Coagulation performance of polyaluminum silicate chloride (PASiC) for water and wastewater treatment

Bao-Yu Gao , Qin-Yan Yue, Yan Wang

School of Environmental Science and Engineering, Shandong University, Jinan 250100, Shandong, PR China Received 22 November 2006; received in revised form 4 February 2007; accepted 4 February 2007

Abstract A series of polyaluminum silicate chloride (PASiC) composite coagulants were prepared by two approaches: (1) hydroxylation of the mixture of AlCl3 and fresh polysilicate (PASiCc ); (2) hydroxylated polyaluminum chloride (PAC) combined with fresh polysilicate (PASiCm ). Laboratory experiments were conducted to evaluate PASiC in comparison with PAC for the coagulation of water and wastewater and to investigate the effects of preparation technique, [OH]/[Al] ratio (i.e. value), pH, Al/Si ratio, and temperature on the coagulation performance of PASiC. The experimental results showed that PASiC performed more efciently than PAC did in removing algae, turbidity, oil, chemical oxygen demand (COD) and total phosphate (TP). At the same Al/Si ratios, PASiCc achieved slightly greater removal of turbidity than PASiCm did. However, the difference became less signicant at higher dosages. The results also demonstrated that the coagulation efciency of PASiC was better at greater values and that PASiC became unstable during aging at very high values. The optimum coagulation pH range of PASiCc at a value of 2.0 and an Al/Si ratio of 10 was found to be 6.08.5, slightly wider than that of PAC (6.08.0). 2007 Elsevier B.V. All rights reserved.
Keywords: Polyaluminum silicate chloride (PASiC) coagulants; Preparation; Coagulation performance; Water and wastewater treatment

1. Introduction Polyaluminum chloride (PAC) [1] has been used for many years at water purication plants throughout the world. PACs advantages over alum include reduced acidity, positively charged monomers and polymers, formation of rapid and denser oc, and reduced sludge. However, concerning its morphology and coagulatingocculating characteristics, PAC remains in a position between the common metal salts and organic occulants [2]. Its molecular weight and size for aggregating action and its stability to resist further hydrolysis are still much lower than those of organic polymer occulants. Recently, it was reported that under certain conditions PAC and activated silica, a polysilicate (PSi), could be combined to get polyaluminum silicate chloride (PASiC), a new type of inorganic polymer coagulant, having a larger particle size and better turbidity removal efciency than PAC [3,4]. In previous investigations, the preparation, chemical species distribution and properties of PASiC were described by Gao and

Yue et al. [3,5]. However, laboratory experiments on the coagulation performance of PASiC in water and wastewater treatment have been lacking. The objective of this laboratory study is to evaluate the coagulation performance of PASiC. It is achieved by examining the effects of [OH]/[Al] ratio (), Al/Si molar ratios, dosage, pH and the preparation technique on the coagulation performance of PASiC, and comparing its effectiveness with that of PAC. 2. Experimental methods 2.1. Preparation of coagulants The preparation of PASiC coagulant was carried out as previously described by Gao et al. [4]. Two approaches to prepare PASiC are briey described below. First, 10.75 ml concentrated waterglass solution (typically 3 M SiO2 ) was introduced slowly (1.0 ml/min) into 10 ml 2 M hydrochloric acid solution while stirring to obtain a PSi solution (pH value of 2.02.2). Next, the fresh PSi solution and 2.5 M AlCl3 solution were mixed at an Al to Si ratio of 5 or greater, and then 1.5 M Na2 CO3 solution was added slowly (0.5 ml/min) with thorough stirring to obtain PASiCc coagulants with various

Corresponding author. Tel.: +86 531 88364832; fax: +86 531 88364513. E-mail address: bygao@sdu.edu.cn (B.-Y. Gao).

1383-5866/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.seppur.2007.02.003

Table 1 Comparison of turbidity removal efciency between PASiCm and PAC for water from Shenzheng Lake Coagulant Dosage (mg/L as Al2 O3 + SiO2 ) 0.8 1.0 1.2 1.5 0.8 1.0 1.2 1.5 Residual turbidity (NTU) 1.08 0.79 0.62 0.48 1.85 1.24 1.05 0.66 Turbidity removal (%) 83.6 88.0 90.6 92.7 72.0 81.2 84.1 90.0 Required dosage when the residual turbidity is equal 1.0 NTU (mg/L as Al2 O3 + SiO2 )

PASiCm , = 2.4, Al/Si = 10

0.86

PAC, = 2.4

1.23

values and Al/Si values, where = [OH]/[Al] in which [OH] and [Al] are the total concentrations of added OH and Al, respectively, in the solution. Initially, 1.5 M Na2 CO3 solution was added at a rate of 0.5 ml/min to the 2.5 M AlCl3 solution under thorough stirring to obtain different PAC solutions, which are characterized with the following properties: = 1.02.4, Al2 O3 content = 9.1010.0%, density (g/cm3 ) = 1.101.22, and pH = 1.83.5. Then, PAC was combined with fresh polysilicate solution at Al to Si ratios of 5 or greater to obtain PASiCm coagulants. The PASiC products prepared by the two methods mentioned above have the following properties: Al2 O3 + SiO2 content = 10.0%, Al/Si = 515, = 1.02.4, pH = 2.03.3, and density (g/cm3 ) = 1.121.25. The PAC used in this study was also prepared in our laboratory. Stock AlCl3 solution (2.5 M) was prepared with AlCl3 6H2 O (A. R.) dissolved in distilled water. Then, Na2 CO3 solution was added at a rate of 0.5 ml/min to the AlCl3 solutions to obtain the PAC solution with desired value. The properties of PAC were: = 1.02.4, Al2 O3 content = 9.1010.0%, density (g/cm3 ) = 1.101.22, and pH = 1.83.5. 2.2. Coagulation test procedures Coagulation tests were performed using samples of surface water or wastewater. All coagulation experiments were conducted in 1.0 L plexiglass beakers using a conventional jar test apparatus, the DC 506 Laboratory Stirrer (Huashui New Technological Development Co., Shanghai, China). Eight hundred milliliter suspensions were dosed with different coagulants. The solutions were stirred rapidly at 120 rpm for 2 min during coagulant addition, followed by stirring at 40 rpm for 10 min and then 15 min of sedimentation. After sedimentation, supernatant samples were taken from a point 3 cm below the surface of the test water sample for analysis. For the experiments on the effect of pH on the oil removal efciency, the pH of the wastewater was adjusted with 0.1 M HCl solution or 0.1 M NaOH solution. 2.3. Analytical methods Turbidity was measured by a Turbidimeter (Model 2100A) and algae cell numbers were counted with a microscope. Chemical oxygen demand (COD) was determined by the potassium

dichromate method, and the total oil was measured with the ultraviolet spectrometer in petroleum ether extract at the wavelength of 254 nm. The above-mentioned parameters and total phosphate (TP) were measured according to the Standard Method for Examination of Water and Wastewater [6]. 3. Results and discussion 3.1. Application of PASiCm to coagulation of surface water from Shenzhen Lake Raw water was taken from Shenzhen Lake, Shenzhen city, which is located in south part of China. The water was characterized by low turbidity (6.6 NTU), low alkalinity (22.5 mg/L as CaCO3 ) and high content of algae (2250 cells/ml). The pH and water temperature of the sample were 6.72 and 22.5 C, respectively. Because higher value (ca. 2.5) of PAC is typical coagulant at water treatment works (WTWs) for the coagulation of low turbidity and low alkalinity surface water in southern China, two coagulants, PASiCm with = 2.4 and Al/Si = 10 and PAC with = 2.4, were tested for comparison of their coagulation efciency in treating actual water of Shenzhen Lake in this work. The results are shown in Tables 1 and 2 and Fig. 1. It can be seen from Tables 12 that PASiCm removed greater percentages of turbidity and algae than PAC at the same dosages. Compared with PAC, a lower PASiCm dosage is required to reach a residual turbidity of 1.0 NTU. Using the same dosage, about 6% more algae was removed by PASiCm at = 2.4 and Al/Si = 10 than by PAC at = 2.4. Fig. 1 shows the settleability of ocs generated by PASiCm and PAC coagulating test water with the same dosages of 1.0 mg/L as Al2 O3 or Al2 O3 + SiO2 , which was obtained by
Table 2 Comparison of algae removal efciency between PASiCm and PAC for water from Shenzheng Lake Coagulant PASiCm , = 2.4, Al/Si = 10 PAC, = 2.4 PASiCm , = 2.4, Al/Si = 10 PAC, = 2.4 Dosage (mg/L as Al2 O3 + SiO2 ) 1.0 1.0 1.5 1.5 Residual algae (cells/ml) 265 384 125 264 Algae removal (%) 88.2 82.9 94.4 88.3

Fig. 1. Change of residual turbidity with settling time (surface water from Shenzhen Lake, initial turbidity of the tested water = 6.6 NTU).

Fig. 2. Comparative coagulation performance of PASiC and PAC ( = 2.0) (surface water from Yellow River, initial turbidity of the tested water = 528 NTU).

measuring the residual turbidity of the coagulated test water at different settling times. The results indicate that the settleability of PASiCm is much higher than that of PAC as PASiCm has a higher molecular weight than PAC [7], which can result in very tough ocs when treating water. 3.2. Application of PASiC to coagulation of surface water from Yellow River Yellow River is the second largest river in China and very important source for drinking water, agriculture and industry of the surrounding area. High suspended solids (SS) and high turbidity characterize the raw water in the river. The raw water used for this study was taken from the Jinan section of the river, located in the province of Shandong (eastern China). The pH, water temperature, SS, alkalinity and turbidity of the sample were 8.22 and 20.0 C, 5846 and 175.1 mg/L as CaCO3 and 528 NTU, respectively. For the treatment of the water with higher turbidity and alkalinity, PAC with value of ca. 2.0 is widely used at WTWs in China. Therefore, coagulants ( = 2.0) after 30 days aging were selected to evaluate their coagulation performance. The results are shown in Fig. 2. It can be seen that all tested PASiC coagulants, except PASiCm with = 2.0 and Al/Si = 5.0, are more effective than PAC in turbidity removal, especially at lower doses. Less Al/Si molar ratio (the higher the concentration of polymeric silicic acid) resulted in better coagulation efciency. The observed results are in general agreement with the results in previous publication which investigate the coagulation efciency of PASiC for treating the synthetic suspension made by micro SiO2 particles [5]. The reason why PASiC with less Al/Si ratio gave higher coagulation efciency is that with increasing the content of polymeric silicic acid in PASiC, the aluminum ion and hydrolysate of aluminum can react with more polymeric silicic acid to form higher molecular weight of PASiC polymers [4,7], which can give stronger bridge-formation for colloidal particles in water. Because PASiCc has higher molecular weight and pos-

itive charge than PASiCm when they have same Al/Si ratios [7], PASiCc achieved slightly greater removal of turbidity than PASiCm , however, the difference between them became negligible with increasing of the dosage. PASiCm with = 2.0 and Al/Si = 5.0 had the worst turbidity removal efciency because some of the polysilicate in the PASiCm product became partly gelatinous and the product became cloudy after 30 days aging, which must have weaken its coagulation capability when used in water treatment. The results mentioned above suggest that the Al to Si ratio for stable and high efciency PASiC products should not be too low, and that the improved turbidity removal could be achieved when PAC and PSi were combined together to form a composite coagulant. In addition, the preparation technique had some effect on the coagulation performance of PASiC coagulants. Furthermore, previous results show that PASiC was characterized by a lower residual aluminum concentration in water compared with PAC [4]. Considering the stability and the coagulation efciency, PASiCc with = 2.0 and Al/Si = 10 was used to investigate the effect of temperature on the coagulation performance in treating the same surface water from the Yellow River mentioned above, in comparison with PAC with = 2.0. The dosage of the coagulants was xed at 1.62 mg/L and the results were shown in Fig. 3, which indicates that in the range of tested temperatures (540 C), PASiCc gave better turbidity removal efciency than PAC, especially at lower temperatures. The difference between the two coagulants became less signicant with the increase of temperature. It was also found from Fig. 3 that temperature had an obvious effect on the coagulation efciency of PASiC and PAC. The higher the temperature, the better the coagulation efciency of PASiC and PAC. 3.3. Application of PASiC to coagulation of wastewater from oil renery Wastewater was taken from Jinan Oil Renery Factory in Shandong Province, China, which contained 308.4 mg/L of oil,

Fig. 3. Effect of temperature on the coagulation efciency of PASiCc and PAC (surface water from Yellow River, initial turbidity of the tested water = 528 NTU).

Fig. 5. Variation of oil removal efciency with Al/Si ratios and dosages of coagulantsc (wastewater from oil renery).

Fig. 4. Variation of oil removal efciency with values and dosages of PASiCc (wastewater from oil renery).

Fig. 6. Effect of coagulation pH on oil removal by PASiCc and PAC at dosage of 2.0 mg/L (wastewater from oil renery).

716.8 mg/L of COD and 267.9 mg/L of SS, respectively. The wastewater samples had a pH value of 8.32. Figs. 46 show the effect of value, Al to Si molar ratios and pH on the efciency of oil removal by PASiCc and PAC. Table 3 shows the COD removal efciency of PASiCc with the same dosages of 2.0 mg/L as Al2 O3 + SiO2 . The oil removal efciency of PASiCc varied
Table 3 Comparison of COD removal efciency between PASiCc with Al/Si = 10 and PAC Coagulants PAC, = 1.0 PASiCc , = 1.0, Al/Si = 10 PAC, = 1.5 PASiCc , = 1.5, Al/Si = 10 PAC, = 2.0 PASiCc , = 2.0, Al/Si = 10 Dosage (mg/L as Al2 O3 + SiO2 ) 2.0 2.0 2.0 2.0 2.0 2.0

with value and the dose (Fig. 4). The oil removal efciency of PASiCc increased with increasing value. The dosage of PASiCc affected the oil removal, especially when the dosage was lower than 2.0 mg/L. When PASiCc was added at a dosage of 2.0 mg/L or more, a very high oil removal efciency (>90%) can be achieved. This is due to fact that PASiCc with large molecular size and high positive charge has strong bridge formation and

COD before treated (mg/L) 716.8 716.8 716.8 716.8 716.8 716.8

COD after treated (mg/L) 213.3 191.2 180.3 147.5 134.3 108.1

COD removal (%) 70.25 73.32 74.85 79.43 81.26 84.90

charge neutralizing capability for negatively charged waste oil emulsions from petroleum reneries [8]. As shown in Fig. 5, PASiCc performed better in oil removal than PAC, especially at low dosages. PASiCc with Al/Si = 10 gives the highest oil removal efciency (ca. 93% at the dosage of 2.0 mg/L or above), compared with PASiCc coagulants with Al/Si = 5.0 or 15. The reason why the Al/Si molar ratio in PASiCc affected its coagulation performance can be explained with the interaction between PSi and hydrolyzed aluminum species, which affects the species distribution of PASiC [9]. The higher Al/Si value in PASiC produced higher positively charged but smaller molecular sized product, and lower Al to Si ratio produces lower positively charged but larger molecular sized product [10]. Only when PASiC has a proper ratio of Al/Si, can the PASiC coagulant with both high positive charge and large molecular size be developed. The proper Al to Si ratio in PASiC depends on the water and wastewater composition. Fig. 6 shows that PASiCc with value of 2.0 and Al/Si ratio of 10 had a slightly wider optimum coagulation pH range and a higher oil removal efciency than PAC with value of 2.0. The optimum pH range of 6.08.0 for PAC was extended to a pH range of 6.08.5 for PASiCc . From Table 3, it can be seen that the value of the coagulants affected the COD removal efciency of both PASiCc and PAC. The higher the value, the greater the COD removal. PASiCc led to higher COD removal efciency than PAC at the same value. The difference of COD removal rate between PASiCc and PAC was in the range of 3.04.6% under the testing conditions. For example, COD removal of 84.90% was obtained using 2.0 mg/L of PASiC with = 2.0 and Al/Si = 10, while PAC with = 2.0 produced 81.26% COD removal. The results presented above show that when PAC and PSi were combined together to the composite coagulant PASiC under the some conditions, the higher coagulation efciency was achieved. 3.4. Application of PASiCc to coagulation of municipal wastewater Municipal wastewater was taken from the Second Municipal Wastewater Treatment Plant of Jinan in Shandong Province, China. The COD, total phosphate (TP) and pH of this wastewater are 348, 3.06 and 7.33 mg/L, respectively. Fig. 7 shows the effect of Al/Si molar ratios and coagulant dosages on the coagulation performances of PASiCc and PAC. It was found in Fig. 7A that PASiCc coagulants, except PASiCc with = 2.0 and Al/Si = 15, are more effective than PAC in COD removal. The coagulants dosage needed to achieve the optimal COD removal was lower for PASiCc than that for PAC. The optimal dosage for PASiCc with different Al/Si ratio is 6.0 mg/L, while the optimal dosage for PAC is 8.0 mg/L. This is because that PASiCc has larger molecular size and higher positive charge, which results in stronger bridge formation and charge neutralizing capability, than PAC for treating municipal wastewater [8]. Less Al/Si molar ratio (the higher the concentration of polymeric silicic acid) resulted in better coagulation efciency. PASiCc with = 2.0 and Al/Si = 5 performed the highest COD removal efciency.

Fig. 7. Effect of Al/Si ratios on COD and TP removal by PASiCc and PAC (municipal wastewater).

It can be seen from Fig. 7B that the TP removal efciency of PASiCc is higher than that of PAC, and the TP removal efciency of PASiCc increased with decreasing Al/Si ratio. At a dosage of 10 mg/L, TP of municipal wastewater treated by PASiCc with = 2.0 and Al/Si = 5 is 0.23 mg/L, which is below the demand (0.5 mg/L) of Discharge Standard of Pollutants for Municipal Wastewater Treatment Plant in China [11]. 4. Conclusions A laboratory study was conducted to evaluate the coagulation performance of PASiC in the treatment of water and wastewater, which was prepared by combining PAC with PSi, and to compare with that of PAC. Experiments were carried out to investigate the effects of [OH]/[Al] ratio (), Al/Si molar ratios, dosage, pH and preparation technique on the efciency of turbidity, algae, COD, oil and TP removal by PASiC coagulation. The results demonstrate that the coagulating performance of PASiC was dependent upon preparation procedure, Al/Si ratio and value. It is concluded that the coagulation efciency of PASiC increased with increasing value, but the products became

unstable during aging at very high value. PASiC performed more efciently than PAC for removing algae, turbidity, oil, COD and TP under the laboratory conditions. The techniques used for obtaining PASiC resulted in different coagulation performances. PASiCc achieved slightly greater efciency of turbidity removal than PASiCm at the same Al/Si ratios. However, the difference became less signicant with increasing dosages. The optimum coagulation pH range of PASiCc at a value of 2.0 and an Al/Si ratio of 10 was found to be 6.08.5, slightly wider than that of PAC (6.08.0). Based on he results of this study, it is suggested that PASiC is a high efciency inorganic coagulant. Acknowledgement

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The authors are thankful to the support of the Chinese National Foundation of Natural Sciences. References

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