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Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 Contents lists available at SciVerse ScienceDirect Journal of the Taiwan Institute of Chemical Engineers journal homepage: An investigation into the adsorption removal of ammonium by salt activated Chinese (Hulaodu) natural zeolite: Kinetics, isotherms, and thermodynamics Aref Alshameri a, Chunjie Yan a,*, Yasir Al-Ani b, Ammar Salman Dawood b, Abdullateef Ibrahim c, Chunyu Zhou a, Hongquan Wang a a b c Engineering Research Center of Nano-geomaterial of Education Ministry, China University of Geosciences, Wuhan 430074, China School of Environmental Studies, China University of Geosciences, Wuhan 430074, China State Key Laboratory of Biogeology and Environmental Geology, China University of Geosciences, Wuhan 430074, China A R T I C L E I N F O A B S T R A C T Article history: Received 2 February 2013 Received in revised form 2 May 2013 Accepted 6 May 2013 Available online 12 June 2013 The development of the process of sodium activation of zeolite has been an effective technique for enhancing the efficiency of ammonium removal. In this research, the optimum conditions for the activation of Chinese (Hulaodu) zeolite of the most effective parameters such as sodium concentration, stirring time, and temperature were determined. The most efficient conditions were selected according to the highest ammonium removal capacity. The characteristics of activated zeolite (ActZ) and its mechanism of ammonium removal were investigated and compared with that of natural zeolite (NZ). Additionally, both zeolites were analyzed by scanning electron microscopy (SEM), Zeta potential, X-ray diffraction (XRD), thermogravimetry (TG) and BET surface analysis. The activated zeolite revealed the highest ammonium removal efficiency reaching up to 98% based on stirring time, zeolite loading, initial ammonium concentration, temperature and pH. The adsorption kinetic was explored and fitted best with the pseudo-second-order model, whereas adsorption isotherm results illustrated that Langmuir model (LM) provided the best fit for the equilibrium data. Moreover, thermodynamic parameters such as change in free energy (DG8), enthalpy (DH8) and entropy (DS8) were also calculated. The parameters revealed that the exchange of ammonium ion by activated zeolite occurred spontaneously at ambient conditions (25 8C). It was concluded that when Chinese (Hulaodu) zeolite is activated under the condition of 1 M NaCl, 70 8C and stirring time of 30 min, an excellent removal of NH4+ was obtained. ß 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved. Keywords: Zeolite (clinoptilolite) Adsorption Activated zeolite Ammonium removal Kinetics and isotherm 1. Introduction Clinoptilolite (Na,K,Ca)6(Si,Al)36O7220H2O is one of the naturally existing zeolites. It is rich in silica and has a lower ionexchange capacity than other zeolites as well as less than that of many of the available synthetic ion-exchange resins. It generally exhibits a high selectivity for ammonium and metallic ions [1,2]. Clinoptilolite from different deposits has been widely reported as adsorbent for ammonium removal from wastewaters [3,4]. Natural zeolite, on the other hand, needs to be purified and modified in order to improve its ion-exchange [5] and adsorption properties before it can be used to remove ammonium effectively. Nitrogen compounds in aqueous environments are usually found in the form of ammonium ions (NH4+). Important sources of NH4+ include effluent from municipal sewage treatment plants, the application of fertilizer in agricultural practices and industrial processes all of * Corresponding author. Tel.: +86 18971579917; fax: +86 027 67885098. E-mail address: (C. Yan). which contributes to the accelerated incidence of eutrophication resulting in algal bloom in lakes and rivers [6–10]. Complete removal of NH4+ is required due to its toxicity to the majority of aquatic life. For example, the ammonium nitrogen concentration for most fish species must not exceed 1.5 mg NH4+ ion [11,12]. NH4+ concentration, in certain surface waters serving as a source of potable water, is much higher than the permissible level, due to large quantities of industrial and municipal wastewater being discharged into existing water resources [5,13]. This threatens the availability of safe drinking water and, thus, human health. For this reason, the prevention of nitrogen pollution with NH4+ removal from wastewater is of great importance [7,9,14,15]. Various methods including air stripping, biological methods and activated carbon have been used for NH4+ removal [16–19]. However, since biological methods do not respond well to shock loads of ammonium, unacceptable peaks of NH4+ over the discharging levels may frequently appear in the effluent. Also, high costs, poor regeneration and uncertainty of outcome are some of the frequently encountered limitations in the application of the biological method. Moreover, there is a high risk to safety during 1876-1070/$ – see front matter ß 2013 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved. A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 Nomenclature 555 2. Materials and methods 2.1. Raw materials the starting equilibrium concentrations (mg/L) C0 the final equilibrium concentrations (mg/L) Ce the volume of the working solution (L) V the mass of added zeolite (g) M k1 and k2 (1/min) and (g/mg min) are constants of adsorption the rate of adsorption (mg/g min) h Langmuir constant (L/mg) K Freundlich adsorbent capacity (mg/g (L/mg)1/n) KF the reciprocal of reaction order n adsorption capacity at time t (mg/g) qt adsorption capacity at equilibrium conditions qe (mg/g) maximum adsorption capacity (mg/g) qmax constant of intraparticle diffusion (mg/g min1/2) Kid a and k0 constants of Bangham equation the volume of solution (ml) of Bangham equation V the weight of adsorbent (g/L) of Bangham equation m the subsequent processing such as the aeration process which causes stripping effects for volatile compounds resulting in accidental releases, often causing odor and aerosol with health implications [20,21]. Contingency on temperature and climate conditions constitutes another disadvantage in this process [22]. Compared with the above mentioned methods, high safety, low cost [13,23–26] and relative simplicity of application and operation are some of the attributes that are attracting an increasing focus on the use of zeolite for environment applications [2,8,11]. The factors that influence ammonium removal performances are mainly pH, temperature, reaction time, initial concentration of NH4+, and adsorbent dosage. Although many previous studies have focused on these factors collectively [3,27,28], however, comparison of the results from the available literature indicates significant variability in the reported behavior. It seems that natural clinoptilolites from different places have different characteristics [9,10,29,30]. These differences in the characteristics of clinoptilolites are probably attributed to the differences in the geological formation of zeolite sources [21,31,32]. Therefore, each special zeolite material has its own special characteristics and still requires to be researched individually [11,27,31]. The main aim of this study is to determine the optimal conditions for the activation of Chinese (Hulaodu) zeolite to get the best results for the adsorption of NH4+ by salt treatment. The main focus of the study is the transformation of low grade Hulaodu’s zeolite to a high cation exchanger under appropriate activation conditions. An investigation and comparison of characteristics and the equilibrium removal of NH4+ ion onto both zeolites was also carried out. The specific objectives of this research is to study the sodium activation of zeolite samples and the effect of various parameters on zeolite activation such as sodium concentration, stirring time, and temperature. And to identify the key processes controlling the rate of ammonium adsorption by zeolite. In addition, the effects of pH, stirring times, initial concentration, adsorbent dosages and temperature on NH4+ removal for both natural and activated samples were investigated and compared. Adsorption isotherms, thermodynamics and reusability of zeolite for the removal of NH4+ ions were examined. A natural zeolite (NZ) was collected from Huludao city in China. Analytical grade inorganic chemicals, such as ammonium chloride (NH4Cl), sodium chloride (NaCl), sodium hydroxide (NaOH) and hydrochloric acid (HCl), were used. 2.2. Preparation and activation of zeolite A natural zeolite (NZ) was ground and passed through 200– 230 mesh sieves. The material was washed with distilled water to remove any non-adhesive impurities, and then dried in an oven at 100 8C for 24 h and finely crushed. The activation process was carried out by mixing NZ powder material with an aqueous solution of sodium chloride under the different conditions detailed below: Effect of sodium concentration: To study the effect of sodium concentration and batch activation, the sodium chloride concentration was varied from 0.5 to 2 mol/L with zeolite/ solution ratio maintained as 1 g/10 ml. The suspension was stirred in conical flasks (500 ml) using a magnetic stirrer water bath at a rate of 120 rpm and 90 8C for 2 h. Subsequently, the suspension was filtered and washed with distilled water. The wet activated material was dried at 70 8C in an oven for 24 h and used in batch adsorption experiments at an initial ammonium concentration of 100 mg/L with a pH 7 at 25 8C and stirring time of 24 h. The best sodium ion concentration for the activation of zeolite was selected as that corresponding to the highest NH4+ removal capacity (mg/g). Effect of time: For determining the optimum time required for activation zeolite from aqueous solution, a weighed quantity of zeolite (1 g) was added into the solution of 1 mol/L sodium chloride concentration and stirring time ranging from 0.5 to 3 h. The conditions applied above on the effect of sodium concentration experiment were repeated. The optimum stirring time for the activation of zeolite was selected as that corresponding to the highest NH4+ removal capacity (mg/g). Effect of temperature: The effect of temperature on activation of zeolite was investigated at different temperature values ranging from 10 to 90 8C. The sodium chloride concentration and stirring time were kept constant at 1 mol/L and 0.5 h, respectively. The optimum temperature for the activation of zeolite was selected as that corresponding to the highest NH4+ removal capacity (mg/g). 2.3. Analysis and characterization The activated and natural zeolites were characterized by XRD, SEM, EDX, TG, Zeta potential, chemical analysis and specific surface area (BET). Identification of mineral species in the zeolite samples was carried out by XRD pattern using a Germany D8-FOCOS X-ray diffractometer with Cu Ka (l = 0.154 nm) radiation operating at 40 kV and 40 mA and a step width of 0.058. Semi-quantitative weight percentages of samples were calculated by using mineral intensity factors. Textural characteristics of the activated and natural zeolites were performed using a Japanese Netherlands FESEM Quanta SU8010 electron microscope, operating at an accelerating voltage of 15 kV for photomicrographs as well as to analyze the Chinese-zeolite composition by Energy Dispersion Xray Spectrometry (EDS), USA, Apolloxp. The sample was initially placed in a vacuum chamber for coating with a thin layer (a few nanometers) of gold (Au). The specific surface area, pore size and volume of the material were evaluated by the nitrogen gas 556 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 adsorption method, with a heating rate of 10 8C/min. N2 adsorption–desorption experiments were performed at 77 K with an Automatic Volumetric Sorption Analyzer (ASAP2020, TSI, America), employing multipoint BET isotherm adsorption data fitting. Zeta potential measurements for the natural and activated zeolites, as a function of medium pH, were determined using Zeta Plusk equipment (zetasizer Nano ZS 90, Malvern, UK). A 103 mol/L solution of KNO3 and 60 mg/L of ammonium concentration were used. The medium pH was controlled by adding HCl (pH < 7) and NaOH (pH > 7) solutions, separately. The water content and zeolite decomposed were determined by a Thermogravimetric (TG) analyzer. TG/DSC analysis was performed on a NEZSCH, STA409PC-Germany, and thermal analysis system was in the range 30– 1200 8C. In addition, the composition of zeolite was analyzed by chemical method. Absorbance values of ammonium ion concentration in solution were read using a Chinese-Shimadzu UV-723Vis spectrophotometer. Quality control testing includes experiments with blanks and duplicates. 2.4. Adsorption rate, batch sorption studies All adsorptions in batch experiments were carried out using stopper conical flasks (500 ml), zeolite/liquid ratio of 1 g/100 ml, magnetic stirring water bath, a stirring rate of 120 rpm and a temperature at 25 8C. A stock solution (1000 mg/L) was prepared by dissolving NH4Cl in distilled water. For determining the optimum time required for ammonium removal by natural zeolite (NZ) and activated zeolite (ActZ) from aqueous solution, a weighed quantity of adsorbent (1 g) was added into solution of 80 mg/L ammonium concentration and was stirred for 10–420 min and 5–60 min of NZ and ActZ, respectively, at a fixed pH of 7. The effect of initial ammonium concentration in batch adsorption experiments was carried out by using initial ammonium concentration in the range of 10–240 mg/L and 10–400 mg/L for 300 min and 40 min for NZ and ActZ, respectively. The effect of pH on adsorption was investigated at initial ammonium concentration of 80 mg/L and performed in different pH values (2–10) at 25 8C. Batch adsorption was conducted at 300 and 40 min for NZ and ActZ, respectively. The pH of the solution was adjusted by 1 M HCl or NaOH solution. For determining zeolites loading effect, zeolite loading was varied from 0.2 to 2.2 g/100 ml at initial ammonium concentration of 80 mg/L. The zeolite–liquid was then stirred for 300 and 40 min for NZ and ActZ, respectively, at temperature 25 8C. Temperature of adsorption isotherms was studied at 25, 35 and 45 8C. A 100 ml of ammonium chloride solution of 80 mg/L concentration was equilibrated with 1 g zeolite for 40 min for ActZ. Samples were filtered through a 0.45 mm filter membrane after adsorption. The residual concentration of ammonium was determined by Nessler’s reagent spectrophotometry method at 420 nm. The removal efficiency (%) of zeolite and the amount of adsorbed ammonium ions (qe) were calculated, respectively, using the following equations: Removal efficiency ð%Þ ¼ qe ¼ C0  Ce  100 C0 C0  Ce M (1) (2) 3. Results and discussion 3.1. Activated zeolite Due to different results in activation of different zeolite samples, parameters, such as sodium concentration, stirring time and temperature, had to be investigated to obtain optimum activation conditions, and the results are shown in Fig. 1a–c. As can be seen from batch adsorption experiments (Fig. 1a–c), the temperature of 70 8C, stirring time of 30 min and 1 mol/L concentration of NaCl were the most effective in adsorption of NH4+ ions on Hulaodu natural zeolite (NZ). The optimum conditions obtained above for the activation of zeolite using NaCl were applied on NaOH for the adsorption of NH4+ ions at 100 mg/L of ammonium concentration, pH 7 and 25 8C. Its NH4+ adsorption capacity (mg/g) was compared with NaCl activation as shown in Table 1. The results showed that NaCl-activated zeolite (ActZ) had a higher NH4+ adsorption capacity value than NaOH-activated zeolite. This result was confirmed by EDS analysis (Fig. 2a and b) which showed that the Na+ content of the NaOH-activated zeolite (1.33%) was lower than that of NaCl-activated zeolite (2.10%). Higher NH4+ adsorption capacity means higher Na+ content [32–34]. From the above discussion, it can be concluded that ion exchange promoted by NaCl-activated zeolite (ActZ) is a more attractive zeolite preparation method than that of NaOH-activated zeolite. Therefore, NaCl-activated zeolite (ActZ) was selected for further study. 3.2. Natural and activated zeolite characteristics SEM and the qualitative composition analysis of EDS obtained from the grain of natural and activated zeolites are shown in Fig. 2. Fig. 2c illustrates that the main chemical elements (Al, Si, O, Na, Mg, K, Ca and Fe) are present in the structure of this natural zeolite, in agreement with the chemical composition (Table 2). Quantitative tests were also performed on both zeolites. The results from elemental analysis by EDS of NZ and ActZ as shown in Fig. 2a and c indicate that the Na+ content in NZ increased from 0.21% to 2.10% after activation. Meanwhile, the content of Ca2+, Mg2+ and K+ decreased from 3.44%, 0.81% and 1.53% to 1.08%, 0.58% and 0.76%, respectively. For this reason, the ammonium capacity of combined activated zeolite increased sharply in microscale [33,34]. The XRD patterns of NZ and ActZ are shown in Fig. 3a. X-ray diffraction did not show any changes in zeolite structure after activation. Mineralogical analysis of the zeolite samples was carried out using X-Ray Diffraction (XRD). The results showed that the natural zeolite contained clinoptilolite in the majority 93%, and small quantity of quartz 7%. Chemical components of natural zeolite are shown in Table 2. The Si/Al ratio calculated from these data was found to be 4.8. The ratio of Si/Al is an important factor in understanding the zeolite structure. When the ratio is over than 4.0, then the zeolite is a clinoptilolite-type and as such, the structure would not be broken easily at high temperature. This result was confirmed by thermogravimetric (TG) analysis as shown in Fig. 3b. It shows that the zeolite could stand temperatures of up to 869.2 8C without being decomposed and that it only undergoes a weight reduction of 0.07% at this temperature. It also, shows that the water content of zeolite was lost at 71.2 8C. The surface analysis of activated zeolite was investigated by Zeta potential and BET standard method and compared with that of natural zeolite. Fig. 3c shows that zeolite surface groups are mainly negative in the studied pH range and that the ammonium removal does not interfere much with the Zeta potential measurements, confirming the theory that the mechanism is not electrostatic (charge neutralization) but a result of an ion-exchange reaction. Moreover, the figure shows that activated zeolite is more negative than natural zeolite. The BET specific surface area, total pore volume, and average width pore size of the natural zeolite were measured to be 25.88 m2/g, 0.0032 cm3/g and 8.72264 mm, respectively. However, these values did not change significantly after activation of A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 Fig. 1. Removal capacity as a function of sodium concentrations (a), stirring time (b) and temperature (c). zeolite, 26.7074 m2/g of specific surface area, 0.004167 cm3/g of total pore volume and 9.64864 mm of average width pore size. These characteristics of activated zeolite have disadvantages for physical adsorption, but the results from equilibrium experiments do not match with this fact because the removal mechanism of ammonium by zeolites follows the ion-exchange reaction. Therefore, ion-exchange capacities of ammonium depend on dielectric strength between ammonium as well as 557 Fig. 2. SEM and EDS spectra analyses zeolite grain of NaCl-activated zeolite (ActZ) (a), NaOH-activated zeolite (b) and natural zeolite (NZ) (c). their affinities to zeolite. The size of micropores of the natural zeolite is in the range of 3–10 A˚ and micropores of the NaClmodified zeolite were more developed at the range of 5 A˚ than other cases. This implies that the NaCl–zeolite could selectively remove NH4+ ions which have a specific size. Also, owing to its small surface area, this zeolite is very stable against heat and acidity as reported by Tehrani and Salari [29] and Gottardi and Galli [35] who found that heat and acid activation does not result A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 558 Table 1 Comparison of NaCl and NaOH in zeolite activation at 100 mg/L of ammonium concentration, pH 7, 25 8C and stirring time of 24 h. Sodium ion used for activation Sodium concentration Ammonium removal (mol/L) capacity (mg/g) NaCl-activated zeolite NaOH-activated zeolite 1 1 5.921 4.552 in drastic changes in zeolite structure but increases Si/Al ratio, as a consequence of heat or acid activation. 3.3. Effect of stirring time As shown in Fig. 4a and b, the removal efficiency of NH4+ ions increased with increasing stirring time. 40% and 92% of NH4+ ions removal were completed within 10 min for NZ and ActZ, respectively, which also confirmed larger adsorption capacity of ActZ compared to NZ. The experimental data show that NZ could exceed 78% percentage removal at 300 min, but then, the removal efficiency plateaus. As to ActZ, the ammonium removal rate exceeds 98% percentage removal at 40 min and became increasingly slow with increasing stirring time. This may be attributed to the utilization of the most readily available adsorption sites of the zeolite that leads to a fast diffusion and rapid equilibrium attainment .On the basis of these results, 300 min and 40 min stirring period was selected for all further studies of NZ and ActZ, respectively. Beyond this level there is no noticeable increase in the adsorption and it is thus fixed as the equilibrium time. It can be said that the NH4+ ions were adsorbed by the exterior surface of the adsorbent. When the adsorption of exterior surface of the adsorbent reached the saturation point, the NH4+ ions enter the adsorbent pores and are adsorbed by the interior surface of the particles [34,36,37]. 3.4. Effect of initial ammonium concentration As shown in Fig. 5, the increment of removal efficiency was achieved in the ranges of 10–50 mg/L of NH4+ concentrations for both NZ and ActZ. This result is similar with that reported by Sarioglu [11] who concluded that the increase in removal efficiency was achieved between 8.8 and 40 mg/L of ammonium concentrations, indicating that the initial NH4+ concentration plays an important role in the adsorption of ammonium onto zeolites. Increasing the initial NH4+ concentration would increase the mass transfer driving force and therefore the rate at which ammonium ions pass from the bulk solution to the particle surface [37]. The result can be generally expected for clinoptilolite having micropores and macropores [7]. After 50 mg/L NH4+ concentration of both zeolites, the removal efficiency of ammonium decreased with increased initial NH4+ concentration. This is because the high initial ammonium concentration provided a greater driving force [38]. As a result, the NH4+ ion could migrate from the external surface to the internal micropores of the zeolite within a given stirring time [32]. The equilibrium was achieved when all the exchangeable ammonium and cation on the external and internal surfaces of the zeolite were reached [31]. Fig. 5 shows that the adsorption capacity of the activated zeolite was higher than that of natural zeolite at each initial ammonium concentration. Fig. 3. The XRD of activated and natural zeolites (a), TG of natural zeolite (b) and Zeta potential of activated and natural zeolites (c). 3.5. Effect of solution pH and the mechanism of adsorption The pH of the aqueous solution is an important factor controlling ammonium adsorption [21]. As shown in Fig. 6, pH played an important role for NH4+ adsorption of NZ and ActZ. The removal efficiency of both zeolites increased with increasing pH Table 2 Chemical composition of the natural zeolite (wt.%). NZ SiO2 Al2O3 TFe2O3 TiO2 MgO Na2O CaO K2O P2O5 MnO H2O L.O.I. 66.34 12.23 0.99 0.16 0.98 0.73 3.17 1.37 0.027 0.026 5.06 13.88 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 559 Fig. 4. Effect of stirring time on NH4+ removal capacity of natural zeolite (a) and activated zeolite (b) (initial NH4+ concentration: 80 mg/L, 25 8C and pH 7). from 2 to 7 and then it decreased gradually from pH 8 to 10 with the maximum value being achieved at pH 7. An almost similar trend has been reported for ammonium adsorption onto zeolite by different researchers [21,30]. The behavior of ammonium as a function of water’s pH can be explained by considering the change in density of hydrogen ions, the dominant ionic species of ammonium and the surface charge of zeolite as a function of water’s pH. The pHzpc of natural zeolite and activated zeolite were 7.7 and 7.8, respectively, implying that the zeolite particle’s surface is uncharged at water pH of 7.7 and 7.8 of natural and activated zeolites; the zeolites particle’s surface has a positive charge at water pH below 7.7 and 7.8, and it is negatively charged at water pH above 7.7 and 7.8. This indicates that the surface of zeolite is negatively charged at pH of above 7 [39]. For ammonium adsorption, according to the relation of ammonium dissociation in water as a function of pH, NH4+ ions is the dominant species of ammonia nitrogen in water at pH of below 7 while the molecular form, ammonia (NH3) is dominant at alkaline pH. By considering the above facts, the increase in adsorption of ammonium with the increase in water’s pH up to the maximum point (pH 7) can be attributed to a decrease of hydrogen ions in solution corresponding to an increase in pH, and thus a reduction of the competition between hydrogen ions and NH4+ ions for adsorption/exchanging sites onto zeolite particles [6,40]. The decrease of ammonium adsorption with the increase of water’s pH above 7 is related to the increase in percentage of molecular ammonium, which resulted in the reduction of ion–exchange potential [10]. Fig. 5. Effect of initial ammonium concentration on NH4+ removal capacity of the ActZ and NZ (stirring time: 40 min and 300 min for ActZ and NZ, respectively, at 25 8C and pH 7). 3.6. Effect of adsorbent dosage As illustrated in Fig. 7, the removal efficiency of NH4+ ions by both zeolites increases with increasing amount of both zeolites. This effect can be attributed to an increased surface area and number of adsorption sites [41]. As can be seen in Fig. 7, the ammonium removal rate of ActZ increases more rapidly than that of NZ and attains a plateau at 98.73% when the adsorbent dosage was 1 g indicating that the NH4+ ions removal was negligible at higher adsorbent dosage. The natural zeolite attains a plateau at 94.5% when the dosage was 1.8 g as shown in Fig. 7. Thus, both of them reached a balance of approximately 98% when the adsorbent dosage for ActZ and NZ was 1 g and 1.8 g, respectively. This may be attributed to a large adsorbent amount which effectively reduces the unsaturation of the adsorption sites and correspondingly, the number of such sites per unit mass comes down resulting in comparatively less adsorption at higher adsorbent amount [37,41]. Hence, when the ammonium is exchanged completely with cations on the zeolite surface at a certain amount of zeolite loading, the NH4+ removal reached equilibrium. 3.7. Kinetics of ammonium exchange To identify the key process controlling the adsorption rate, several models must be checked for suitability and consistency over a broad range of the system parameters. Pseudo-first- and -secondorder and Bangham equations as well as the diffusion-based Fig. 6. Effect of pH on the removal of NH4+ ions (adsorbent dosage: 1 g/100 ml; stirring time: 40 min and 300 min for ActZ and NZ, respectively; initial NH4+ concentration: 80 mg/L at 25 8C). 560 A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 Fig. 7. Effect of adsorbent dosage on the removal of NH4+ ion (stirring time: 40 and 300 min for ActZ and NZ, respectively; initial NH4+ concentration: 80 mg/L at 25 8C and pH 7). Weber–Morris model are used to fit the experimental data and can be summarized as follows. The linear form of pseudo-first, pseudo-second order models for boundary conditions of q = 0 at t = 0 and qt = qe at t = te are as follows: The pseudo-first-order Eq: : lnðqe  qt Þ ¼ ln qe  k1 t (3) t 1 1 ¼ þ t The pseudo-second-order Eq: : qt k2 q2e qe (4) h ¼ k2 q2e     C0 k0 m ¼ log þ a log t Bangham Eq: : log log 230V C 0  qt m (5) The adsorption kinetics of ammonium by ActZ and NZ are presented in Fig. 8a–e. The kinetic data were better fitted by the pseudo second order model than other models as indicated by higher R2 values (Table 3). Also it shows a higher sorption rate for ActZ than NZ. The pseudo second order model indicates that chemisorption dominated in the adsorption process [42]. The difference in the adsorbed concentration of adsorbate at equilibrium (qe) and at time t (qt) is the key driving force for the adsorption, and the adsorption capacity is proportional to the number of active adsorption sites on the adsorbent [43]. There are three steps involved in pseudo second order kinetic model: (i) the ammonium ions diffuse from liquid phase to liquid–solid interface; (ii) the ammonium ions move from liquid–solid interface to solid surfaces; and (iii) the ammonium ions diffuse into the particle pores [23]. Herein, the diffusion of ammonium ions from aqueous phase was much faster than the surface and intraparticle diffusion processes because the adsorption was performed under stirring conditions [22]. To reveal the relative contribution of surface and intraparticle diffusion to the kinetic process, the kinetic adsorption data were further fitted with the Weber–Morris model using Eq. (6). WeberMorriss Eq: : qt ¼ kid t 1=2 þ C (6) Intraparticle diffusion is assumed to be the sole rate-controlling step if the regression of qt versus t1/2 is linear and the plot passes through the origin [44]. Our fitting results show that the regression was linearly, but the plot did not pass through the origin (C 6¼ 0). Therefore, the adsorption kinetics of NH4+ ions on zeolite was regulated by both surface and intraparticle diffusion processes. As can be seen from Fig. 8d and e, ammonium exchange by both zeolites involves two stages. These two stages suggest that the ammonium exchange process proceeds by surface sorption and intraparticle diffusion. It has been suggested that the first one can be attributed to the instantaneous occupation of most available surface sites by exchanging NH4+ ions onto zeolites particles. The surface of zeolites was negatively charged at water pH below 7 (Fig. 6) and its rate is very fast. The second region is due to a gradual adsorption stage, where the ammonium ions enter into zeolites particle by intraparticle diffusion through the pores. The values of intercept C provide information about the thickness of the boundary layer and the resistance to the external mass transfer increases as the intercept increases. The constant C was found to increase from NZ (1.3642 mg/g) to ActZ (3.7406 mg/g) as shown in Table 3, which indicates the increase of the thickness of the boundary layer and decrease of the chance of the external mass transfer and hence increase of the chance of internal mass transfer [37,41]. Table 3 presents the results of fitting experimental data to the pseudo-first, pseudo-second-order, Bangham and intraparticle diffusion models. It can be seen from Table 3 that the correlation coefficient R2 varies in the order: pseudo-second order > Bangham > intraparticle diffusion > pseudo-first order model under all experimental conditions, which indicates that the pseudo-second-order model is most suitable in describing the adsorption kinetics of ammonium on zeolite. 3.8. Ammonium exchange isotherms Isotherm fitting with model equations is a key issue to explore adsorption mechanisms. Langmuir model (LM) and Freundlich model (FM) were evaluated as follows: LM is based on the assumption that each active site can only hold one adsorbate molecule. The linear form of LM is expressed as: Ce 1 1 ¼ þ Ce kqmax qmax q (7) FM endorses the heterogeneity of the surface and assumes that the adsorption occurs at sites with different energy of adsorption. It is described as: log q ¼ log kF þ 1 log C e n (8) The linear plot of Langmuir isotherm of ActZ and NZ is shown in Fig. 9a. It is noted that the values of qmax and k were calculated from the slope and the intercept of the plot using Eq. (7) and are given in Table 4. It will be seen that applicability of the simple Langmuir equation for the present isotherm data indicates that the Langmuir equation was able to properly describe the isotherm of ammonium on the two zeolites (correlations coefficient >0.97). As shown in Table 4, the ActZ had much higher ion exchange capacity than NZ. A comparison with other zeolites from various literature reviews, Nguyen and Tanner [14] reported a qmax value of 5.76 mg/g ammonium adsorption on Australian natural zeolite. It has also been reported that the qmax of ammonium removal using a Turkish natural clinoptilolite was 8.1 mg/g [8]. Meanwhile a qmax value of 0.085 mg/g was reported by Demir et al. [36]. Fig. 9b shows the linearized Freundlich adsorption isotherm of ammonium curve and the Freundlich parameters is presented in Table 4. The FM of ActZ provides a slightly more consistent fit to the data compared with the FM of NZ. Similar values of 1/n which are less than 1 have been reported for NH4+ removal using natural zeolites from different countries [11,36]. To sum up, for the two zeolites, the experimental data are better fitted by the LM than FM as can be seen from the higher R2 in A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 561 Fig. 8. Pseudo-first order (a), pseudo-second-order (b), Bangham kinetic plots (c) and intra-particle diffusion of both zeolites ActZ (d) and NZ (e) for NH4+ removal. Table 4. In Langmuir and Freundlich equations, coefficients K and KF represent the maximum amount that can be sorbed. Both values for K and KF indicated that the activated zeolite has the higher sorption capacity than the natural zeolite as shown in Table 4. Table 3 Kinetic parameters for NH4+ removal using various kinetic models. Kinetic model Parameters Pseudo-first order K1 (min1) qe (mg/g) R2 Absorbent ActZ NZ 0.0888 0.0165 0.119123 2.5126 0.954 0.918 Kinetic model Parameters Pseudo-second order h (mg/g min) qe (mg/g) R2 Absorbent ActZ NZ 2.7156 0.1646 3.821 3.28 0.999 0.997 Kinetic model Parameters Bangham model K0 a R2 Absorbent ActZ NZ 201.609 25.616 0.0379 0.2981 0.979 0.958 Kinetic model Parameters Intraparticle diffusion model Kid C R2 Absorbent ActZ NZ 0.0102 0.0977 3.7406 1.3642 0.957 0.966 3.9. Thermodynamic study The effect of temperature on ammonium exchange was studied at 25, 35 and 45 8C. Fig. 10 indicates that the amount of ammonium exchanged onto zeolite increases with a decrease in temperature. A similar trend was also observed of some adsorbents, including Turkish clinoptilolite [8], Turkish zeolite [3], flyash and sepiolite [40], and NaA zeolite [45]. This may be due to a tendency for the ammonium molecules to escape from the solid phase to the bulk phase with the solution temperature increase [3,45]. In contrast, increases in the NH4+ adsorption capacity with increasing temperature have been reported for some other adsorbents [2,9]. Therefore, by comparing the results of the present work with those of the literature, it can be concluded that the effect of temperature on the adsorption of ammonium depends on both the nature of the adsorbent and the selected experimental conditions [21]. Furthermore, ammonium exchange capacity decreases with increasing temperature due to a weakening of the attractive forces between NH4+ and adsorbent sites [41] and when the temperature increases, solubility of ammonium increases and its adsorption decreases [37]. The thermodynamic parameters, such as Gibbs energy (DG8), enthalpy (DH8), and entropy (DS8), for the adsorption of ammonium on zeolites were calculated using the following equations: K0 ¼ qe Ce DG ¼ RT ln K 0 (9) (10) A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 562 Fig. 9. The linearized Langmuir (a), Freundlich (b) of ActZ and NZ and Langmuir (c), Freundlich (d) adsorption isotherm of NH4+ curve at different temperature of ActZ. Table 5 Change of thermodynamic parameters with temperature. DG ¼ DH  T DS ln K 0 ¼  DH  RT þ (11) DS (12) R Eq. (12) represents a mathematical relationship between K0 and 1/T. The values of K0, DG8, DH8 and DS8 parameters are summarized in Table 5. Change in the standard free energy DG8 has negative values (2.8662 and 1.3052 kJ/mol) at 25 and 35 8C, respectively, but positive value (0.224 kJ/mol) at 45 8C. The negative values of free energy change (DG8) indicate that this adsorption process is spontaneous; therefore, no energy input to the system is required. The higher negative value reflects a more energetically favorable adsorption [46]. For that reason, more energetically favorable adsorption occurs at 25 8C. Change in the standard enthalpy DH8 indicates a negative value of 49.384 kJ/mol; therefore, ammonium exchange is an exothermic process. Also, Temperature (8C) K0 DG8 (kJ/mol) DH8 (kJ/mol) DS8 (kJ/mol) 25 35 45 2.89 2.01 0.82 2.8662 1.3052 0.224 49.384 0.1561 the negative value of the standard entropy change DS8 (0.1561 kJ/ mol) suggests that the randomness decreases the removal of NH4+ ions on the clinoptilolite [47]. The linear plot of LM and FM isotherm of ActZ at 25, 35 and 45 8C is shown in Fig. 9c and d. The LM and FM parameters are presented in Table 5. The maximum value of K and KF at 25 8C indicates that the NH4+ adsorption process is most effective at 25 8C. Comparing the correlation coefficients in Table 5 reflects Table 4 Constants for equilibrium isotherm models of NZ and ActZ. Isotherm model Parameters Langmuir Qmax (mg/g) K (L/mg) R2 9.515 9.533 9.794 0.444 0.313 0.123 0.9982 0.9986 0.967 3.445 0.1998 0.9772 ActZ 25 8C 35 8C 45 8C NZ 25 8C Isotherm model Parameters Freundlich KF ((mg/g)/(mg/L)1/n) 1/n R2 3.5743 3.0634 2.0305 0.2992 0.3043 0.3938 0.9716 0.9442 0.8867 1.252 0.5192 0.7363 ActZ 25 8C 35 8C 45 8C NZ 25 8C Fig. 10. Effect temperature on the exchange isotherm of NH4+ on activated zeolite (ActZ). A. Alshameri et al. / Journal of the Taiwan Institute of Chemical Engineers 45 (2014) 554–564 References Table 6 Data about adsorption and regeneration of zeolite. Cycles Ammonium adsorption capacity (mg/g) 563 1 2 3 4 5 5.633 5.03 4.51 3.78 3.11 that LM yields a much better (R2 = 0.967–0.998) fit than that of the FM (R2 = 0.887–0.971). 3.10. Desorption and reusability Accordingly, the ion-exchange and electrostatic adsorptions are probably the main mechanisms for NH4+ ions removal by zeolite under the selected conditions, through the following reactions (Eq. (13)): Ammoniumremoval : ðzeoliteNaþ Þ þ NH4 þ ! ðzeoliteNH4 þ Þ þ Naþ (13) In this study, adsorption experiments were performed using 1 g zeolite and 100 ml of 60 mg/L NH4+ at 25 8C for 40 min, and desorption of adsorbed NH4+ onto zeolite was studied using 1 mol/ L NaCl, with zeolite/liquid ratio of 1 g/10 ml for 30 min at 70 8C, and consecutive adsorption–desorption cycles were repeated four times. The results are shown in Table 6. There was a slight decrease with the increase of cycle times in adsorption efficiency from 5.633 mg/g for the first cycle to 3.11 mg/g for the fifth cycle. The zeolite that was regenerated by four cycles in sodium solution had high ammonium-removal efficiency with its adsorption efficiency of 3.11 mg/g which is close to that of natural zeolite (3.344 mg/g). 4. Conclusion The characteristics of Chinese (Hulaodu) natural zeolite (NZ), activated zeolite (ActZ) and their efficacy in removing ammonium were investigated. The following conclusions were made from the experimental results:  1 mol/L of NaCl, stirring time of 30 min and 70 8C were found to be the optimum activation conditions for the zeolite with excellent removal of NH4+.  The highest adsorption capacity was obtained at pH 7 for both zeolites and the maximum ammonium adsorption was rapidly attained within 40 min and 300 min for activated zeolite and natural zeolite, respectively.  Langmuir adsorption isotherm of both zeolites fit well with the equilibrium adsorption data, and this adsorption process agrees very well with pseudo-second-order kinetics rate model.  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