ELI Work
ELI Work
ELI Work
This research was carried out to improve the application of activated carbon which is one of the
fastest growing areas in environmental applications such as wastewater treatment due to the
increase in contamination of wastewater by heavy metals. The activated carbon was produced
from Apple of Sodom plant stem for the removal of heavy metal ions (Pb +2 and Ni+2) in the
hospital waste water sample. The precursor material was collected, washed, sundried and oven
dried at105° for 24 hours. The activated carbon produced was prepared by chemical activation
using nitric acid (HNO3) as activating agent. Proximate composition analysis (bulk density,
moisture content, ash content) of the activated carbon produced were determined and recorded
as 2.06g/ml, 26.5%, and 0.85% respectively. The initial concentrations of the heavy metal ions
(Pb+2 and Ni+2) present were determined and recorded as 2.915mg/L and 1.87mg/L respectively.
The final concentrations of the heavy metal ions (Pb +2 and Ni+2) present were determined and
recorded as 1.92mg/L and 1.02mg/L respectively. The amount of Pb +2 and Ni+2 absorbed is 7.08
and 11.625 respectively. The surface morphology as well as the surface functional groups
present were determined using the Scanning Electron Microscope (SEM) and Fourier Transform
Infrared (FTIR) spectroscopy equipment respectively.
Table of Contents
Title Page i
Declaration ii
Certification iii
Acknowledgement iv
Abstract v
CHAPTER ONE
1.0 INTRODUCTION - - - - - - - - 1
CHAPTER TWO
2.1.4 Human Exposure & Health Hazards Associated with Heavy Metals10
2.4.1 Pyrolysis/Carbonization21
2.4.2 Activation22
CHAPTER THREE
4.1 Results33
4.2 Discussions43
CHAPTER FIVE
5.1 Summary46
5.2 Conclusion46
5.3 Recommendation47
References48
iv
LIST OF TABLES
Table 4.2 Initial and Final Concentrations of the Metal ions present.
Table 4.3 Amount of Pb+2 and Ni+2 absorbed and percentage removed.
Table 4.4 FT-IR analysis wave numbers and corresponding functional groups present.
v
CHAPTER ONE
INTRODUCTION
Recently, carbon has been one of the magnificent elements which have revolutionized material
science. From carbon we obtain the best porous absorber (activated carbon) with excellent
Activated Carbon (AC) is the common term used for a group of absorbing substances of
crystalline form, having a large internal pore structures that make the carbon a good absorbent.
These properties are obtained when a char is subjected to controlled gasification by oxidizing
gases, or when a raw material impregnated with dehydrating agents is subjected to carbonization
homogenous structure with high surface arca and shows radiation stability (Ahmad, I., 2005).
The process for producing efficient activated carbon is not completely investigated in developing
countries. Furthermore, there are many problems with the generation of used activated carbon
In this research, the local agricultural product used is Apple of Sodom (Calotropis procera) plant
stem to produce an activated carbon due to the availability and inexpensive material with high
By now, a lot of research has been done on to improve the application of activated carbon. One
of the fastest growing areas is in environmental applications such as wastewater treatment. In the
1
treatment of wastewater, it is used for purification, decolorization and the removal of toxic
Waste materials that have been successfully used to manufacture activated carbon in the recent
past include sago waste (K. Kadirvelu, and C. Karthika, 2005), coir pith (C.Namasivayam, and S.
Kumar, 2001), orange peel (Khaled et al., 2009), coffee husk(Ahmad and Rahman, 2011), pine
sawdust (Gecgel and Kolancilar, 2012), rice husk(Yahaya et al., 2011), oil palm fruit fibre
(Bello, 2013), sugarcane dust (S. Khattri, and M.Singh, 1999), rubber wood sawdust (K.
Vasanth, and S. Sivanesan, 2007), moss peat (D.JohnWase et al., 1995) tea waste(E. Malkoc,and
The importance of activated carbon cannot be over emphasized, thus leading to the search of
means for its production other than the known traditional methods, due to its applicability in all
or almost all of life's endeavors. The production of activated carbon from agricultural byproducts
has both economic and environmental effects, as it converts unwanted, low-value agricultural
Since the second part of 20th century, there has been growing concern over the diverse effects of
heavy metals on humans and aquatic ecosystems. Environmental impact of heavy metals was
earlier mostly attributed to industrial sources. In recent years, metal production emissions have
and altered industrial activities. Today and in the future, dissipate losses from consumption of
various metal containing goods are of most concern. Therefore, regulations for heavy metal
2
A significant part of the anthropogenic emissions of heavy metals ends up in wastewater. Major
industrial sources include surface treatment processes with elements such as Cd, Pb, Mn, Cu, Zn,
Cr, Hg, As, Fe and Ni, as well as industrial products that, at the end of their life are discharged in
wastes. For some applications which during the last decade have been phased out in some
countries, there may, however, today be significant differences in uses (Hui, K. et al.,2005).
Most common sources of heavy metals to waste and/or waste water are;
i. Minning and extraction; a significant part of the four heavy metals with mining waste
actually concerns the presence of the heavy metals in waste from extraction of other
metals like zinc, copper and nickel. It should however be kept in mind that mining
ii. Primary smelting and processing; a minor part of the heavy metals will end up in
iii. Use phase; a small part of the heavy metals may be lost from the products during use
by corrosion and wear. The lost material may be discharged to the environment or
iv. Waste disposal; the main part of the heavy metals will still be present when the
discarded products are disposed off. The heavy metals will either be collected for
liquid waste. A minor part will be disposed of as chemical waste and recycled or land
3
v. Metallurgical industries. Actually, metal pollutants are neither generated nor
completely eliminated; they are only transferred from one source to another. Their
chemical forms may be changed or they are collected and immobilized not to reach
The term bioavailability is more appropriate to define the potential toxicity of metallic elements
physicochemical properties of metallic elements, their ions, and compounds. These in turn
depend upon the atomic structure of the metallic elements. Thus, any classification of the
metallic elements to be used in scientifically based legislation must itself be based on the
periodic table or some subdivision of it. In conclusion, heavy metals commonly used in industry
and generically toxic to animals and to aerobic and anaerobic processes, but all of them are not
dense or entirely metallic. Includes As, Cd, Cr, Cu, Pb, Hg, Ni, Se, Zn. All of them pose a
number of undesired properties that affect humans and the environment (Duffus, J.,2002).
Effluents from textile, leather, tannery, electroplating, galvanizing, pigment and dyes,
metallurgical and paint industries and other metal processing and refining operations at small and
large-scale sector contain considerable amounts of toxic metal ions (Ahluwalia, S. and Goyal, D.,
2007). The toxic metals and their ions are not only potential human health hazards but also to
other life forms. Toxic metal ions cause physical discomfort and sometimes life-threatening
illness including irreversible damage to vital body system (Malik, A., 2004). From the eco-
toxicological point of view, the most dangerous metals are mercury, lead, cadmium and
chromium (VI). Metal ions in the environment bioaccumulate and are biomagnified along the
food chain. Therefore, their toxic effect is more pronounced in animals at higher tropic levels.
4
Among commonly used heavy metals (III), Cu, Zn, Ni and V are comparatively less toxic than
Fe and Al. An effluent treatment facility within the industry discharging heavy metals
contaminated effluent will be more efficient than treating large volumes of mixed wastewater in
a general sewage treatment plant. Thus, it is beneficial to devise separate treatment procedures
for scavenging heavy metals from the industrial wastewater (K. Kadirvelu et al.,2001).
The analysis of wastewater for trace and heavy metal contamination is an important step in
ensuring human and environmental health. A variety of inorganic techniques can be used to
measure trace elements in waste water including flame atomic absorption spectrometry (FAAS)
and graphite furnace (or electrothermal) atomic absorption spectrometry (GFAAS) or ETAAS),
inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled
expected concentration range of analytes and the number of samples to be run, the most suitable
In recent years, some new processes such as biosorption, neutralization, precipitation, ion
exchange, adsorption etc. Have been developed and extensively used for the heavy metal
The aim of this research is to produce activated carbon from the local agricultural waste which is
Apple of Sodom (Calotropis procera) plant stem impregnated with 1M HNO3 for removal of
5
1.2 Objectives of the Research
ii. To examine the characteristic of powdered activated carbon produced (i.e., proximate
iii. To evaluate the potential application of locally produced activated carbon in removal
This work focuses on the production and characterization of activated carbon produced from
Apple of Sodom. The raw material activated will be carbonized under certain temperature(0-
In this research, the production and characterization of the activated carbon produced were
performed by using several analyses such as the elemental analysis, proximate analysis, pore size
analysis, surface functional groups analysis and adsorption capacity (Mohan, D.,2007).
6
CHAPTER TWO
LITERATURE REVIEW
A metal of relatively high density (specific gravity greater than 5) or of high relative atomic
weight is defined as a heavy metal. The term "Heavy metals" is used to describe more than a
dozen elements that are metals or metalloids (Karvelas, M., 2003); e.g., chromium, arsenic,
cadmium, lead, mercury, manganese, etc. Because they cannot be degraded or destroyed, heavy
metals are persistent in all parts of the environment. Living organisms require varying amounts
of "heavy metals". Iron, cobalt, copper, manganese, molybdenum, and zinc are required by
humans. Excessive levels can be damaging to the organisms (Vogel's, 1989). Therefore, heavy
metals can be described as any metallic element that has a relatively high density and is toxic or
poisonous at low concentrations. Humans are also responsible for altering the chemical forms of
heavy metals released to the environment. Such alterations often affect a heavy metal's toxicity
by allowing it to bioaccumulate in plants and animals, bioconcentrate in the food chain, or attack
specific organs of the body. Bioaccumulation refers to an increase in the concentration of a metal
in a biological organism over time, compared to the normal concentration in the environment. In
small quantities, 289 certain heavy metals are nutritionally essential for a healthy life (e.g., iron,
copper, manganese, and zinc). Some of these are referred to as the trace elements (Demirbas, A.,
2008).
Metals may be present as individual elements, and as organic and inorganic compounds. The
geosphere is the original source of all metals (except those that enter the atmosphere from space
7
in the form of meteorites and cosmic dust). In the hydrosphere, metals occur as dissolved ions
and complexes, colloids, and suspended solids. In the atmosphere, metals may be present as
gaseous elements and compounds and as particulates and aerosols (Sag, Y., 2001). Gaseous and
particulate metals may be inhaled and solid and liquid (aqueous-phase) metals may be ingested
or absorbed, thereby entering the biosphere (Adrienne et al., 2008). In addition to being the
original source of all terrestrial metals, the geosphere may represent a sink for metals. A
reservoir may act as a catalyst for changes of state of metals and metal compounds, without
actually having incorporated those metals, as in the case of some biologically mediated reactions
(Volesky, B.,2007).
A number of biogeochemical processes take place at the heterogeneous interface between the
rock, soil, water, air and living organisms (Spark, 2005). These processes or interactions in turn
control the solubility, mobility, bioavailability and toxicity of metals (Sparks, 2005).
Microorganisms can transform metals such as Hg, Se, Sn, As and Cr by means of oxidation-
reduction and methylation (the process of replacing an atom, usually a H atom, with a methyl
group) mechanisms and demethylation reactions. These processes affect transport or mobility
For example, methylated (organic) forms of Hg are more toxic than inorganic forms of the
8
i. Cadmium is mainly used in batteries, plastics and it is also found in cigarette smoke,
ii. Mercury is found in batteries, dental amalgam, vacuum pumps and valves, jet fuel
iii. Arsenic is present in wood preservatives, herbicides, corrosion inhibitors, in lead and
copper alloys.
iv. Chromium is found in fresh foods, copy machine toner and nickel in coins, kitchen
i. V. Copper is essential to all living organisms and has a wide range of effects
v. Lead has been used in batteries, electronic equipment’s, in petrol, toys, paint, etc.
2.1.4 Human Exposure and Health Hazards associated with Heavy Metals
Metals and their compounds can accumulate in the body tissues, such as bones or nerves. They
can cross the placenta and harm an unborn child in pregnant women. The health hazards
presented by heavy metals depend on the level and the length of exposure (Thomson,2005). In
some cases, the health effects are immediately apparent while in others, the effects are delayed.
ii. Arsenic (As): skin, liver, kidney, and lymphatic cancer (Shi H. et al.,2004).
9
iii. Cobalt (Co): sterility, hair loss, vomiting, bleeding, and diarrhea.
iv. Copper (Cu): anemia, liver and kidney damage, gastrointestinal problems (Nuhoglu
vi. Mercury (Hg): acrodynia or pink disease, rashes, deafness, brain damage, digestive
vii. Nickel (Ni): damage to lungs, the nervous system, and mucous membranes (Nicholas
et al., 2003).
viii. Lead (Pb): headache, hypertension, abdominal pain, renal dysfunction, arthritis,
intellectual disability, birth defects, autism, psychosis, etc. and even death
(Papanikolaou, N.,2005).
immune systems, chromosomal damage, shortage of red blood cells, and brain
damage.
stomach and intestines, damage to the nervous system. bleeding of livers and kidneys,
paralyses.
xi. Zinc (Zn): retarded growth, chromosomal abnormalities, dwarfism, poor appetite,
mental lethargy, stomach cramps, nausea, vomiting, and central nervous system
disorder.
10
11
2.2 Review of Instrumental Techniques for Metal Analysis
mass spectrum (Skoog D., 1998). In the atomic absorption process, if light of just the right
wavelength impinges on a free, ground state atom, the atom may absorb the light as it enters an
excited state. Atomic absorption measures the amount of light at the resonant wavelength which
is absorbed as it passes through a cloud of atoms. As the number of atoms in the light path
increases, the amount of light absorbed increases in a predictable way. By measuring the amount
of light absorbed, a quantitative determination of the amount of analyte element present can be
made. In atomic emission, a sample is subjected to a high energy, thermal environment in order
to produce excited state atoms, capable of emitting light. The energy source can be an electrical
arc, a flame, or plasma. The emission spectrum of an element exposed to such an energy source
consists of a collection of the allowable emission wavelengths, commonly called emission lines,
because of the discrete nature of the emitted wavelengths. This emission spectrum can be used
both for qualitative and quantitative identification of the element. The technique of flame
Atomic fluorescence technique incorporates aspects of both atomic absorption and atomic
emission. The intensity of this "fluorescence" increases with increasing atom concentration,
providing the basis for quantitative determination. The source lamp for atomic fluorescence is
mounted at an angle to the rest of the optical system. So that the light detector sees only the
fluorescence in the flame and not the light from the lamp itself. It is advantageous to maximize
12
lamp intensity since sensitivity is directly related to the number of excited atoms which in turn is
The ease and speed at which precise and accurate determinations can be made have made atomic
absorption one of the most popular methods for the determination of metals among the three
An ICP-MS combines a high-temperature ICP (Inductively Coupled Plasma) source with a mass
spectrometer. The ICP source converts the atoms of the elements in the sample to ions. These
ions are then separated and detected by the mass spectrometer. ICP technology was built upon
the same principles used in atomic emission spectrometry. Samples are decomposed to neutral
elements in high temperature argon plasma and analyzed based on their mass to charge ratios. An
13
ICP-MS can be thought of as consisting of four main processes, including sample introduction
and aerosol generation, ionization by an argon plasma source, mass discrimination, and the
Infrared absorption spectroscopy is the study of interaction of infrared radiation with matter as a
specific information about the vibration and rotation of the chemical bonding and molecular
structures, making it useful for analyzing organic materials and certain inorganic materials. An
infrared spectrum represents a fingerprint of a sample with absorption peaks which correspond to
the frequencies of vibrations between the bonds of the atoms making up the material. Therefore,
different kind of material. In addition, the size of the peaks in the spectrum is a direct indication
14
of the amount of material present. With modern software algorithms, infrared is an excellent tool
The IR region is commonly divided into three smaller areas: near - IR (400 - 10 cm-1), mid - IR
(4000 - 400 cm-1), and far - IR (14000 - 4000 cm-1). Chemical bonds vibrate at characteristic
frequencies, and when exposed to infrared radiation, they absorb the radiation at frequencies that
match their vibration modes. Measuring the radiation frequency produces a spectrum that can be
used to identify functional groups and compounds (Yahaya et al., 2010). There are three basic
beam splitter.
The beam splitter is a semi-reflecting device and is often made by depositing a thin film of
germanium onto a flat KBr substrate. Radiation from the broadband IR source is collimated and
directed into the interferometer, and impinges on the beam splitter. The basic instrument design
15
i. The Source: Infrared energy is emitted from a glowing black-body source. This beam
passes through an aperture which controls the amount of energy presented to the
ii. The Interferometer: The beam enters the interferometer where the 'spectral encoding'
takes place. The resulting interferogram signal then exits the interferometer.
iii. The Sample: The beam enters the sample compartment where it is transmitted
through or reflected off of the surface of the sample, depending on the type of
analysis being accomplished. This is where specific frequencies of energy, which are
iv. The Detector: The beam finally passes to the detector for final measurement. The
detectors used are specially designed to measure the special interferogram signal.
v. The computer: The measured signal is digitized and sent to the computer where the
Fourier transformation takes place. The final infrared spectrum is then presented to
16
2.2.4 Scanning Electron Microscopy (SEM)
Accelerated electrons in an SEM carry significant amounts of kinetic energy, and this energy is
electrons are decelerated in the solid sample. These signals include secondary electrons (that
(DBSE, that are used to determine crystal structures and orientations of minerals), photons
(characteristic X-rays that are used for elemental analysis and continuum X-rays), visible light
Secondary electrons and backscattered electrons are commonly used for imaging samples:
secondary electrons arc most valuable for showing morphology and topography on samples and
back scattered electrons are most valuable for illustrating contrasts in composition in multiphase
samples (i.e., For rapid phase discrimination). X-ray generation is produced by inelastic
collisions of the incident electrons with electrons in discrete orbitals (shells) of atoms in the
sample. As the excited electrons return to lower energy states, they yield X-rays that are of a
fixed wavelength (that is related to the difference in energy levels of electrons in different shells
for a given element). SEM analysis is considered to be "non-destructive"; that is, x-rays
generated by electron interactions do not lead to volume loss of the sample, so it is possible to
17
iii. Sample Stage
Infrastructure Requirements:
i. Power Supply
18
The SEM is routinely used to generate high-resolution images of shapes of objects (SEI) and to
iii. Compositional maps based on differences in trace element (typically transition metal
The SEM is also widely used to identify phases based on qualitative chemical analysis and/or
crystalline structure. Precise measurement of very small features and objects down to 50 nm in
Activated carbon also called activated charcoal, is a form of carbon that has been processed with
oxygen to create millions of tiny pores between the carbon atoms. Commercial activated carbons
have internal surface area ranging from 500 to 1500 m 2/g. The most common feed stocks used
for the production of activated carbon are wood, coconut shell, bituminous coal, peat etc. The
chars obtained from them could be activated easily to produce reasonably high-quality activated
carbons. During the activation process, the unique internal pore structure is created, which
provides the activated carbon its outstanding adsorptive properties. Activated carbons have a
number of unique characteristics such as large internal surface area, well-developed internal
micro porosity, and wide spectrum of surface functional groups. According to IUPAC definitions
three groups of pores can be identified (Guo and Lau, 2003), which includes;
19
i. Macropores (above 50nm diameter)
Micropores generally contribute to a major part of the internal surface area. Macro and
micropores can generally be regarded as the highways into the carbon particle, and are crucial for
kinetics. The desired pore structure of an activated carbon product is attained by combining the
20
2.4 Preparation of Activated Carbon
2.4.1 Pyrolysis/Carbonization.
This process is to eliminate most of the non-carbon elements such as hydrogen, nitrogen, oxygen
and Sulphur as volatile gaseous products. Low molecular weight volatiles are first released,
followed by light aromatics and finally the hydrogen gas, the resultant product being a fixed
carbonaceous char. The residual carbon atoms are grouped into condensed sheets of aromatic
ring with a cross-linked structure in a random manner. The mutual arrangement of these aromatic
sheets is irregular and leaves free interstices between the sheets, which may be filled with the
tarry materials.
To remove these tarry materials, activation process is carried out. It also enlarges the diameters
of the pores, which were created during the carbonization process and creating new porosity
(Smisek &Cerny,1970).
2.4.2 Activation
The basic characteristics of a carbon are established during the pyrolysis, and the ensuing
oxidation step must be designed to complement the pyrolysis step. During this step, the oxidizing
agent increasingly erodes the internal surfaces of the carbon, develops an extensive and fine
network of pores in the carbon, and changes the atoms lying on the surface to specific chemical
forms which may have selective adsorption capabilities. This activation step is done by two
between 750 and 1100°℃ using oxidants such as steam, carbon dioxide, air or mixture of these
gases. Chlorine, Sulphur vapors, Sulphur dioxide, ammonia and a number of other substances
having activation effects are rarely used. Gasification of the carbonized material with steam and
The reaction of steam with carbon is accompanied by the water gas formation reaction. Which is
Since the reaction of carbon with steam and with carbon dioxide is both endothermic. External
heating is required to drive the reactions and to maintain the reaction temperature. The activation
temperature, steam and CO2 flow rates control the pore development, which in turn affect pore
size distributions and the level of activity of the activated carbon (Guo and Lau,2003).
Chemical activation is usually carried out by impregnating the raw or pre-carbonized material
with an activating agent and pyrolyzed between 400 and 800° ℃ in the absence of oxygen. The
22
most commonly used activating agents are phosphoric acid, hydrochloric acid, Sulphuric acid,
alkalis namely KOH and NaOH, zinc chloride and alkaline metal compounds. Phosphoric acid
and zinc chloride are used for the activation of lignocellulosic materials. Phosphoric acid is the
most preferred activating agent because of its low environmental impact when compared to zinc
chloride. The resultant activated carbon is washed, dried till constant weight is obtained and
ground to required size. Activated carbons produced by chemical activation generally exhibit a
very open structure and bottle shaped, ideal for the adsorption of large molecules (O.Ekpele et
al,2011).
A combination of activated Carbons with a Very high surface area and porosity adequate for
certain specific physical and chemical activation can be tested to Prepare granular applications
such as gasoline vapor, control, gas storage, etc. Activated carbons of this type have reported
using lignocellulosic precursors chemically activated with been phosphoric acid and zinc
chloride and later activated under a flow of carbon dioxide. Uniform, medium-size microporosity
and surface areas above 3600 ㎡/g are obtained with this mixed procedure (Bansal,1988).
i. Granular Activated Carbon (GAC) - are irregular shaped particles with sizes ranging
from 0.2 to 5mm. This type is used in both liquid and gas phase applications.
23
ii. Powdered Activated Carbon (PAC) - are pulverized carbon with a size
predominantly less than 0.18mm (US Mesh 80). These are mainly used in liquid
iii. Extruded Activated Carbon (EAC) - are extruded and cylindrical shaped with
diameters from 0.8 to 5mm. These are mainly used for gas phase applications because
of their low pressure drop, high mechanical strength and low dust content.
Activated carbon is a unique and effective agent for purification and isolation and recovery of
trace material. The various applications can be broadly divided into two categories,
i. Liquid-phase applications.
i. This includes separation, gas storage and catalysis. These products are generally more
ii. Natural gas purification; removal of H2S and BTX Flue gas cleaning at waste
iii. Exhaust air treatment following production processes for the removal of organic
impurities. Purification of process gases, e.g., CO2; scrubbing and separation of oil
exhaust systems.
24
iv. Emission control, e.g., at filling stations and during tank ventilation for motor vehicle
v. Pollutant removal in car interior ventilation systems in gas masks, and as a carrier
In the water treatment sector, activated carbon is used cither in powdered (suspension process) or
granular (fixed bed process) form, depending upon the specific application and process.
Increasingly exacting quality requirements for drinking water, coupled with increasing pollution
levels in untreated water (groundwater and surface water), have led10 the optimization of
activated carbon as a means of guaranteeing acceptable drinking water quality (O. Ekpete et
al,2011).
In recent years, the use of activated carbon processes has become widely established in drinking
water treatment, groundwater rehabilitation and the treatment of service water. Likewise,
activated carbon is being used to an increasing extent in waste water treatment, whether it be in
the systematic treatment of individual effluent streams (e.g., in the chemicals industry), in the
water treatment, where effluent restrictions are particularly severe (P. Sugumaran, et al., 2012).
The use of activated carbon is especially advisable in cases requiring the removal of toxic
substances or pollutants that are not easily biodegradable. Activated carbon is almost always
employed in the treatment of waste water in the paper, textile and petrochemical industries
25
2.7 Hospital Wastewater
Wastewater can be defined as any water, whose quality has been adversely being abused by
anthropogenic influence which includes liquid waste discharged from domestic home, industries,
Previous study had shown that the volume of water generally generated from hospitals varies
from 400 to 1200L/day/bed. This volume of water produces by the hospital contain micro-
organisms, heavy metals, toxic chemicals and radioactive elements which results in the
production hybrid wastewater as the combination of domestic, industrial and effluents of care
and medical research. The hospital wastewater is also found to contain chlorinated molecules in
high concentrations and heavy metal such as mercury and silver. The occurrence of
strong painkillers, tranquilizers and chemotherapy chemicals given to cancer patients excreted by
humans and domestic animals are distributed into the environment by flushing toilets and
spreading manure and sewage sludge onto and into soil (Emmanuel et al., 2002). From WHO
report,85% of hospital waste is non-hazardous, 10% infective and 5% not infective but
Waste water from hospital may come from few categories of hospital facility which are clinical
and research laboratories, medical waste incinerators and hospital laundries (Niumpang,2006).
26
CHAPTER THREE
MATERIALS AND METHOD
3.1 Sample Collection and Pretreatment
3.1 The Apple of Sodom (Calotropis procera) plant stems were collected from trees located at
kamazou and janruwa roadside, new road, Kaduna North, Kaduna. The stems collected were
then washed with Tap water to wash of all dirt and dusts and sun dried for 3days. Afterward
washed with distilled/deionized water and then oven dried at 105°for 24hours.The hospital
wastewater was collected from the maternity ward at Barau Dikko Teaching hospital Kaduna
state, Kaduna. The listed procedures below were then carefully carried out.
The Apple of Sodom (Calotropis procera) plant collected was dried and pounded then, sieved
Open Carbonization was done using the hot plate for 15min and afterward carbonization using
the muffle furnace at a temperature of (0 - 400° C) for 1hr. The sieved product was allowed to
cool down in the desiccator and activated using prepared 1M HNO3 as activating agents. The
activated carbon was produced with a slight modification using standard methods of Ekpete (O.
Ekpete, et al., 2011) and Sugumaran (P.Sugumaran, et al., 2012).In a beaker,15g of the
carbonized Pride of Barbados was impregnated with 60mL 1M HNO 3. The beaker contents (15g
of the carbonized sample and 60mL 1M HNO 3) were thoroughly mixed using a heating mantle at
a constant temperature of 80° C until it formed a paste (the activating agent was fully absorbed
by the raw material). The paste was then transferred into a crucible. The carbonized sample was
allowed to cool to room temperature and was washed using hot water and was further washed
27
with distilled water to remove residual acid until a neutral pH of 6.1 was obtained. It was then
oven-dried at 105° C for 6hrs, and then kept in air tight pack for further analysis and labelled as
CAHAC (Carbonized Apple of Sodom HNO3 Activated Carbon), and UAC (Untreated Apple of
Sodom Carbon).
The activated carbon sample was dried to avoid relatively high surface tension and micro-ripping
of the surface upon leaving. The surface dusts were removed using acetone. Hexamethyldisilane
(HMDS) was used in cell preparation and after a short (3 minutes) incubation, it was removed
and excess was left to evaporate. The sample was mounted on a metal stub using a sticky carbon
disc which increases conductivity. The sputter was coated with a conductive material (gold) to
prevent charge buildup on sample surface. The metal was applied in a controlled manner in the
sputter coater. The coating thickness was around 10nm to prevent charging and to ensure clarity
of the sample surface details. The sample was completely dried before loading into SEM
A Zeiss EVO-50 Scanning Electron Microscope (SEM) was used to determine the surface
morphology of the activated carbon produced at magnifications of 255, 350, 500, 1000, 1500 and
A glass cylinder(25mL) was filled to a specified volume with 1.0g 2mm powder carbon sample
of each of CAHAC, and dried in an oven at 105°C for 6hr.The cylinder was tapped for 1-2
28
minutes to compact the carbon (P.Sugumaran, et al., 2012).The bulk density calculated and
(3.1)
Thermal drying method was used in the determination of moisture content of the samples.1.0g
carbonized sample was weighed in triplicate and placed in clean, dried, and weighed crucible.
The crucible was placed in an oven at 105°C to constant weight for 4hrs according to the method
of Rengaraj (S. Rengaraj, et al., 2002). The difference between the initial and final mass of the
carbon represents the moisture content. The percentage moisture content (%) was computed as
follows:
Moisture (%) = Loss in weight on drying (g) ÷ Initial weight x100 (3.2)
For ash content determination, crucibles were preheated to about 105°C for 45min,then cooled in
a desiccator for 15min, and weighed. 1.0g of each sample was transferred into the crucibles and
reweighed. The crucibles containing the samples were then placed in the oven and the
temperature was allowed to rise to 105℃ for about 3hr and allowed to cool in a desiccator to
room temperature (30°C) and reweighed (S.Rengaraj, et al., 2002). The ash content was
Ash (%) dry = Ash weight (wet) (g) ÷ Oven dried weight (g) x 100 (3.3)
29
3.7 The Fourier Transform Infrared (FTIR) Analysis
For sample analysis, 0.5g of activated carbon was mixed with about the same amount of
potassium bromide KBr. The mixture thus obtained was crushed in a mortar to obtain a
homogeneous powder which was then introduced into a mould to obtain very fine plates. The
plates were then introduced into the spectrophotometer for analysis. The wave number was found
to vary between 4000 and 650cm-1. The Fourier Transform Infrared (FTIR)analysis of the
samples was carried out using FTIR equipment of Happ-Genzel for the examination of the
2g of the activated carbon was mixed with 100mL of the hospital wastewater in a 100mLconical
flask and stirred at room temperature of 32°C for 15 min and allowed to stand for 50 min to
ensure equilibrium. It was then filtered using the filter paper. The concentration of Pb +2 and Ni+2
in the hospital wastewater was determined before and after interaction with the activated carbon
using Hanna Instrument Multi-Parameter Photometric with COD (Apiprecya, et al., 2006), The
amount of metal ions adsorbed by the adsorbent was determined using the equation;
The percentage of metal ions removed was obtained from the equation;
31
CHAPTER FOUR
4.1 Results
The proximate composition analysis (bulk density, moisture content and ash content)
The heavy metal ions present in the wastewater sample were analyzed using the Hanna
Ni+2 present. The initial and final concentrations of Pb +2 and Ni+2 present in the wastewater is
shown in table 4.2 and the quantity of metal ions removed and percentage removed are shown in
table 4.3.
32
Table 4.1 Proximate composition of activated carbon from apple of Sodom plant stem.
Parameters Values
Table 4.2 Quantity of Pb+2 and Ni+2 in waste water before and after treatment with activated
carbon.
Table 4.3 The quantity of metal ions (Pb+2 and Ni+2) and percentage removed after treatment
with activated carbon.
33
Percentage (%) yield = weight of final activated carbon x 100
(3.5)
15g
The FTIR spectroscopy analysis results show these Infrared Spectra which are generally
informative about what functional group are present. The result is shown in figure 4.1.
Fig 4.1 The FTIR spectroscopy analysis of activated carbon produced from apple of Sodom
plant stem.
34
4.1.4 Sample surface morphology: - The scanning electron microscopy (SEM)
The scanning electron microscope images of activated carbon produced from apple of Sodom
plant stem activated using nitric acid (HNO 3) are shown in plates 4.1(a-f) at 255, 350, 500, 1000,
35
Plate 4.1a
36
Plate 4.1b
37
Plate 4.1c
38
Plate 4.1d
39
Plate 4.1e
40
Plate 4.1f
41
4.2 Discussion
4.2.1 The proximate composition analysis of activated carbon from Apple of Sodom Plant
Stem
The proximate analysis of activated carbon from apple of Sodom plant stem (Table 4.1) was
carried out to determine the percentage by mass of the moisture content, carbon content, ash
content and bulk density which was gotten as 4.03%, 20.13%, 7.03% and 2.06g respectively. The
above result goes in agreement with other research work when compared (Kalpana Patidar and
Manish vashishtha, 2019, characterization and isotherm study of activated carbon production
from mustard stalk by Zncl2 activation) results where; moisture content 9.58%, carbon content
12.65%, ash content 0.01%. (Mohd Iqbaldin MN, Khudzir I, Mohd Azlan MI, Zaidi AG, surani
B and Zubri Z, 2013, properties of coconut shell activated carbon), results where; ash content
0.8% and carbon content 21.38%. (Noor Shawal Nasri et al,2020, synthesis and characterization
of green porous carbon with large surface area by two steps chemical activation with KOH),
results where; moisture content 8.21%, ash content 0.01%, carbon content 18.6%. So therefore,
from the above results compared to this investigation, it shows one thing in common, i.e., they
all have a high carbon content and a low ash content, proving that basically researches on
activated carbon has a high carbon content and low ash content. The significance of ash content
and carbon content in activated carbon is that, the ash content is an actual property of activated
carbon, it decreases the effectiveness of the activated carbon, you will find low ash content in all
activated carbon products, while the carbon content on the other hand gives an indication of the
42
4.2.3 The FTIR spectroscopy analysis of activated carbon produced from apple of Sodom
The FTIR absorption bands of the apple of Sodom plant stem activated carbon revealed that the
carbon contains the following functional groups; alkene(C-H), amine salt (N-H), alkane (C-H),
thiocyanate (SC≡N), conjugate alkene (C=C), nitro compounds (N-O), sulfoxide (S=O), halo
compound (C-Cl), halo compound (C-Br) and halo compound (C-I). The assignment of the
specific wavelength to some functional group was not possible because the adsorption bands of
various functional groups overlap and shift depending on their molecular structure and
environment.
43
Table 4.4 FTIR analysis wave length and standard IR wave number and corresponding
700 ± 20 694.80 - - -
44
These results are in agreement with the findings of other research work on activated carbon.
shariatmadari, C. beiver and J. bedia, 2019, phenol adsorption on high microporous activated
carbons from oily sludge) results were; 3422, 1455, 1090, 800 which are amine, alkene, alkane,
secondary alcohol and halo compound c-cl. (Yufeng zhao, chul-woong cho, longzhe cui, wei
wei, 2019, adsorption removal of endocrine disruption compounds and a pharmaceutical using
activated charcoal from aqueous solution) results were; 3422, 2924, 2854, 2346, 2086, 1622,
1444, 1118,874 which are amine, alkane, carbon dioxide, isothiocyanate, alkene, secondary
alcohol. (Cafer saka, 2012, iodine number analysis and preparation of activated carbon from a
corn shell by chemical activation with ZnCl2) results where; 2919, 2853, 2325, 1743, 1544,
1145, which are alkane, carbon dioxide, ester, nitro compound and sulfone.
From the above different works on activated carbon compared to this investigation, the results
gotten where similar, the little differences may result from the solvent that was used for the
chemical activation. For the work of (N. mirghaffari, M. Soleimani, H. shariatmadari, C. beiver
and J. bedia, 2019) the research uses phenol as the solvent for chemical activation and the only
different functional groups from this research are secondary alcohol and carbon dioxide. For the
work of (Yufeng zhao, chul-woong cho, longzhe cui, wei wei, 2019) the research uses KOH as
activating agent and the only different functional group for this research is secondary alcohol.
For the work of (Cafer saka, 2012) the research uses ZnCl 2 as solvent for chemical activation and
the only different functional group sulfone, esters and carbon dioxide.
The slight reason for the differences observed in these researches compared to this investigation
was because nitric acid (HNO3) was used as solvent for chemical activation. Comparing with the
45
standard and the above works on activated carbon, it falls with the normal recommended
4.2.3 Assessment of the activated carbon produce from the apple of Sodom plant stem for
Based on equilibrium studies, the activated carbon produced from the apple of Sodom plant stem
removal capacity for the two heavy metal ions (Pb +2 and Ni+2) studied, appears to be greatest for
Pb+2 followed by Ni+2 due to the percentage removal value determined and recorded as 47.86%
Comparing the metal ions percentage removed of this investigation which are (Pb +2 45.45% and
Ni+2 47.86%) with (Hala Ahmed Hegazi, 2013, removal of heavy metals from wastewater using
agricultural and industrial waste as adsorbents) the percentage of metal ions of Fe 2+, Pb2+, Cd2+,
Cu2+, and Ni2+ are 68.59%, 22.22%, 26.04%, 24.49% and 94.885% respectively. The difference
occurs in the usage of adsorbents, in this investigation agricultural waste was used and the results
gotten were (Pb+2 45.45% and Ni+2 47.86%) but in the above research work, agricultural and
industrial waste was used as adsorbents and the percentage of the metal ions was high. From the
work of (Benard E, Jimoth A. and Odigure J.O, 2013, heavy metal removal from industrial
wastewater by activated carbon prepared from coconut shell). The percentage of the metal ions
Cu2+, Fe2+, Zn2+ and Pb2+ are 43.50%, 16.60%, 17.40 and 0.005% respectively. From the above
research the adsorbent was industrial waste and metal ion percentage were Cu 2+, Fe2+, Zn2+ and
Pb2+ are 43.50%, 16.60%, 17.40 and 0.005% respectively. Compared to these investigation,
agricultural waste was the adsorbent and the metal ion percentages (Pb +2 45.45% and Ni+2
46
47.86%). So therefore, it was observed that different wastewater has numerous percentages of
4.2.4 The surface morphology images of activated carbon from the apple of Sodom plant
stem
The scanning electron microscopy images of activated carbon produced from the apple of Sodom
plant stem using nitric acid (HNO3) are shown in fig 4.1(a-f) at 255, 350, 500, 1000, 1500 and
2000 magnifications. The SEM photograph showed that wide varieties of pores are present in the
activated carbon which revealed that it is porous in nature and thereby, a good adsorbent.
Compared to the research of (Benard E, Jimoth A. and Odigure J.O, 2013, heavy metal removal
from industrial wastewater by activated carbon prepared from coconut shell). Which shows in
plate 1 and 2 the image of activated carbon with the pores on them proving that they are good
adsorbent.
47
CHAPTER FIVE
SUMMARY AND RECOMMENDATION
5.1 Summary of Results
As the activated carbon produced is highly dependent on the raw materials used, Apple of
Sodom was used due to its high carbon content. The activating agent used HNO3 was used
because acid activated carbon performs better in the low concentration range. The activation
process is also essential for production of a good adsorbent; the activated carbon was prepared
by chemical activation because it gives higher yield of carbon as well as larger pore size in the
The activated carbon produced was analyzed for the following; bulk density, moisture content,
ash content, percentage adsorption/removal capacity of Pb+2 and Ni+2 and recorded as
includes; alkene(C-H), amine salt (N-H), alkane (C-H), thiocyanate (SC≡N), conjugate alkene
(C=C), nitro compounds (N-O), sulfoxide (S=O), halo compound (C-Cl), halo compound (C-Br)
and halo compound (C-I). The surface morphology determined is shown in Plate 4.1a-f.
In conclusion, the production of activated carbon from agricultural waste materials using
chemical activation process for use as adsorbent provides an environmentally friendly source of
alternative energy. The HNO3 activation develops good porous structure; HNO 3 etches the
carbon surface through vigorous reaction while acting as a dehydrating agent to force all
48
5.2 Recommendations
Due to the duration and cost implication of this research work, only few analysis were carried
1.Research on the production and characterization of activated carbon from Apple of Sodom by
varying the absorbent dosage activation time and temperature respectively should be carry out.
2. More in-depth analysis on production of activated carbon from pride of Apple of Sodom using
other activating agents such as; phosphoric acid (H3PO4) and sulphuric acid(H2SO4) should be
carried out.
3. Similar research using different precursor material with additional analysis such as; adsorption
isotherms, pore volume estimates, kinetic studies and gravimetric analysis to estimate porosity
49
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