ABSTRACT
In this study, calcined eggshell powder was used as low-cost adsorbent to remove copper (II) ion from aqueous solution by adsorption. Effects of operational parameters such as contact time, adsorbent dosage, initial concentration and temperature were determined for optimum removal. Results shows a maximum removal of 99.96167% at 30 minutes, 1.5g, 300mg/L and 35 . Equilibrium adsorption isotherms, kinetics and thermodynamics were investigated. Langmuir and Freundlich models were used to analyse the experimental data and the isotherm data fitted well to the Langmuir isotherm with monolayer adsorption capacity of 4.5024 mg/g. Adsorption kinetic study revealed that pseudo-second order with correlation coefficient value of 0.9361 best fit to experimental data compared with pseudo-first model. Thermodynamics studies describes the adsorption reaction process as non-spontaneous, increasing in rate with increase in temperature, endothermic and irreversible in nature.
TABLE OF CONTENTS
CERTIFICATION………………………………………………………………………………………………………. iii
DEDICATION…………………………………………………………………………………………………………… iv
ACKNOWLEDGEMENT…………………………………………………………………………………………….. v
ABSTRACT………………………………………………………………………………………………………………. vi
TABLE OF CONTENTS……………………………………………………………………………………………….. vii
CHAPTER ONE………………………………………………………………………………………………………… 1
INTRODUCTION………………………………………………………………………………………………………. 1
CHAPTER TWO………………………………………………………………………………………………………… 7
LITERATURE REVIEW……………………………………………………………………………………………… 7
- Pollution……………………………………………………………………………………………………………. 7
CHAPTER THREE…………………………………………………………………………………………………… 28
MATERIALS AND METHOD…………………………………………………………………………………….. 28
CHAPTER FOUR…………………………………………………………………………………………………….. 34
RESULTS AND DISCUSSION………………………………………………………………………………….. 34
- Characterisation of Eggshell Adsorbent………………………………………………………………. 34
CHAPTER FIVE………………………………………………………………………………………………………. 51
CONCLUSION AND RECOMMENDATION…………………………………………………………… 51
LIST OF TABLES
Table 2.1: Effects and Toxicological Symptoms of Some Heavy Metals Table 2.2: Physical / Organoleptic Parameters
Table 2.3: Inorganic Constituents
Table 2.4: General Characteristics of Physisorption and Chemisorption Table 2.5: Chemical Composition of Eggshell before Calcination
Table 2.6: Chemical Composition of Eggshell before Calcination Table 3.2 Equipment Used
Table 4.1: Results from X-Ray Fluorescence (XRF) Analysis Table 4.2: Comparison of the Isotherm for the adsorption of Cu2+ Table 4.3: Results of thermodynamic study
LIST OF FIGURES
Figure 3.1: preparation of eggshell powder a) soaked chicken eggshelll b) washed and cleaned chicken eggshells c) oven dried eggsehll d) chicken eggshell powder
Figure 3.2: Batch adsorption process a) 50 ml of copper solution b) The mixture of adsorbent and copper solution placed on the hot plate
Figure 4.1: scanning electron micrograph of A) raw B) calcined eggshell Figure 4.2: FTIR spectra of raw eggshell adsorbent
Figure 4.3: FTIR spectra of calcined eggshell adsorbent Figure 4.4: FTIR spectra of used eggshell adsorbent
Figure 4.5: Graph of removal efficiency (%R) vs. contact time Figure 4.6: Graph of removal efficiency (%R) vs. temperature Figure 4.7: Graph of removal efficiency (%R) vs. adsorbent dosage
Figure 4.8: Graph of removal efficiency (%R) vs. initial concentration Figure 4.9: Graph of log (qe – qt) vs. t
Figure 4.10: Graph of t/qt vs. t Figure 4.11: Graph of Ce/qe vs. Ce
Figure 4.12: Graph of log qe vs. log Ce Figure 4.13: Graph of vs. 1/T
CHAPTER ONE INTRODUCTION
Background
Water is an essential substance for the existence of mankind on earth because of its vital function to man and his environment. The sources of water are; surface water such as streams, rivers, lakes, seas and oceans, ground water such as wells, boreholes, and rain water which is obtained from the physical action of condensation of water vapour that evaporates from the surface of the earth. The rain water replenishes underground and surface water. It is interesting to note that 71% of the earth’s surface is covered by water. This is unevenly distributed between seas and oceans, ground water, glaciers and ice cap and in air (as vapour clouds and precipitation) in percentages of 96.5%, 1.7%, 1.7% and 0.001% respectively. Of these, only 2.5% is fresh water and 98.5% of that water is ice and ground water.
With the increase in industrialisation, water pollution has been a major issue of hazard to man and his environment. Water pollution as defined by Wikipedia is the contamination of water bodies. These contaminants are classified as; physical contaminants (primarily impact the physical appearance or other physical properties of water), biological contaminants (organisms in water), radiological contaminants (chemical elements with an unbalanced number of protons and neutrons resulting in unstable atoms that emit ionizing radiation) and chemical contaminants (elements or compounds including nitrogen, bleach,, salts, pesticides, toxins produced by bacteria, and human or animal dung and metal) of which this study falls under. (USEPA, 2016). Two different groups are used to categorise the factors that are instrumental in water pollution namely; point sources and non-point sources. (Menon, 2011). Point sources are direct sources of water pollution that are identified and controlled (reduced
and monitored) easily, some examples are factories, sewage systems, power plants, underground coal mines, oil wells. Non point sources are ambiguously defined and harder to control they include a wide range of sources such as; when rain or snow moves through the ground and picks up pollutants as it moves towards a major body of water, the runoff of fertilizers from farmland, air pollutants deposited on earth. This has necessitated the need for water treatment process. (Menon, 2011).
The wellbeing of the environment, society and the economy is a factor of the quality of water (Corcoran et al.; 2010). Waste water is water that has been negatively affected in quality by anthropogenic influences. Wastewater is defined as a combination of one or more of; domestic effluents consisting of black-water (excreta, water and faecal sludge) and grey water (kitchen and bathing wastewater); water from commercial establishment and institutions, including hospitals ; industrial effluent, storm water and other urban run-off; agricultural, horticultural and aquaculture effluent, either dissolved or as suspended matter (Corcoran et al; 2010).
Heavy metals are naturally occurring elements that play major roles in the industry. Heavy metals present in trace amounts are required in some biological processes; Iron and copper (oxygen and electron transport); zinc (hydroxylation); cobalt (complex syntheses and cell metabolism) (Nielboer and Richardson, 1978) to mention but a few. Although heavy metals have proven to be useful in the industry, some have negative effect on both the environment and on man hence the need for their removal from waste water.
Methods such as chemical precipitation, chemical coagulation, ion-exchange, electrochemical method, membrane process and ultrafiltration can be employed in removal of heavy metals from water. The methods are relatively expensive and the agencies responsible for the provision and distribution of potable water; water board, waste sewerage authority
(WASA), rural urban development agency (RUDA), rural urban water supply agency (RUWASA), water resources employ the conventional water treatment process (involving a series of steps; aeration, coagulation, flocculation, sedimentation , clarification, filtration and disinfection), which is sufficient in the removal of physical and biological contaminants only and not chemical contaminants.
Research efforts has/is been made in the determination of a cheap, easily accessible and replicated method of hard metal removal. In developing countries such as Nigeria, water treatment plants are expensive. The ability to pay for services is minimal and skills as well as technology are scarce. In other to alleviate the prevailing difficulties, approaches should be focus on sustainable water treatment systems that are low cost, robust and requires minimal maintenance and operating skills. Locally available materials can be exploited towards achieving sustainable safe potable water supply (Aho and Lagasi, 2012). This makes adsorption and the use of eggshell as an adsorbent a contender as a substitute method of water treatment.
Heavy metals have a wide application in the industry, hence they are present in the industrial effluents generated at the end of a process. They are introduced into the environment during these effluents disposal and generally enter the body by ingestion, inhalation and adsorption through the skin or mucous membrane (Jackson and Henderson, 2016) adversely affecting the system; environment and man. Methods of heavy metal removal is therefore required and important to avoid this.
Research Problem
The generation of waste water containing heavy metals has become an issue as their release into the environment has increased as a result of industrialisation. This waste water contains amounts of heavy metal that are harmful to the environment and man who is likely to come in contact and use this water. Legislations have been put in place prompting industries to treat the waste water they generate before it is disposed of. This increases the operational cost of a manufacturing process and hence the need for a relatively cheap, easily accessible and replicated method of waste water treatment. The need for the proper disposal of eggshell currently being used as landfills also makes this study important.
Aim and Objectives
The aim of this research is to study the effectiveness of eggshell as an adsorbent in the removal of cobalt ii ion from aqueous solution providing an affordable and easy substitute for water treatment. The objectives are:
- Preparation of adsorbent from waste chicken eggshell.
- Characterisation of adsorbent using FTR, SEM, and XRD techniques.
- Testing the adsorption capacity of as-synthesised eggshell adsorbent.
- Optimisation of adsorption variables; contact time, temperature, adsorbent dosage and initial concentration.
Research Scope and Limitation
To achieve the objective of this research, the listed scopes and limitations have been identified.
- The scope of this research is limited to prepared aqueous solutions with known concentration of copper and zinc ion, egg shell from chicken sourced from ABUAD cafeteria.
- The capacity of egg shell as an adsorbent will be investigated and evaluated.
- Analytical tools easily found in ABUAD and surrounding institutions also serves as a limitation.
- The study is limited to inorganic contaminants that pollutes water.
Justification of study
The inefficiency of the government to provide potable water for her citizens coupled with the increasing rate of pollution of the available fresh water mainly by heavy metal from the industry has made the search for a cheap and easily replicated method of water treatment common these days. The increasing rate of pollution caused by human activities (industrialisation, waste generation and improper disposal), has stimulated the need for environmental control measure. This study focuses on the removal of heavy metal from water (waste water treatment) making it suitable for use and also on the reduce, reuse, and recycling of eggshell. In addition to the provision of an alternative waste water treatment, it provides a suitable means of egg shell disposal as improper disposal leads to inbreeding of rodents which feed on the membrane, subsequently leading to the spread of disease such as rat bite fever, leptospirosis and the most recent Lassa fever (Orkin LLC, 2016) and also attract its predators; snakes.
The provision of cheap, simple and easily available method of waste water treatment to the industries before their disposal as well as the masses affected by environmental pollution will be achieved in the case of the success of this research as well as an avenue for eggshell recycling solving the problem of improper disposal.
CHAPTER TWO
Pollution
LITERATURE REVIEW
Pollution is defined by Wikipedia as the introduction of contaminants into the natural environment that causes adverse change. Environmental pollution is the contamination of the earth/atmosphere system to an extent that normal environmental processes are adversely affected. (Kemp, 1998). Pollution can also be defined as the addition of any substance or form of energy (e.g. heat, sound, and radioactivity) to the environment at a rate faster than the environment can accommodate it by dispersion, breakdown, recycling, or storage in some harmless form. (Guinness and Walpole, 2015). Environmental pollution is often as an outcome of energy conversion and the use of resources resulting in their by-products in water, soil and air (Coker, 2009). As at 2006, the National Population Commission recorded a population of 140 million, with a growth rate of 3.5%, the country’s population is now estimated at 182 million (NPC, 2017) , this coupled with the increase in manufacturing industries in the country has made environmental pollution a major issue.
There are various types of pollution; water, thermal, land, radiation, noise and air pollution. This study is concerned with water pollution. Water pollution is defined as the introduction into fresh or ocean waters contaminants of chemical, physical, or biological material that degrades the quality of the water and affects the organisms living in it. (Coker 2009). Professor Akinwale O. Coker supports that pollutants that contaminate water are of two categories; Conventional or classical pollutants which are mainly human waste product. These are municipal waste water and consist a variety of nutrients, suspended solids, dissolved solids, oil, metals (arsenic, chromium, lead, iron and manganese), and biodegradable organic carbon in concentrations that pose a problem to the body of water they are introduced to. The unconventional pollutants are waste produced from the industries;
manufacturing construction, etc. they range from biologically inert material to toxic and insidious materials (mirex, kepone, heavy metals, etc.) their effect on the environment.
Waste Water
Water is an essential substance that supports life on earth. One atom of oxygen is chemically bonded to two atoms of hydrogen resulting in a molecule of water H2O. Water in nature exists in the three phases; liquid, solid and gases. It however does not consist of only hydrogen and oxygen. Water in nature consists of constituents classified as;
- Dissolved gases: nitrogen, carbon dioxide, ammonia, sulphurous gases.
- Mineral constituents; hardness salts, sodium salts (chloride, sulphate, nitrate, bicarbonate, etc.), salts of heavy metals and silica.
- Organic matter: both of animal and plant origin, oil, trade waste (including agricultural) constituents and synthetic detergents.
- Microbiological forms: various types of algae and slime forming bacteria doctors.org/Corrosion-by-Water/Constituents.htm)
The concentration of the various substances in water (dissolved, colloidal or suspended form) are usually very low and differ. When the concentration of these constituents increases due to human activities affecting negatively the quality of the water, they are considered as pollutants and the water body is termed waste water. The business dictionary defines waste water as spent or used water with dissolved or suspended solids, discharged from homes, commercial establishments, farms and industries. Waste water is generally classified as industrial waste water and domestic wastewater (sewage or municipal wastewater). Composition of industrial waste water is dependent on the industry as well as the process (Tandon, 2015).
Irrespective of the composition of the waste water, it has a negative effect on man and his environment. The receiving water body is degraded resulting in decreased levels of dissolved oxygen, physical changes to receiving water, release of toxic substances, bioaccumulation in aquatic life and increased nutrient load resulting in Eutrophication and reduction in ground water quality when nutrients leach down the soil. As a result of the boom in aquatic life, diseases caused by bacteria, viruses and protozoa are more likely to affect man and animals
(Okereke et al., 2016) in contact/use with this wastewater, the individual constituents ( heavy metals and their compounds) also act in their generic manners adversely affecting man’s health. To avoid this, waste water must be treated to meet certain standards before their introduction to the environment.
