Ammonium removal from aqueous solution by silver nano particles

THAI NGUYEN UNIVERSITY UNIVERSITY OF AGRICULTURE AND FORESTRY VU TRA GIANG AMMONIUM REMOVAL FROM AQUEOUS SOLUTION BY SILVER NANO PARTICLES BACHELOR THESIS Study Mode: Full-time Major: Environment Science and Management Faculty: Advanced education program office Batch: 2014 - 2018 Thai Nguyen, May 31, 2018 Thai Nguyen University of Agriculture and Forestry Degree Program Bachelor of Environmental Science and Management Student name Vu Tra Giang Student ID DTN 1454290072 Thesis title Ammonium removal from aqueous solution by silver nano particles Supervisor(s) Dr Van Huu Tap (Thai Nguyen University of Science) Supervisor’s signature (s) Abstract: NH4+ is a pollutant from human activities that affects the health of plants, animals and human It’s very important to remove it from contaminated waters This study aims at synthesizing silver nanoparticles (AgNPs) by chemical reduction method In this work, silver nanoparticles were prepared using silver nitrate with a reducing agent is sodium borohydride and Poly Vinyl Pyrrolidone (PVP) which is used as stabilizing agents The size of crystalline for AgNPs was measured by UV– vis spectroscopy and flourier transform infrared (FTIR) The properties of nanosilver particles (AgNPs) have been studied using scanning electron microscope (SEM) The capability of nanoparticles to remove NH4+ from contaminated solution was then studied Parameters like types of AgNPs, pH of ammonium solution, contact time, adsorbent dosage and initial ammonium concentration were studied Ammonium removal increased when increased in the adsorbent dosage (from 0.228 i mg/25mL to 2.28 mg/25mL), pH from to 9, contact time from to 60 and decreased in initial concentration of NH4+ The most appropriate conditions for Ammonium adsorption onto AgNPs in batch experiments obtained at pH 9, contact time of 60 min, 1.824 mg AgNPs/25 mL of Ammonium solution with initial concentration of mg/ L At this condition, the highest adsorption capacity of Ammonium onto AgNPs reached 100.48 mg/g Isotherm adsorption was also described by the Langmuir model with a constant correlation (R2) is 0.9339 With highest R2 (0.885), the adsorption kinetic of Ammonium onto AgNPs obeyed Elovich model with the chemical sorption process Keywords Ammonium, AgNPs, Adsorption Number of pages: 41 Date of submission: 15/09/2018 ii ACKNOWLEDGEMENT I would like to express my special thanks of gratitude to Dr Van Huu Tap who in spite of being extraordinarily busy with his duties, took time out to hear, guide, keep me on the correct path and complete report during the time of conducting the research, which also helped me know about so many new things I am really thankful to him I would also like to express my great appreciation to Dr Vu Xuan Hoa for his constant support, patient guidance and suggestions related to my work Finally, I would also like to thank my parents and friends who helped me a lot in finalizing this project within the limited time frame Thank you all very much! Thai Nguyen, August 2018 Student Vu Tra Giang iii TABLE OF CONTENTS ACKNOWLEDGEMENT iii LIST OF FIGURES vi LIST OF TABLES vii LIST OF ABBREVIATIONS viii PART I INTRODUCTION 1.1 Research rationale 1.2 Research’s objectives 1.3 Research’s questions and hypothesizes 1.4 Limitations PART II LITERATURE REVIEW 2.1 Ammonium ion 2.1.1 Ammonium ion in water 2.1.2 Sources of Ammonium pollution 2.1.3 Standard of Ammonium ion in water 2.2 Effect of Ammonium 2.3 Silver nanoparticles 2.4 Adsorption 2.5 Research projects on ammonium treatment 10 PART III METHODOLOGY 11 3.1 Materials 11 3.1.1 Laboratory instruments 11 3.1.2 Ammonium NH4+ solution 11 3.1.3 Preparation of adsorbent (AgNPs) 11 3.2 Adsorption experiments of Ammonium (NH4+) onto AgNPs 12 3.2.1 Method of ammonium analysis 14 3.2.2 Measurements 15 3.2.3 Data analysis 16 PART IV RESULTS AND DISSCUSSION 17 4.1 Characterization of Silver nanoparticles (AgNPs) 17 iv 4.2 Effect of type AgNPs 19 4.3 Effect of pH 19 4.4 Effect of contact time 21 4.5 Effect of adsorbent dose 23 4.6 The effect of NH4+ concentrations 24 4.7 Adsorption isotherm 25 4.8 Adsorption kinetics of AgNPs 29 PART V CONCLUSIONS 33 REFERENCES 34 v LIST OF FIGURES Figure 1: The relationship between Ammonia Ionization and pH Figure Characteristic of AgNPs: (a) The absorption spectra of silver solution; (b) The TEM image of the AgNPs; (c) The distribution of AgNPs size obtained from Fig 2b; (d) FTIR spectra of pure starch and ST0.2 sample; (e) XRD patterns of synthesized AgNPs 18 Figure Effect of types of AgNPs on adsorption of Ammonium 19 Figure Effect of pH on adsorption of Ammonium by AgNPs 21 Figure Effect of contact time on adsorption of Ammonium by AgPNs 22 Figure Effect of AgPNs dose on adsorption of Ammonium 23 Figure Effect of initial Ammonium concentration 25 Figure Equilibrium adsorption prediction of Ammonium on AgNPs by Langmuir and Freundlich models (contact time= 60 min, Co =10 mg/L) 27 Figure Kinetics modelling of NH4+ sorption onto AgNPs (Co: 10 mg/L; adsorbent dose: 1.6 mL/25 mL; initial pH: 9) 31 vi LIST OF TABLES Table 1: Adsorption isotherm parameters and correlation coefficients of Langmuir and Freundlich models for Ammonium adsorption on AgNPs 28 Table 2: Calculated kinetic parameters of models of Ammonium adsorption on AgNPs 30 vii LIST OF ABBREVIATIONS NPs Nano particles AgNPs Silver nano particles Hb Hemoglobin NH4+ Ammonium ions WHO World Health Organization viii PART I INTRODUCTION 1.1 Research rationale The treatment of nitrogen compounds (nitrate, nitric and ammonia nitrogen) directly from water plants or indirectly from agriculture and filtering from sludge into landfill and fields led to eutrophication of the muscles, water body It has been widely reported that ammonium nitrate (NH4+-N) is a very common chemical species in aquatic ecosystems and its toxic effect on life is very high (Haseena.P.V et al., 2016) Water contains ammonium, nitrite, and nitrate, the result of the decomposition of organic matter or pollution from waste water In particular, ammonium is the most toxic for fish and aquatic species Nitrite is formed from the reaction of organic and ammonium nitrate and with the participation of bacteria The nitrite is then oxidized to nitrate In addition, nitrate is present in the water source due to wastewater from the chemical industry, from the field using chemical fertilizers, landfill leaks, and rain water runoff The presence of nitrogen compounds in the chemical composition of water indicates signs of water pollution Clean water standards specify that ammonium is less than mg/l The drinking water standard specifies that Ammonium is less than 1.5 mg/l (WHO) Ammonium itself is not too toxic to the body, but if it is present in water at levels beyond the allowed standard it can be transformed into carcinogens and other dangerous diseases Studies have shown that 1g of ammonia is converted to 2.7 g of nitrite and 3.65 g of nitrate while the content of nitrite is 0.1 mg / liter and nitrate is 10-50 mg / liter (Europura, 2016) Langmuir model In this model, adsorption occurs uniformly on the active sites of the adsorbent, and once the active sites are occupied by adsorbents, the adsorption is naturally terminated at this site The non-linear Langmuir equation is (Shen W et al., 2009, Ho YS et al., 2005): (1) Where KL is the equilibrium constant (L mg−1), qmax is the maximum adsorption capacity (mg g−1) of adsorbent, C is the equilibrium concentration (mg L−1), q is the amount of metals adsorbed at equilibrium (mg g−1) The linear Langmuir model is given by following equation: (2) Where qm and b are the saturated monolayer adsorption capacity and the adsorption equilibrium constant A plot of Ce/qe versus Ce would result in a straight line From the slope and intercept, the maximum adsorption capacity and bond energy of adsorbates can be calculated Freundlich adsorption isotherm 26 The Freundlich equation is an empirical model allowing for multilayer adsorption on sorbent The non-linear form of Freundlich model is (Rahmani A et al., 2010): (3) The linear form of Freundlich model can be expressed as: (4) where qe is loading of adsorbate on adsorbent at equilibrium (mg g-1); KF is indicator of sorption capacity (mg1-n Ln g−1), n is adsorption energetics and Ce is aqueous concentration of adsorbate at equilibrium (mg L−1) Figure 8: Equilibrium adsorption prediction of Ammonium on AgNPs by Langmuir and Freundlich models (contact time= 60 min, Co =10 mg/L) 27 Based on the results of the ammonium adsorption (NH4+) analysis at concentrations on AgNPs, the Langmuir and Freundlich adsorption models were determined to calculate the adsorption parameters The results are shown in Table Table 1: Adsorption isotherm parameters and correlation coefficients of Langmuir and Freundlich models for Ammonium adsorption on AgNPs Unit Value Langmuir model Qomax m/g 263.37 KL L/mg 0.518 R2 — 0.9339 KF (mg/g)(mg/L)n 128.14 nF — 0.559 R2 — 0.9086 Freundlich model Table shows that calculated maximum adsorption capacity (Qmax) of AgNPs for NH4+ reached maximum value of 263.37 mg/g at 1.824 mg/25mL of AgNPs dose in Langmuir model KL is the Langmuir constant (L/mg) it explains the ability of a specific adsorbent to be in equilibrium with adsorbate In Freundich model, the calculated value of KF and nF (Table 1) was 128.14 and 0.559, respectively, proved that NH4+ adsorption process was favorable 28 It was observed from experimental data as shown in Fig that an increase in the initial concentration led to an increase in the amount of NH4+ adsorbed by AgNPs The various fitting parameters of the sorption isotherms along with the goodness of fit (R2) are listed in table It was observed that both the isotherms gave satisfactory fitting though the best fit was observed for Langmuir isotherm as evident from its R2 value of 0.9339 Increasing concentration also results in a higher equilibrium capacity being obtained for any given set of conditions Initially a sharp increase in capacity can be observed with increasing concentration, reaching a maximum This maximum value is indicative of the fact that the ion exchange surface is increasingly saturated with the ammonium ion and is reflected by the accompanying reduction in removal efficiency The same trend has been demonstrated through research by (Liang et al., 2016) and Ivanova et al., 2010) 4.8 Adsorption kinetics of AgNPs The kinetic of Ammonium adsorption on AgNPs was determined by using kinetic models, including pseudo-first-order kinetic, pseudo-second-order (Lagergren et al., 1898, Ganesapillai et al., 2018) and Elovich models (Yangyang Li et al., 2009) The linear form of pseudo first-order kinetic model (Hossain et al., 2012) is as follows: ln(qe  qt )  ln qe  kl t (4) The adsorption rate (kl) is calculated from linear regression analysis from the slope of linear plot of experimental data The kinetic data were also analyzed by pseudo-second order equation and the linear form (Ho YS et al., 1998): 29 t 1   t qt k qe qe (5) where, k2 is the constant of pseudo-second-order rate; qe is the sorption capacity at equilibrium; and qt is the adsorption capacity at time t If the initial adsorption rate, as h = qt/t when t approaches to 0, h (mg/g.min) (Ho YS et al., 2000) as: h  kqe2 (6) Equation of Elovich model is presented as follows: qt= β.ln(αβt) Where, α is the initial adsorption rate (mg/g.min); β is the adsorption constant (g/mg) The model’s parameters are presented in Table Table 2: Calculated kinetic parameters of models of Ammonium adsorption on AgNPs Model Parameter Value Model Parameter Value Pseudo- qe (mg/g) 149.98 Pseudo- qe (mg/g) 153.61 first order K1 0.491 second order K 2 R 0.1589 Elovich 0.0088 R 0.653 α 5.529  0.180 R 0.885 30 Figure 9: Kinetics modelling of NH4+ sorption onto AgNPs (Co: 10 mg/L; adsorbent dose: 1.6 mL/25 mL; initial pH: 9) Fig presented the model prediction and experimental data for pseudo-first order, second order and Elovich Table summarized calculated parameters of the models The applicability of each model was determined by the correlation coefficient, R2 from these plots From Fig and Table 2, it can be seen that Elovich model fit the most well with experimental data with highest R2 (0.885) The R2 values of two left models: Pseudo-first orders, pseudo-second order, respectively, were 0.1589 and 0.653 proved that the experimental data is not well fitted for kinetic equation of these models The low values of qe (149.98 mg/g) and K1 (0.491), for pseudo-first order, were also in close agreement to those obtained experimentally in the case of the pseudo-first-order 31 model Fig showed that the calculated qe value by Elovich model was closer to the experimental data than that of other models The model suggests that the rate-limiting step is chemisorption (Chi-Chuan Kan et al., 2017) The mechanism may involve sharing of valence electron forces or through ion exchange between the adsorbent and the adsorbate (Yadav S et al., 2013) 32 PART V CONCLUSIONS The silver nano particles (AgNPs) is an interesting capacitate, high effective and low cost adsorbent for removal from aqueous solutions The adsorption process of AgNPs was highly depended on pH of solution The pH of and the contact time of 60 minutes for adsorption of NH4+ was the optimum condition in this study The results also indicate that the adsorption capacity of NH4+ decreased when the dose of AgNPs and NH4+ concentration increased The maximum adsorption capacity of NH4+ by AgNPs obtained 100.48 mg/g within 60 minutes with 1.6 mL/ 25mL of AgNPs at 5mg/L initial NH4+ Experimental data follows Langmuir model with R2 value of 0.9339 From this study, it can be concluded that AgNPs is an effective absorbent to remove NH4+ from aqueous solutions with new material in Vietnam 33 REFERENCES Ali I (2012) New generation adsorbents for water treatment Chem Rev (in press) Amrut S Lanje, Satish J Sharma, Ramchandra B Pode (2010) Journal of 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silver nanoparticles were prepared using silver nitrate... urea, ammonium and salt production Ammonium from fertilizers, from rotting and from domestic wastewater and industrial effluent These substances, by surface water, penetrate downwards from the