A PILOT PLANT STUDY ON USING SEAWATER AS A MAGNESIUM SOURCE FOR STRUVITE PRECIPITATION

K. Kumashiro1, H. Ishiwatari2, Y. Nawamura3*

1

Water Quality Control Section, Construction Bureau, 96-3 Nishiminato-Mati, Kokurakita-Ku, Kitakyushu, 803-0801,

Japan.2Japan Institute of Wastewater Engineering Technology (JIWET), Ikebukuro Chitose Blg. 7F 1-22-8 Nishiikebukuro, Toshima-ku, Tokyo, 171-0021, Japan. 3Nishihara Environmental Sanitation Research Corporation Ltd., 3-618 Shibaura, Minato-Ku, Tokyo, 108-0023, Japan email : yoshiharu_nawamura@nishihara.co.jp Abstract In recent years, a number of biological treatment processes have been developed for phosphorus (P) as well as combined nutrient (N&P) removal. In anaerobic/oxic (A/O) and anaerobic/anoxic/oxic (A2/O) processes, it is necessary to lower the concentration of P in the sidestream from the sludge treatment facilities. To accomplish this, the magnesium-ammonium-phosphate (MAP) system (P removal from the sidestream by MAP crystallization) has been developed and applied to full scale plants. However, because the earlier systems need chemicals such as magnesium chloride as the source of magnesium (Mg) as well as sodium hydroxide (NaOH) for pH control, they were found to be economically less viable. To lower the operational cost of the MAP system, seawater was substituted for chemicals and succeeded in developing a new MAP system. In this paper, we focus on the relationship between P removal efficiency and operational conditions. By feeding 50.5 to 110 (mg/l) in dissolved phosphorus (D-P) having pH above 7.77 from sidestream, together with a 9.0 to 10 % seawater inflow into the reactor, holding a 4.3 to 13 % volume of MAP (MV), and with 29 minutes HRT, over 70 % D-P removal efficiency was achieved without pH control. Although the use of seawater requires the power cost for pumping, substantial cost reduction can be achieved when compared with chemicals. Also, the method using seawater is superior, as it can simplify the facilities and operation, and does not affect the existing treatment facilities. Keywords: Crystallization, MAP, Phosphorus Removal, Seawater, Sidestream INTRODUCTION In last two decades, a number of advanced biological treatment processes have been developed for P as well as combined N & P removal. These processes have considerable appeal to designers and operators because the use of chemicals has been eliminated or reduced substantially. In 1994, the design manual for anaerobic/oxic (A/O) and anaerobic/anoxic/oxic (A2/O) processes was issued. It made a major contribution toward encouraging municipalities to adopt both processes for their plant [1]. In A/O and A2/O processes, it is necessary to lower the concentration of P in sidestreams from the sludge disposal processes [2]. For this purpose, the magnesium-ammonium-phosphate (MAP) system (technology for P
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removal from the sidestream by crystallization of MAP) has been developed [3] and applied to full-scale plants [4].

MAP is a raw material for fertilizer, and due to the rich content of phosphorus and its refractory nature, it has a characteristic for excellent slow fertilizer. It is also an environmentally friendly, as it does not increase the electrical conductivity of soil, due to less excess salt contents. The MAP system can be recognized not only as one of the advanced wastewater treatment systems but also as a P recycling system. However, because previous MAP systems need chemicals such as magnesium chloride as the source of magnesium (Mg) as well as sodium hydroxide (NaOH) for pH control [4,5,6], they are economically less viable. As Japan is surrounded by seas and many of wastewater treatment plants are located near the sea, so it is easy to keep the seawater as a Mg source for MAP system. By substituting seawater for chemicals, operational cost of the MAP system can be substantially reduced. In this paper, we focus on the relationship between P removal efficiency and operational conditions in the newly developed MAP process using seawater as Mg source. The target P removal efficiency was 70% in terms of D-P [7]. A study was also conducted to increase the value of the product as fertilizer, and to promote the beneficial use of the product with higher marketability.

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OPERATIONAL FACTORS OF MAP SYSTEM MAP crystallizes by the reaction of magnesium ion (Mg2+), ammonium ion (NH4+), and orthophosphate ion (HPO42-) on an equal mole basis as follows [4]. Mg2++NH4++HPO42-+OH-+6H2O MgNH4PO46H2O+H2O (i)

The solubility of MAP is dependent on pH. It increases with the lowering of pH and vice versa. The P removal efficiency is affected by the molar ratio of dissolved magnesium (D-Mg) to dissolved phosphorus (D-P) in the mixture of influent and the chemicals added as the source of Mg (Mg/P). The nucleus of the MAP system is considered to be circulating MAP particles in the reactor. The concentration of MAP particles is relevant to the reaction rate [4]. The longer the hydraulic retention time of the reactor (HRT), the higher is the P removal efficiency [4]. Therefore, pH, Mg/P, MAP concentration in the reactor, and HRT are important operational factors of the MAP system. METHODOLOGY Pilot plant The MAP pilot plant was constructed at Hiagari Sewage Treatment Plant (HSTP) in Kitakyushu City. The process flowsheet is shown in Figure 1. This objective is to treat wastewater from sidestreams, such as dewatering effluent containing high concentration of ammonium (NH4+) and orthophosphate ions (HPO42-). By converting phosphorus as MAP particles, the concentration of phosphorus in mainstream is reduced. Furthermore, another aim was to recycle MAP particles as fertilizer. The reactor developed for this study is shown in Figure 2. The reactor is concentric cylinder type. The upper part of reactor has a larger diameter, and the separation of treated water and MAP particles taking place in that settling space. Air is blown into the inner cylinder, and that causes upward flow in inner cylinder and downward flow between inner and outer cylinder. Influent, seawater and MAP particles are mixed and circulated, and causes MAP particles to grow larger by crystallization. The mixed liquid flows to settling space and MAP particles settles there, and treated water overflows from the top of settling space. The treated water is returned to mainstream. There are baffles in settling space to guide downward flow. The volume of the inner cylinder is 99 L and the outer is 218 L. The volume of the settling space is 792 L. The produced MAP particles are drawn off from the bottom of reactor alongwith water by opening the solenoid valve for about a half minute. The produced MAP particles are white color, about 1 mm in diameter, and hard type granular material. The water is easily separated by fine screen with 0.2 to 0.3 mm bar spacing. The seawater was pumped up from the sea near the treatment plant. It contains around 1250 (mg/l) of Mg2+.

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Experimental conditions and Analysis The experiment was carried out from January 23rd 1996 to January 30th 1997. Three different influents with varying P concentration fed to the reactor. The experimental conditions are summarized in Table 1. Table 1. Experimental Conditions Exp. 1 2 3 Date 23.1.1996 to. 29.5.1996 30.5.1996 to. 15.7.1996 16.7.1996 to. 5 .1. 1997 Influent Flow (m3/d) 14.4-43.2 14.4-21.6 7.2-57.6 Source Belt Press and Centrifuge Diluted filtrate from Belt Press Filtrate from Belt Press RSF % 2-12 10 10-15 HRT Min 9.5-29 19-29 7-58 MV % 3.3-15 10-11 2.3-16

RSF-The ratio of seawater to the influent flow MV-The ratio of MAP to the reactor in volume

Influent

Grit chamber

Primary settling tank

Aeration tank

Final settling tank

Disinfect i -on tank

Effluent

Return sludge

Gravity overflow Flotation effluent Gravity thickening Flotation thickening Excess sludge

Digestion tank

Dewatering machine

Dewatered cake

Dewatered effluent

Seawater

MAP reactor

MAPParticles

Dryer etc

Rycycle as fertilizer

Figure 1 Flow of MAP pilot system

During the initial period, pH was controlled from 7.66 to 8.4 using NaOH to study the relation between pH and P removal efficiency. During the latter period, pH was controlled from 7.65 to 7.96 using NaOH due to the significant decrease of influent pH caused by the malfunction of sludge digestion. There is no data directly measured the velocity of circulation flow but the linear velocity (LV) of inner cylinder is 9.5 to 76.4 m3/m2h, and the air supply of airlift for circulation is 130 m3/ m2h.. The analysis of temperature, pH, T-P, D-P, NH4-N, D-Mg, and SS of the influent and effluent was conducted according to Sewage Analysis Methods [8].

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F 1200 mm

Settling space baffle Crystallization space outer cylinder f 350 mm inner cylinder f 200 mm sampling mouth

effluent

sampling mouth

influent

seawater air MAP collection mouth

Figure 2 Schematic of Pilot Scale Reactor

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3700 mm

RESULTS & DISCUSSIONS Influent and effluent The average influent water quality, effluent quality, P removal efficiency, and Mg/P are shown in Table 2. Table2 Influent & Effluent quality, P Removal Efficiency, and Mg/P Temp pH T-P D-P NH4-N D-Mg SS Mg/P (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) influent 19.4 7.75 Experiment 1 effluent 21.1 7.86 removal eff. influent Experiment 2 effluent removal eff. influent Experiment 3 effluent removal eff. 26.3 7.75 28.6 7.88 29.5 7.71 31.1 7.76 73.1 69.6 32.1 19.1 56% 73% 66.5 64.3 20.2 15.9 70% 75% 121 110 32.2 26.4 73% 76% 423 383 9% 623 517 17% 9.4 88 14.3 67 136 188 38 45 49 63 2.2 2.4 1.6

The T-P removal efficiency of Experiment 1, 2, and 3 were 56, 70, and 73%. The D-P removal efficiency of Experiments 1, 2, and 3 were 73, 75, and 76%, respectively. The T-P removal efficiency of Experiment 1 was low compared with other experiments although the D-P removal efficiencies are almost same. The reason is the high effluent SS concentration. The average effluent SS concentration of Experiment 1 was 188 (mg/l) which was around 3.0 to 4.2 times higher than the other effluents. Removal efficiency and operational conditions The relation between influent pH and D-P removal efficiency for the different HRTs is shown in figure 3. All data was taken without pH control.

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100 90 80 70 60 50 40 30 20 10 0 7.2 7.3 7.4 7.5 7.6 7.7 nfluent pH 7.8 7.9 8 8.1 8.2

D-P Removal (%)

HRT=1012min HRT=1419min HRT=29min

Figure 3. Relation between Influent pH and D-P Removal Efficiency When the HRT is 10 to 12 minutes and the influent pH is higher than 8.03, the D-P removal efficiency is above 70%. However, the efficiency is below 70% when the influent pH is 7.82 to 7.98. It is considered difficult to meet the D-P removal efficiency of 70% under this condition. When the HRT varies from 14 to 19 minutes and the influent pH is higher than 7.8, most results shows efficiency less than 70%. Again, it is considered difficult to meet the D-P removal efficiency of 70% due to this condition. When the HRT is 29 minutes and the influent pH is higher than 7.77, the D-P removal efficiency is above 70%. In this case, the influent D-P concentration was from 50.5 to 110 (mg/l), the Mg/P ratio was 1.4 to 3.1, the RSF was 9.0 to 10%, and the MV was 4.3 to 12.6%.

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Relation between influent flow and D-P removal efficiency

100 90 80 D-P Removal 70 60 50 40 30 20 10 0 0 10 (13.3) 20 30 (26.5) (39.8) 3 Influent Flow m /d 40 (53.1) 50 (66.3) 60 (79.6) y = -0.5411x + 87.131 2 R = 0.8812 y = -0.0476x + 83.752

Low Concentration Influent pH Unadjusted

y = -0.673x + 85.038 2 R = 0.7792

High Concentration Influent pH Unadjusted High Concentration Influent pH7.8 Adjusuted High Concentration Influent pH8.0 Adjusted

Figure 4. Relation between influent flow and D-P removal

In the low concentration influent (EXPERIMENT 1), D-P removal efficiency is more than 70% at influent flow of 22m3/d (LV29.2m/h, 4.1 kg/m3/d loading). In the high concentration influent without adding alkali (EXPERIMENT 3), D-P removal efficiency became more than 70% at treated water flow of 30 m3/d (LV39.8m/h, 9.5 kg/m3/d loading).If the pH is adjusted above 7.8, decrease in phosphorus removal was not observed thus showing its high dependency on pH.

Relation between influent phosphorus loading and effluent phosphorus concentration

50

Effluent P Concentration mg/l

40

30

20

Low Concentration Influent

10
(3.2)

High Concentration Influent (9.5) (15.8)

0 0.0 0.5

1.0

1.5 2.0 2.5 3.0 3.5 4.0 Influent P Loading kg/d kg/m3 d

4.5

5.0

Figure 5 Relation between influent phosphorus loading and effluent phosphorus concentration

In both low and high concentration influent, it was observed that there was a tendency that effluent phosphorus concentration becomes higher as the loading increases, although there was a limit in the effluent phosphorus concentration (Fig.5). In other words, in case of low concentration influent, effluent phosphorus concentration reaches to reaction equilibrium concentration by operational conditions such as pH and brings the phosphorus removal low, while in the case of high concentration influent, operation at higher loading condition was
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possible to achieve phosphorus removal at 70% or more.

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Relation between effluent pH and P removal efficiency Experimental result on varying the effluent pH in high concentration influent from unadjusted (7.65) to 8.6, while maintaining the influent flow in constant condition at 43.2m3/d (LV57.3m/h) is shown in Fig. 6.
100 90 80 70 P Removal % 60 50 40 30 20 10 0 7.4 7.6 7.8 8 8.2 Effluent pH 8.4 8.6 8.8 D-P Removal T-P Removal High Concentration Influent Treated Water Flow 43.2m3/d y = 210.24Ln(x) - 356.29 2 R = 0.8979 y = 210.41Ln(x) - 359.65 2 R = 0.9683

Figure 6. Relation between effluent pH and P removal The pH without adding alkali was 7.65, and the removal efficiency was approximately 70% for both D-P and T-P. It was observed that higher the operational pH, better removal efficiency could be obtained, thus showing the high dependency of phosphorus removal on pH.

Ratio of seawater to the influent flow (Mg/P) The figure 7 shows the relation between influent Phosphorus (P) ratio and seawater (Mg) injection ratio (Mg/P), and D-P removal efficiency. There was no clear relation between them at the time of pilot test but beaker test shows that when Mg/P ratio is high, removal ratio of D-P is high. To achieve 70% removal ratio of P, Mg/P ratio was required over 1.5. Therefore, Mg/P ratio for operating at pilot plant was set higher than 1.5 to react with variable P concentration influent.

100 90 80 D-P Removal 70 60 50 40 30 20 10 0 0 0.5 1 1.5 Mg/P Ratio 2 2.5 3 y = 20.011Ln(x) + 59.991 2 R = 0.7174

Figure 7 Relation of Mg/P and D-P removal efficiency

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The influence of seawater injection was studied based on the calculation at 200,000 m 3/d HSTP influent, digested sludge dewatering effluent was about 760 m3/d, and seawater injection was about 76 m3/d (10% of dewatering effluent). Therefore, the ratio of influent and seawater injected was 76/200,000 = 0.038%, the increase in concentrations of Na, Cl, and SO4 (as S) were 3.99 mg/l, 7.22 mg/l, and 0.32mg/l, respectively. From these values, we can say that seawater injection does not influence the treatment of mainstream.

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Relation between MV and D-P removal efficiency Relation between MV (MAP volume) and D-P removal efficiency was studied, as it was observed that phosphorus removal efficiency of MAP forming reaction becomes higher when the surface area of MAP in the reactor increases. The
100 90 80 D-P Removal 70 60 50 40 30 20 10 0 0.0 2.0 4.0 6.0 8.0 10.0 12.0 (Surface Area m2) 14.0 16.0 18.0 (65) Influent Flow 28.8m 3/d Low Concentration Influent pH Unadjusted High Concentration Influent pH7.8 Adjusted (114) (189) (236) (284) (50) (83) (117 (151)

result of the study is shown in Fig. 8. Figure 8. Relation between MV and D-P removal In the study using low concentration influent, decrease in D-P removal efficiency was observed when MV was lowered than 3.3%, however, in high concentration influent, D-P removal efficiency remained constant while MV was varied in the range of 4 to 12%. Relation of effluent SS Concentration and Phosphorus removal efficiency The T-P removal efficiency goes down when effluent SS concentration is high because of fine MAP particles were washout with SS (Fig.9). There are no relation between D-P removal and SS concentration of treated water. Produced MAP and Operation Cost The figure 10 shows produced MAP particles. The produced MAP particles are white color, about 1 mm in diameter,
100 90 80 Removal 70 60 50 40 30 20 10 0 0 50 100 150 200 250 Effluent Concentration mg/l 300 350 T-P Removal D-P Removal

and hard type granular material. The table 3 shows constitution and component of produced MAP particles. Figure 9 Relation of effluent SS concentration and P removal
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Table 3 Constitution of produced MAP particles Item N (%) P (%) Mg (%) K (mg/kg) Water content (%) As (mg/kg) Hg (mg/kg) Cd (mg/kg) Theoretical values 5.7 12.6 9.9 44.0 Measurement values (average) 5.5 12.5 9.6 565 41.8 0.7 <0.003 Less than quantitative limit

Figure 10 MAP particles The constitution of N, P, Mg and water content in MAP pellets are almost same as theoretical values. The constitution of As, Hg and Cd shows that MAP pellets are no problems for using as fertilizer. Operational cost for producing 1 kg of MAP was 56 yen (Table 4). The electric power consumption per 1 kg of produced MAP particles was 1.41 kWh and the heavy oil consumption were 57.5 ml.The personal expense and expense of expendable supplies are also required. Table-4Operational Cost (ScaleTreated flow 760m3/dMAP products 505kg/d) Item Operational Cost(yen/kgMAP)Remarks Electric power(8 yen/kwh) 11.3 1.4kwh/kgMAP Heavy oil (40 yen/l) 2.3 57ml/kgMAP Labor(2.8 million yen/year) 21.6 0.7 person/d Repair(2.7 million yen/year) 20.8 Total 56.0 CONCLUSIONS Operational condition of MAP production Pilot testing was conducted in order to develop a MAP system using seawater. By feeding the sidestream having 50.5 to 110 (mg/l) dissolved phosphorus (D-P), pH above 7.77, together with a 9.0 to 10 % seawater inflow into the reactor, holding a 4.3 to 13 % volume of MAP (MV), and with 29 minutes HRT, over 70 % D-P removal efficiency was achieved without pH control. It was observed that higher the operational pH, better removal efficiency could be obtained. Evaluation on using sea water as Mg source In the operation using seawater as Mg source, when Mg/P ratio was maintained above 1.5 (about 10% of influent), a stabilized result was obtained for phosphorus removal efficiency (70% of D-P), and the operation was easy in spite of the
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variation in influent phosphorus concentration. Chemical cost for using magnesium chloride and magnesium hydroxide for Mg source are quite high and also associated with handling problems. Therefore, it can be said that the method using seawater is able to reduce the production cost substantially, and is advantageous from the point of facilities and operation. Also, it was confirmed that seawater had no influence to the mainstream operation. Furthermore, the produced MAP can be used as fertilizer and it has equal or better quality as a fertilizer, and is an environmentally friendly product.

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ACKNOWLEDGEMENTS This study was conducted under the cooperative project of Kitakyushu City and JIWET with the help of the technical advisory committee. The authors appreciate the contribution of committee members and financial support from the Ministry of Construction. REFERENCES 1) Y., Suzuki, Advanced wastewater treatment technology and the 8th five year sewerage implementation plan, Journal of Sewerage, Monthly, .20, No.5, (1997), (in Japanese). 2) Wastewater Management Department Ministry of Construction, PLANNING AND DESIGNING GUIDELINE FOR SEWERAGE, 134-138, (1994), (in Japanese). 3) Murrel, L. S., Martia G. D., Kenneth M. R., and Joseph J. S., Ultimate Disposal of Phosphate from Waste Water by Recovery as Fertilizer, Effluent and Water Treatment Journal, Oct., 509-519, (1972). 4) S., Abe, Phosphate removal from dewatering filtrate by MAP process in full scale experiment at Seibu Wastewater Treatment Plant, Proceedings 4th CIWEM & JSWA Technology Exchange Workshop, 260-277, (1995) 5) N., Sugimori, T., Ito, T., Nakamura, Phosphorus recovery from sidestreams, Proceedings of the 32nd Annual Conference on Sewerage Research, 400-402, (1995),(in Japanese). 6) H., Tsuno, I., Somiya, M., Yoshino, Study on struvite recovery from digester supernatant, Journal of Japan Sewage Works Association, Research Journal, 28, No. 324, 58-77, (1991), (in Japanese). 7) Tentative Report of Study on Phosphorus Recycle using Seawater, Sewerage Bureau Kitakyushu City & JIWET, (1996), (in Japanese). 8) Wastewater Management Department Ministry of Construction and Water Management Department Ministry of Health, SEWAGE ANALYSIS METHODS, Japan Sewage Works Association, (1997), (in Japanese).

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