THAI NGUYEN UNIVERSITY NATIONAL CHIAO TUNG OF AGRICULTURE AND FORESTRY UNIVERSITY NGUYEN DUC MANH COMPARISON STUDY OF AMMONIUM IONS ADSORPTION ON ZEOLITE, ACTIVATED CARBON AND AMINO-FUNCTIONALIZED SILICA IN AQUEOUS SOLUTIONS BACHELOR THESIS Study Mode : Full-time Major : Environmental Science and Management Faculty : International Programs Office Batch : 2013 - 2017 Thai Nguyen, 2017 c Thai Nguyen University of Agriculture and Forestry Degree Program Bachelor of Environmental Science and Management Student name Nguyen Duc Manh Student ID DTN1354110099 Thesis Title Comparison Study of Ammonium ions Adsorption on Zeolite, Activated carbon and Amino-functionalized silica in aqueous solutions Supervisor(s) 1. Sue-Min Chang 2. Nguyen Thi Ha Supervisor’signature Abstract: This study examined the capability of Amino-functionalized silica, Activated carbon and Zeolite, to remove ammonium ions from water. Studies were conducted to examine the ammonium removal capacity of these three materials under various experimental conditions of contact time and ammonium concentration.
The adsorption materials were prepared and investigated by various techniques including Fourier transform infrared spectroscopy (FTIR), Brunauer–Emmett–Teller (BET) to examine the functional groups and surface areas, respectively. The pseudo first- order, pseudo second-order kinetic models were used to describe the kinetic data. The ammonium removal data for Amino functionalized silica and Activated carbon c most highly correlated with pseudo-first-order adsorption reaction model, whereas Zeolite was best fitted with pseudo-second-order model. The Langmuir and Freundlich models were applied to describe the equilibrium isotherms for ammonium adsorption capaciy.
The findings showed that the adsorption of ammonium on the Activated carbon was best fitted with the Langmuir model,Zeolite was best fitted with the Freundlich model, Amino functionalized silica could be described by both Langmuir and Freundlich model. The results also indicated a significant potential of the Amino functionalized silica as an alternative adsorbent material for ammonium removal from aqueous solutions. Keywords Amino groups, Adsorption, Amino- functionalized material, ammonium ion ( ). Number of pages 47 Date of submission 20/9/2017 c ACKNOWLEDGMENT The completion of this thesis would not have been possible without the help of many people.
At this very moment of accomplishment, I would like to express my sincere gratitude to my supervisor Prof. Sue Min Chang, Professor Institute of Environmental Engineering National Chiao Tung University, Taiwan. Thanks for giving me the opportunity to be a student of Environmental Nanomaterial Lab, as well as who suggested the topic and support me during the internship time. Secondly, I would like to express my sincere gratitude to Assoc.
Nguyen Thi Ha, Faculty of Environmental Science, VNU University of Science, Ha Noi, Viet Nam. Thanks for her guidance, encouragement and support throughout the entire study and complement of this thesis. I am thankful to Environmental Nanomaterial Laboratory of National Chiao Tung University for providing me facilities to conduct my research work. I am also thankful to all members in the laboratory for their help during my internship course.
Student guy n c nh ~i~ c TABLE OF CONTENTS ACKNOWLEDGMENT. i LIST OF FIGURES. iv LIST OF TABLES. v LIST OF ABBREVIATIONS.
vi PART 1 : INTRODUCTION. 3 PART 2 : LITERATURE REVIEW.1 General introduction to ammonium nitrogen .2 Methods for removing ammonium form water .3 Basic of adsorption theory.4 Introduction of Activated Carbon .5 Introduction of Zeolite.6 Introduction of Amino functionalized silica. 18 PART 3 : MATERIALS AND METHODOLOGY .1 Synthesis Amino-functionalized silica .2 Prepare water sample .3 Investigate the adsorption capacity .4 Investigate the kinetic of ammonium adsorption .5 Investigate the isotherm of ammonium adsorption. 22 PART 4 : RESULTS AND DISCUSSION .2 Results of ammonium removal capacity investigation .1 Effect of contact time .2 Effect of ammonium concentration .3 Results of Kinetic model and Isotherm model investigation .1 Results of Kinetic model investigation.2 Results of Isotherm model investigation.
30 PART 5 : CONCLUSION AND RECOMMENDATION .2 Recommendation for future study. 36 ~ iii ~ c LIST OF FIGURES Figure.1: Ammonium chemical structure Figure.2: Formation of Ammonium Figure.3: Schematic Representation of (a) graphitizing and (b) non-graphitizing structure of carbon.4: Micropore, Mesopore and Macropore Regions of Activated Carbon Figure.5: Primary structural units of zeolite – tetrahedron ; ; Figure.6: Secondary structure units of the zeolite Figure.7: Synthesis Amino functionalized silica process.8: BET surface area of Amino functionalized silica, Zeolite and Activated carbon.9: FTIR spectra of Amino functionalized silica, Zeolite and Activated carbon.10: Ammonium removal efficiency using Amino functionalized silica, Activated carbon and Zeolite Figure.11: Effect of initial ammonium concentration to equilibrium adsorption Figure.12: Linear plot of Langmuir isotherm of ion adsorption on three sample.13: Linear plot of Freundlich isotherm of ion adsorption on three samples ~ iv ~ c LIST OF TABLES Table 1. Ammonium ion adsorption on some adsorbents. Summarizes basic structural data of some common zeolite Table 3.
Kinetic parameters for ammonium removal using the pseudo-first-order model and pseudo-second-order model Table4. Isotherms constants for the ammonium exchange by three sample ~v~ c LIST OF ABBREVIATIONS AC : Activated Carbon BET : Brunauer–Emmett–Teller FTIR : Fourier Transform Infrared Analysis : concentration in the solution at equilibrium (mg/L) : Pseudo-first-order adsorption constant : Pseudo-second-order adsorption constant and n: Freundlich constant : Lang-muir constant : Adsorption capacity at equilibrium conditions : Maximum adsorption capacity ( mg/g) : Adsorption capacity at time t : Correlation coefficient value ~ vi ~ c PART 1 : INTRODUCTION 1.1 Research rationale Water is one of our most important natural resources. However, Due to increased anthropogenic activities and thus increased waste generated which causes environmental pollution, supplying safe drinking water is the highest challenge of communities during the current century(Moussavi et al. For all practical purposes, water pollution is the addition by humans of something to the water that alters its chemical composition, temperature, or microbial composition to such an extent that harm to aquatic life and on those who consume the water (Lioyd,1992).
One of the sources that cause water pollution is Nitrogen and its compounds. Nitrogen compounds are very essential elements for living organisms. However, the presence of excess Nitrogen compounds causes environmental pollution. Agriculture activities are associated with use of fertilizers on a large scale, industrial wastewater, domestic wastewater which rich of Nitrogen compound discharged into the environment causing adverse effect to aquatic ecosystems.
Ammonia and ammonium ions are the more commonly encountered Nitrogen compounds in waste water, these nutrients in aquatic ecosystems cause diverse problems such as imbalance of natural ecological systems and increase of eutrophication, depletion of dissolved oxygen in surface waters which kills fishes and create septic condition, odor problems, increase risks to human health (Carpenter et al. Therefore, the control on them has vital importance for the protection of public health. ~1~ c Several physicochemical and biological methods, including biological nitrification– denitrification, break-point chlorination, chemical precipitation, and air-stripping have been widely applied to remove ammonium from aqueous. However, there are some problems when using these methods such as: complex operations and biomass waste for biological methods, moreover the treatment of ammonium nitrogen wastewater of low organic content by a biological process usually needs to be supplemented with a carbon source, which may add to the treatment cost (H.
Huang et al. Higher energy consumption and produce secondary pollution for Air stripping method. Currently, adsorption/ion exchange is believed to be a simple and effective technique for water and wastewater treatment and the success of the technique largely depends on the development of an efficient adsorbent. Adsorption/Ion-exchange process have been used in various fields in recent years, including the ammonium ions removal from wastewater due to their many unique characteristic, such as simple operations, high treatment capacity, high removal efficiency, fast kinetics and low cost (Cooney et al.
1999; Kang et al. Activated carbon, Zeolite derived from different materials has been widely used for sequestering ammonium ions from aqueous solutions. However, with the increase of industrial wastewater containing different concentrations of ammonium ions, there is a growing demand to develop new materials for the efficient removal of ammonium ions from aqueous environments rather than the high cost activated carbon in which its full- scale application has been limited (Zheng, Zhang, and Wang 2009). Recently, application of some compounds containing due to its exchange property has been considered as an efficient approach to adsorb various ions such as ammonium from aqueous solutions (Soltani et al.
~2~ c Hence, in the present work, I studied the application of Amino-functionalized silica ( ) for adsorption of ammonium ions, and also evaluate the ammonium removal capacity of this material in comparison with common adsorbent: activated carbon and zeolite.2 Research’s Objective Evaluate the capability of Amino-functionalized silica for removing ammnium Compare the properties and ammonium adsorption capacity between: Activated carbon, Zeolite and Amino-functionalized silica Assess the potential of Amino-functionalized silica as alternative solution for purifying water.3 Research’s Contents 1) Literature review about ammonium and ammonium contaminated in water, its adverse effects on ecosystem and human health. 2) Synthesis and investigate the characteristics of Amino-functionalized silica. 3) Investigate the ammonium adsorption capacity of Amino-functionalized silica and compare with Activated carbon, Zeolite and Amino-functionalized silica under different experimental conditions in aqueous solution.4 Research’s Scope The sample of contaminated solution that contains ammonium ion were prepared in Environmental Nanomaterial Laboratory, Chiao Tung University, Taiwan. The experimental process was done in the laboratory.
~3~ c PART 2 : LITERATURE REVIEW 2.1 General introduction to ammonium nitrogen Ammonium is an important source of nitrogen for many plant species, However, it is also toxic to most crop species and is rarely applied as a sole nitrogen source. The ammonium cation is a positively charged polyatomic cation with the chemical formula It is formed by the protonation of ammonia ( ). Ammonium chemical structure Molecular nitrogen ( ) present in the earth atmosphere has to be reduced to ammonia ( ) by nitrogen-fixing bacteria living independently in the soil or in the root of leguminous plants before it is utilized by humans. Ammonia dissolves in water to form ammonium ions ( ) and this form of reduced nitrogen is assimilated into amino acids and other nitrogencontaining molecules.
In aqueous solution, ammonia acts as a base, acquiring hydrogen ions from to yield ammonium and hydroxide ions, according to the reversible reaction: (1) ~4~ c The double arrow in the equation indicates that an equilibrium is established between dissolved ammonia gas and ammonium ions ( When pKa = 9. The degree to which ammonia forms the ammonium ion depends on the pH of the solution. If the pH is low ( pH<9.3), the equilibrium shifts to the right: more ammonia molecules are converted into ammonium ions and vice versa (Adeva et al. 2012; Graham and MacLean 1992).
Formation of Ammonium ion Ammonium is an important nitrogen ion form in aqueous solution. Its pollution mainly comes from different resource: Agricultural: The primary agricultural sources include accidental releases of ammonia-rich fertilizer during transport (because of vehicle accident, faulty hose connections, and human error); and livestock waste (from barnyards, feedlots, pastures, and rangeland). Residential and Urban: Household use of ammonia-containing cleaning products, on- lot septic systems, and improper disposal of ammonia products may contribute to nonpoint pollution. Atmospheric deposition: available data suggests nitrogen (directly and via rainfall) constitutes a large portion of total nitrogenous inputs to estuarine and marine systems and a somewhat lesser portion of total N inputs to freshwater systems Ammonia in the ~5~ c atmosphere is derived from combustion processes such as domestic heating, burning of municipal waste, and internal-combustion engines.
The presence of normal levels of ammonium nitrogen usually does not have a direct effect on aquatic insects or fish. However, excess levels of ammonium nitrogen in water can create conditions that make it difficult for aquatic insects or fish to survive. Some effects due to excess nitrogen resource are: Eutrophication: The process by which a body of water acquires a high concentration of nutrients, especially phosphates and nitrates. These typically promote excessive growth of algae.
As the algae die and decompose, high levels of organic matter and the decomposing organisms deplete the water of available oxygen, causing the death of other organisms, and fishes.