, both PAC-Al13 (r=2.0) (Fig.2C) and PAC-Al13 (r=2.2) (Fig.2D) give high intensity and sharp peaks in the range of 2 from 5to 25, which indicates that there is much more Al13 species in PAC-Al13 than in PAC. This result is in good agreement with the 27Al-NMR results above. In addition, all the tested
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samples appear diffraction peaks of NaCl in the range of 2>25. NaCl is the by-product formed during hydrolyzation and polymerization of Al(), and can not be removed during the separation and purification process. XRD is sensitive to NaCl, and even a very low content of NaCl can give fairly strong signals, so NaCl signals appear in all tested samples in the range of 2 >25.

Fig.2 Analysis of the XRD spectrum of nano-sized PAC A: PAC (r =2.0) B: PAC (r =2.2) C: PAC-Al13 (r =2.0) D: PAC-Al13 (r =2.2)

3.2. Coagulation test results 3.2.1. Turbidity removal efficiency for actual surface water Actual surface water with turbidity of 151 NTU and pH value of 8.12 was taken from Yellow River, Jinan, China. The water in Yellow River is a very important drinking-water resource for north part of China. Coagulants AlCl3, PAC and PAC-Al13 were selected to compare their turbidity removal efficiency. The results are shown in Figs.3 and 4. It can be seen from Fig. 3 that PAC-Al13 and PAC performed much better than AlCl3 for turbidity removal. Compared with PAC, PAC-Al13 gave better turbidity removal results. During the experiment, it was also found that the flocs formed by PAC-Al13 were larger than those formed by AlCl3 and PAC when treating the test water. Fig.4 show that PAC-Al13 possesses stronger charge-neutralization than PAC and AlCl3. Because the good turbidity removal effect occurs when the flocs possesses negative charge, this suggests that both PAC-Al13 and PAC play coagulation/flocculation by charge-neutralization and bridge-formation mechanism. 3.2.2. Turbidity and humic acid removal efficiency for the kaolinite and humic acid suspended water sample A synthetic suspension containing 50mg/L kaolinite and 10mg/L humic acid, which was made up of 50% deionized water and 50% tap water, was used as the test water. The initial turbidity, absorbance at 254 nm and pH of the suspension were 31.0 NTU, 0.167 and 7.02,
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respectively. The turbidity and UV254 removal efficiency of PAC-Al13 for the test water, in comparison with PAC and AlCl3 were shown in Figs.5 and 6. It can be seen that the PAC-Al13 achieves more removal of turbidity and humic acid than PAC and AlCl3. When PAC-Al13 was used at the dosage of 4.0 mg/L as Al, about 90 % humic acid could be removed. These results indicate that PAC-Al13 with higher Al13 content has the advantage of higher coagulation performance than PAC with lower Al13 content. It is confirmed that Al13 species is the most effective polymeric Al species in water and wastewater treatment.
100 90 80 Residual turbidity (NTU) 70 60 50 40 30 20 10 0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
-15 -16 0.0 Zeta potential (mv)
PAC r=2.0 PAC-Al13 r=2.0 AlCl3

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PAC r=2.0 PAC-Al13 r=2.0 AlCl3

0.5

1.0

1.5

2.0

2.5

3.0

Coagulant dosage (mg/L as Al)

Coagulant dosage (mg/L as Al)

Fig.3 Comparison of turbidity removal efficiency between PAC-Al13, PAC, and AlCl3

Fig.4 Effect of dosages of coagulants on zeta potential of flocs for surface water treatment

35 30 Turbidity(NTU) 25 20 15 10 5 0 0 1 2 3 4 5
AlCl 3
UV254 removal efficiency (%)

100 AlCl3 80 PAC r=2.0 PAC-Al13 r=2.0

PAC r=2.0 PAC-Al13 r=2.0

60

40

20

0 0 1 2 3 4 5 Coagulant dosage (mg/L as Al)

Coagulant dosage (mg/L as Al)

Fig.5 Comparison of turbidity removal efficiency between PAC-Al13, PAC and AlCl

Fig.6 Comparison of color removal efficiency between PAC-Al13, PAC, and AlCl3

3.2.3. Color removal efficiency for dye-containing wastewater A synthetic dye wastewater prepared by adding 1 g of reactive blue (K-GL) into 10 L of tap water was treated by PAC-Al13, PAC and AlCl3 in order to compare their color removal efficiency. The absorbance of the tested water is 1.832 at the maximum absorbance wavelength (max) of 598 nm, determined by running a scan on a spectrophotometer. During experiment, max was used for all the absorbance readings. Percentage of color removal was calculated by comparing the absorbance values for the wastewater after treatment to the absorbance value for the original dye wastewater. Deionized water served as a reference. The coagulation performance of PAC-Al13, PAC and AlCl3 for color removal was shown in Figs.7 and 8. The results given in Figs.7 and 8 show that the color removal efficiency of the tested water and
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the zeta potential on microflocs freshly formed during coagulation varies with increasing of dosages PAC-Al13, PAC and AlCl3. PAC-Al13 achieved greater removal of color and had highest charge-neutralizing ability than PAC and AlCl3. It can be seen from Fig.7 that PAC-Al13 achieved much more greater color removal results than PAC and AlCl3 at low dosage, however, the difference in color removal efficiency between PAC-Al13, PAC and AlCl3 became slight with increasing of coagulant dosage. PAC-Al13 gave almost 100% color removal when its dosage was equal to or more than 15 mg/L as Al. But for PAC and AlCl3, the same result could be achieved only when their dosages were higher than 27 mg/L as Al and 32.4 mg/L as Al, respectively. Again, the results above confirm that Al13 species is the higher positive-charged and most effective polymeric Al species in water and wastewater treatment.
100 90 Color removal efficiency (%) 80

4 2 0 -2 Zeta potential (mv) -4 -6 -8 -10 -12 -14 -16 -18 -20

0 5 10 15 20 25 30 35
PAC r=2.0 PAC-Al13 r=2.0 AlCl3

PAC r=2.0 PAC-Al13 r=2.0 AlCl3

70 60 50 40 30 20 Coagulant dose (mg/L as Al)

10

15

20

25

30

35

Coagulant dosage (mg/L as Al)

Fig.7 Comparison of color removal efficiency among PAC-Al13, PAC and AlCl3

Fig.8 Effect of dosages of coagulants on zeta potential of flocs for dye wastewater treatment

4. Conclusion
The results investigated by 27Al NMR and XRD show that PAC-Al13 prepared from PAC by SO42-/Ba2+ replacement method contains more Al13 species than original PAC. The coagulation experiments results show that PAC-Al13 gives the greatest turbidity, humic acid and color removal effect, and achieves the highest charge-neutralizing ability than PAC and AlCl3 when treating tested synthetic water samples or actual surface water. The results above confirm that Al13 species is a higher positive-charged and most effective polymeric Al species in water and wastewater treatment and indicate that both PAC-Al13 and PAC play coagulation/flocculation by charge-neutralization and bridge-formation mechanism. Acknowledgements The authors thank the National High-Tech Research and Development Program (863), the Specialized Research Fund for the Doctoral Program of Higher Education (SRFDP) and the Shandong Natural Science Foundation for support.

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