Adsorption Properties of Modified Zeolite for Ammonia Removal

Zuo Jinlong
Department of Environmental Engineering Harbin University of Commerce Harbin 150076, China; mdjzjl@163.com AbstractIn order that ammonia could be removed effectively from wastewater, zeolite has been modified and be used for adsorbing the ammonia. Meanwhile the chemical ingredient and surface analysis of zeolite has been investigated. SEM of modified zeolite showed that there were lots of cavities and multitudinous holes with medium and macropores diameters. Such structure would be very useful to help NH4+ ions enter into the pore in the zeolite. And the pore system of modified zeolite was simple, the pore diameter was middle pore with fewer surface areas. These structures of modified zeolite would be helpful to carry out ions exchange. The adsorption results showed that the data were fit to Langmuir isotherms for ammonium ion uptake onto modified zeolite. Thus the modified zeolite was suggested as a suitable material for adsorbing ammonia.
Keywords-modified zeolite; SEM; chemical ingredient analysis; surface analysis; ammonia adsorptive capacity; ion exchange;

TABLE I. % by wt. TABLE II.

CHEMICAL ANALYSIS OF MODIFIED ZEOLITE 70.03 15.78 0.37 2.65 0.38 9.55 1.77 RAW WATER QUALITY IN THE EXPERIMENT

Constituent SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O

Parameter pH COD BOD5 SS NH4+-N -1 Average (mg.L ) 7.07.6 40100 1550 1560 2040

II.

MATERIALS AND METHODS

A. Materials and wastewater quality The virgin zeolite used in the experiments was produced by Hailin of Heilongjiang province. The chemical analysis of the virgin zeolite sample is given in Table 1. The wastewater used in this project was from Harbin University of Commerce residential area wastewater, and the average wastewater quality was shown in Table 2. B. Experimental Apparatus The system is composed of the following items: 28 liter reactor made from 200 mm diameter transparent PVC pipe; the reactor is filled with 2000 g modified zeolite, under the modified zeolite was gravel bed with height of 100 mm. An acrylic plate was placed in the bottom of the column to support the modified zeolite and distribute backwash water and supply air. C. Experimental Methods During batch and continuous experiments, the ammonia nitrogen adsorptive capacities of virgin modified zeolite and biofilm covered modified zeolite was examined. The continuous experiment showed as Fig.1. The DO, ammonia of the influent and effluent was measured respectively, by adopting the Chinese EPA standard methods [23]. Preparation of biofilm covered modified zeolite: Firstly, the activated sludge was pumped through the modified zeolite column for several cycles, then the column operated in a batch mode (no outflow) and air was supplied for three days. When the biomass was found on the surface of modified zeolite, the influent solution was shifted to cultured solution. The conditions were controlled as follows: DO was maintained at

I.

INTRODUCTION

Because the stringent nutrient levels are being required in the effluents to protect water body, removal of nutrient from discharged wastewater has been required in many wastewater treatment plants. Ammonia nitrogen in the effluent has harmful effects on water resources [1-3]. Thus wastewater with high ammonia concentration must be treated before arriving at the receiving water [4-6]. The three most widely used methods for removal of ammonia from polluted water are air stripping, ion exchange and biological nitrification denitrification[7-9]. The ion exchange method is preferred over the other methods since it is stable, suits automation and quality control, and is easy to maintain [10-12]. As a kind of aluminum silicate minerals with a framework structure, zeolite has a high cation exchange capacities and high ammonia selective properties [13-16]. Furthermore it can act as a bio-carrier for nitrifying bacteria which oxidize ammonia to the nitrate anion [17-20]. Zeolite is a natural mineral that has been known for their ability to remove ammonia from polluted waters [20-22]. In this paper, zeolite is used for adsorbing the ammonia from waster water, moreover chemical and biological regeneration for ammonia removal was investigated. This study specifically aimed to: (1) modified zeolite properties such as SEM, chemical ingredient and surface analysis; (2) modified zeolite and biofilm modified zeolite for ammonia adsorption and ion exchange;
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TABLE III.
air pump

THE CHEMICAL INGREDIENT OF MODIFIED ZEOLITE

Content SiO2 TiO2 Al2O3 Fe2O3 MgO CaO MgO K2O Na2O P2O5 % 67.99 0.23 13.25 0.67 0.16 2.92 0.89 1.27 2.65 0.013

absorption phase regeneration phase back wash phase

NaHCO 3

3.5 3 2.5 ( ) 2 1.5 1 0.5

Before modification

After modification

influent solution peristaltic pump

regeration solution back wash pump

Figure 1. Schematic diagram of the continuous experiment

0 CaO Na2O Metal oxidation K2O

2.0mg/L-2.5mg/L, water temperature was kept at 20C-25C. Then biofilm covered modified zeolite was washed with distilled water to remove the remaining regenerant solution. III. RESULTS AND DISCUSSION

Figure 3. The metal oxides content in zeolite before and after modification

A. SEM of Modified Zeolite It can be seen from Fig.2, the structure of modified zeolite was very incompact, and there were lots of cavities and multitudinous holes with medium and macro pore diameters. And the pore diameter was mean. Such would be useful to help some ions such as NH4+ enter into the pore in the zeolite, or it was attachable as the carrier for the nitrifying biomass, moreover the ion exchange and chemical adsorption could be happen in the zeolite. B. Chemical Ingredient and Surface analysis To investigate the main contents change after modified methods, the chemical ingredient was analyzed of metal oxidants, the results was shown as Table 3. Because the cation NH4+ is easy to exchange with Na+ and 2+ Ca in zeolite, while the K+ cation cannot exchange with Na+ and Ca2+. As can be seen from Fig.3, after modification the content of Na+ and Ca2+ in zeolite increased from 1.77% and 2.6% to 2.65% and 2.92% respectively.

TABLE IV.

THE SURFACE ANALYSIS OF COMBINED MODIFIED ZEOLITE BET surface(m2/g) 6.88 7.59 7.95 Pore volume Mean pore (ml/g) diameter () 0.0195 0.0211 0.0299 114.33 166.45 186.49

Diameter(mm) 310 13 <1

But the content of K+ in zeolite decreased from 2% to 1.27%. This is the reason why the ammonia capacity of modified zeolite increased sharply in micro scale. The surface analysis of modified zeolite was investigated by BET standard methods, the results was shown in Table 4. As can be seen from Table 4, the properties of zeolite pore system have lots of difference from some others pore materials such as activated carbon usually used in water treatment process. Because the pore system of activated carbon was very complicated with the surface area of 1000 m2/g ~1300 m2/g, which consist of micropores (pore meter less than 1 nm), mespores (pore meter at the range of 1 nm~25 nm) and macropores (pore meter more than 25 nm). So the activated carbon has a porous micropores structure. Compared with activated carbon, the surface analysis in Table 4 showed that the pore system of modified zeolite after modification was simple, and the pore diameter was middle pore with fewer surface areas. These characteristics of modified zeolite have disadvantages of physics adsorption, but due to the diffusion pressure in the pore decreased; these structures of modified zeolite would be helpful to carry out ions exchange. C. Ammonia Adsorption Experiment 1) Batch Experiment

Figure 2. SEM photo of modified zeolite

TABLE V.

DATA OF ADSORBED AMMONIA BY VIRGIN MODIFIED ZEOLITE

DURING STATIC EXPERIMENT

Number Original concentration(mg/L)

1 50

2 100

5 250

6 300

150 200

Equilibrium concentration Ce(mg/L) 12.20 31.20 45.10 80.60 110.10 153.60 Ammonia adsorption capacity q(g/mg) 1/Ce 1/q TABLE VI. 3.78 6.88 10.49 11.94 13.99 14.64 6.51

According to Langmuir isotherms, the maximal NH4+ exchange per unit weight of virgin modified zeolite was 20.39 mg, and the maximal NH4+ exchange per unit weight of biofilm covered modified zeolite was obtained 16.75 mg. It was concluded that no significant differences in the adsorption capacity were detected between virgin modified zeolite and biofilm covered modified zeolite. 2) Breakthrough Experiment Fig.4 presents the results of a breakthrough curve with the ammonia nitrogen concentration of 20 mg/L and hydraulic loading rate of 2m3/m2.h. Fig.5 presents the results of a breakthrough curve with the ammonia nitrogen concentration of 10mg/L and hydraulic loading rate of 8m3/m2.h. As can be seen from Fig.4 and Fig.5, the hydraulic loading rate decreased from 8 m3/m2.h to 2 m3/m2.h, although the influent ammonia concentration increased from 10 mg/L to 20 mg/L, the breakthrough value was 560 BV in the virgin modified zeolite and 530 BV in the biofilm covered modified zeolite respectively. The results showed that longer retention times caused the similar ammonia adsorptive capacity with virgin modified zeolite or biofilm covered modified zeolite, the modified zeolite did not lose its adsorption capacity in spite of the biofilm covered.

81.97 32.05 22.17 12.41 9.08

264.55 145.35 95.33 83.75 71.48 68.31

DATA OF ADSORBED AMMONIA BY THE BIOFILM COVERED MODIFIED ZEOLITE DURING STATIC EXPERIMENT 1 50 2 10 3 150 4 200 5 250 6 300

Number Original concentration(mg/L)

Equilibrium concentration Ce(mg/L) 14.20 40.20 55.10 91.60 124.10 169.60 Ammonia adsorption capacity q (g/mg) 1/Ce 1/q 3.58 5.98 9.49 10.84 12.59 13.04 5.90

70.42 24.88 18.15 10.92 8.06

279.33 167.22 105.37 92.25 79.43 76.69

The ammonia adsorption capacity of virgin modified zeolite of and biofilm covered modified zeolite were shown in Table 5 and Table 6. As shown in Table 5 and 6, when the ammonia concentration in the solution increased, the ammonia adsorption capacity of virgin modified zeolite and biofilm covered modified zeolite was also increased. According to the Langmuir isotherm is always employed to describe the ion exchange process. So in this paper such ammonia exchange properties were described by Langmuir isotherm. The Langmuir isotherm is defined as: q = abCe/ (1+bCe) (1)

Where q is the amount of NH4+ exchange per unit weight of modified zeolite, Ce is the NH4+ concentration in the solution; The values of a and b are model parameters, a is the maximal NH4+ exchange per unit weight of modified zeolite, b is the Langmuir energy constant. Usually (1) also can be rearranged as follow: 1/q = (1/a) + (1/ (abCe)) (2)

Figure 4. Breakthrough curve with hydraulic load of 2m3/m2h

The data of virgin modified zeolite and biofilm covered modified zeolite gave good fit for Langmuir isotherm. Two Langmuir isotherms were good linear form, and the linear form related coefficients were 0.9895 and 0.9674 respectively. The results showed that the data obtained from batch studies were fit to Langmuir isotherms for ammonium ion uptake onto modified zeolite.

Figure 5. Breakthrough curve with hydraulic load of 8m3/m2h

Thus during the ammonia adsorptive experiment, the results of batch and breakthrough experiments showed that the difference of ammonia adsorption capacity between biofilm covered modified zeolite and virgin modified zeolite was not obvious. IV. CONCLUSIONS

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SEM of modified zeolite showed that there were lots of cavities and multitudinous holes with medium and macropores diameters. Such would be useful to help some ions such as NH4+ enter into the pore in the zeolite, or it was attachable as the carrier for the nitrifying biomass. The chemical ingredient and surface analysis of the modified zeolite showed that after modification the content of Na+ and Ca2+ in zeolite increased from 1.77% and 2.6% to 2.65% and 2.92% respectively, while the content of K+ decreased from 2% to 1.27%. The pore system of modified zeolite was simple, and the pore diameter was middle pore with fewer surface areas. These structures of modified zeolite would be helpful to carry out ions exchange. The results of batch and breakthrough experiments showed that the difference of ammonia adsorption capacities of virgin modified zeolite and biofilm covered modified zeolite were not obvious. V. ACKNOWLEDGMENT

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This research was supported by the 863 High Technology Research and Development Program2003AA601060 REFERENCES
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