INTRODUCTION

With the ever-increasing use of water for municipal and industrial purposes, it has become
necessary to appraise water quality on a continuous basis. Water treatment process selection
is a complex task involving consideration of many factors which include, available space for
the construction of treatment facilities, reliability of process equipment, waste disposal
constraints, desired finished water quality and capital and operating costs. The treatment of
wastewaters to make them suitable for subsequent use requires physical, chemical and
biological processes. A number of technologies are available with varying degree of success
to control water pollution. Some of them are coagulation, foam flotation, filtration, ion
exchange, aerobic and anaerobic treatment, advanced oxidation processes, solvent extraction,
adsorption, electrolysis, microbial reduction, and activated sludge. However, most of them
require substantial financial input and their use is restricted because of cost factors overriding
the importance of pollution control .Among various available water treatment technologies,
adsorption process is considered better because of convenience, ease of operation and
simplicity of design. Oil is one of the most important energy sources in the developed world.
However, oil spill accidents often take place during the oil utilization process, resulting in
energy loss as well as threats to the environment. Oil transportation is a risky business and oil
spills require immediate attention. It is important that after an oil spill the marine cleanup
operation should collect or adsorb quickly a major part of the oil spilled, especially in coastal
areas. Oil-polluted water often contains other substances as well as oil. Therefore the existing
cleaning processes are complex and may consist of different water purification units. Oil and
chemical spill accidents can be caused by human mistakes and carelessness, deliberate acts
such as vandalism, war and illegal dumping, or by natural disasters such as hurricanes or
earthquakes. Offshore and shoreline waters can be polluted by oil drilling operations,
accidents involving oil tankers, runoffs from offshore oil explorations and productions, and
spills from tanker loading and unloading operations. Massive marine oil spills have occurred
frequently and resulted in a great deal of damage to the marine, coastal and terrestrial
habitats, economical impacts on fisheries, mariculture and tourism, and loss of energy source.
Inland water bodies can be polluted by leaking of oil through pipelines, refineries, and
storage facilities, runoff from oil fields and refinery areas and, in some cases, process effluent
from petroleum refineries and petrochemical plants. A number of materials have been
extensively investigated as adsorbents in water pollution abatement. Some of the important
ones include silica gel, activated alumina, zeolites and activated carbon. One of the most
economical and efficient methods for combating oil spills is oil removal by adsorbents. Oil
sorbents are able to concentrate and transform liquid oil to the semi solid or solid phase,
which can then be removed from the water and handled in a convenient manner without
significant oil draining out. The preferable sorbent materials are those which, besides being
inexpensive and readily available, demonstrate fast oil sorption rate, high oil sorption
capacity, low water pickup high oil retention capacity during transfer, high recovery of the
absorbed oil with simple methods, good reusability, high buoyancy, and excellent physical
and chemical resistances against deformation, photo degradation, and chemical attacks. There
are three major classes of oil sorbents, namely, inorganic mineral products, organic synthetic
products and organic natural products. At present, most of the commercially available oil
sorbents are organic synthetic products such as polypropylene (PP) and polyurethane.
However, they are non-biodegradable and can be difficult to deal with after use due to their
xenobiotic nature. The mineral products used as oil sorbents include perlite, exfoliated

1
graphite, vermiculites, organoclay, zeolite, silica aero gel and diatomite. Most of them have
poor buoyancy and oil sorption capacity. In addition, they are difficult to handle on site due to
their granular or powder forms. Most of them also exhibit poor reusability and oil recovery.
Due to inadequate hydrophobicity, they may also experience collapse of their microstructure
due to sorption of water. While exfoliated graphite and silica aero gel are excellent oil
sorbents, they are fairly expensive. The limitations of the mineral products and organic
synthetic products have led to the recent interest in developing alternative materials,
especially biodegradable ones such as natural agro-based products. Agricultural products
which have good oil absorbency are Egg shell, Banana peel, Rice husk, Ground Corn cobs,
straw. These agricultural products and residues are inexpensive and available locally. Some
are waste materials and hence their reuse will result in savings in disposal fee. The cellulosic
products which exist in fibrous form can be easily formed into mats, pads, and nonwoven
sheets for convenient applications. In this study, eggshell, banana peel and saw dust were
used in the biosorption of dissolved and dispersed oils from oil contaminated water.

1. MATERIALS AND METHODS

2
2.1. PROCESSING OF ADSORBENTS

i) Eggshell powder-
Egg was boiled and peeled off for its shell and the shell was air or sun dried to
dryness. Then, it was heated in hot air oven for 1 - 2 hrs until shell gives
pungent smell, at 150o C. The egg shell was treated with HCl solution. It was
washed with water and once again kept in hot air oven for dryness at 150 o C.
After half an hour, it was removed from hot air oven, crushed manually with
Mixture grinder, to increase surface area, for better result.

Figure 1 :Egg shell Powder

ii) Banana Peel

Powder-
Banana peel was obtained from fruit market in fancy bazaar.
The banana peel obtained was washed with ordinary water to remove suspended
particles and then sun dried. The dried material was then washed severally with
distilled water to remove water soluble materials and later dried in sunlight again
until constant weight. After that the dried banana peels are cut into small pieces
with a knife and grinded into fine powder in a mixture grinder.

iii) Rice Husk- Figure 2 :Banana peel Powder

The rice husk is obtained from
rice mills. The rice husk is the continuous layer
of the paddy grain that is separated from the rice grains during the milling
process. The husk obtained was washed to
remove suspended particles
and then sun dried. The dried
husk then grinded into fine
powder with the help of
grinding mixer.

3
 Figure 3 :Rice husk

2.2. EQUIPMENT AND APPARATUS

i) One litre container
ii) Pipette
iii) Beaker
iv) Filter Paper
v) Test Tubes
vi) Knife
vii) Mixer Grinder
ix) Electronic Balance -
An electronic balance is a device used to find accurate
measurements of weight. It is used very commonly in laborites for
weighing chemicals to ensure a precise measurement of those
chemicals for use in various experiments. Laboratory Balances
offered by us are easy to clean, precise as well as simple to usage
in given laboratory environment. Being simple in set up, these
come with spill-resistant housing and are made available in
Figure 4: different model options as per the end applications these are used
Electronic in.
Balance

ix) Mechanical Stirrer -

A mechanical stirrer is a laboratory equipment used to
mix, blend or agitate substances in a testube, flask or
beaker .It contains an oscillating board which is used to
place the flasks, beakers, test tubes, etc. Although
the magnetic stirrer has come to replace the uses of
stirrer lately, the stirrer is still a preferred choice of
equipment when dealing with such
large volume substances, or simultaneous agitation is
Figure 5 :Mechanical Strirrer
required.

x) UVVIS Spectrophotometer -

4
Ultravioletvisible
spectroscopy or ultraviolet-visible
spectrophotometer (UV-VIS or UV/Vis) refers
to absorption spectroscopy or reflectance
spectroscopy in the ultraviolet-
visible spectral region. This means it uses
light in the visible and adjacent (near-UV
and near-infrared [NIR]) ranges. The
absorption or reflectance in the visible range Figure 6 :UV-VIS Spectrophotometer
directly affects the perceived color of the
chemicals involved. In this region of the electromagnetic
spectrum, atoms and molecules undergo electronic transitions. Absorption
spectroscopy is complementary to fluorescence spectroscopy, in
that fluorescence deals with transitions from the excited state to the ground
state, while absorption measures transitions from the ground state to the excited
state.

xi) Sonicator -

Sonication is the act of applying sound energy to

agitate particles in a sample, for various
purposes. Ultrasonic frequencies (>20 kHz) are
usually used, leading to the process also being
known as ultrasonication or ultra-sonication.

In the laboratory, it is usually applied using

an ultrasonic bath or an ultrasonic probe,
colloquially known as a sonicator. In a paper
machine, an ultrasonic foil can distribute cellulose
fibres more uniformly and strengthen the paper. In our project we used this instrument to
Figure 7: Sonicator make a oil-water emulsion out of it.

2.3. PROCEDURE OF THE EXPERIMENT-

i) At first the calibration graph (Adsorption vs Concentration) was prepared using UV-VIS
Spectrophotometer. The oil sample was weighted using electrical balance. Various samples of
concentration were prepared for the calibration curve. The emulsion was prepared using
sonicator. From the Adsorption vs Concentration graph, obtained from UV-Vis
Spectrophotometer, the calibration curve is obtained. This calibration graph is used for
determining the concentration of unknown sample, after finding out their adsorption from the
UV-Vis Spectrophotometer.

Figure 8 :Dried Sample

Figure 9 :Weighted
Sample
 ii) An emulsion of 1000 ppm oil-water
solution of
200ml is
prepared for
the purpose
of carrying
out our

experiments. 200mg of the crude oil sample is carefully weighted

in an electronic balance. After that it is mixed with 200ml of water.
The solution is kept in sonicator for 1 hour to prepare a stable
emulsion.

iii) 20ml of emulsion is collected in three sets of three

Figure 10: Final sample for UV-Vis
Test for Banana Peel
specified time.
conical flasks . Initially egg shell powder was added
in amounts 1gm, 1.5gm and 2gm in each set of
conical flasks respectively. After that the conical
flasks are kept on mechanical stirrer for 15 minutes.
After that 5 ml of the mixture is pipetted out, filtered
and collected in test tubes after 5 minutes, 10 minutes
and 15 minutes respectively.
The sample from the test tubes are filtered using filter
paper, to remove the adsorbents along with the oil
adsorbed by them in the

iv) The above step is repeated for the other two adsorbents i.e.
Banana peel powder and Rice Husks.
v) The filtered samples from the test tubes are now put into the
UV-Vis Spectrophotometer. The adsorbent data obtained from the
UV-Vis Spectrophotometer. From the calibration curve previously
generated, the concentration of the unknown samples are found out.
The amount of oil adsorbed is calculated as:
Figure 11: Final
Amount of oil adsorbed = 1000 ppm Final conc. of the sample sample for UV Vis
for Egg shell
3. RESULTS AND DISCUSSION
i) The calibration curve was prepared using the following data.

6
 Sl. No Oil Amount(mg/200ml water) Concentration(ppm)
1 307.5 1537
2 204.4 1022
3 152.2 761
4 129 645
5 110 550
6 79.6 398
7 55.6 278
8 37 185
9 22.4 112
10 10.6 53

Table 1: Concentration Data for Calibration Curve

Using the data obtained from UV-VIS Spectrophotometer, the absorption versus
concentration curve is obtained.
The equation of the curve is given by :-
y = 0.001x + 0.571 ; R = 0.935 (obtained from excel)

7
 Abs
3

2.5 f(x) = 0x + 0.57

R = 0.93
2
Abs
Linear (Abs)
1.5

0.5

0
0 200 400 600 800 1000 1200 1400 1600 1800

Fig : 12 Absorption vs Concentration Plot

ii) After the adsorbents were added to the 1000 ppm emulsion, the following data is obtained
from UV-Vis Spectrophotometer.

8
 SL No. Weight (g) Time Concentration Amount of oil Adsorbed
(minutes) (ppm) (ppm)
5 789.77 210.13

1 1 10 786.76 213.24
E
15 783.45 216.55
G
G 5 685.74 314.26

S 2 1.5 10 681.98 318.02

H
E 15 679.64 320.36
L
L 5 685.54 314.46

3 2 10 680.02 319.98

15 679.23 320.77

Table 2: Adsorption Data for Egg Shell

Table 3: Adsorption Data for Banana Peel

SL No. Weight (g) Time Concentration Amount of oil Adsorbed
(minutes) (ppm) (ppm)
5 973.43 26.57

1 1 10 973.43 26.57
B
15 973.43 26.57
A
N 5 972.33 27.63
A
N 2 1.5 10 972.33 27.63
A
15 972.33 27.63
P
E 5 970.87 29.13
E
3 2 10 970.87 29.13
L
15 970.87 29.13

Table 4: Adsorption Data for Rice Husk

9
 SL No. Weight (g) Time Concentration Amount of oil Adsorbed
(minutes) (ppm) (ppm)
5 1000 00.00

1 1 10 1000 00.00
R
15 1000 00.00
I
C 5 1000 00.00
E
2 1.5 10 1000 00.00
H
U 15 1000 00.00
S
K 5 1000 00.00

3 2 10 1000 00.00

15 1000 00.00

Table 5: Comparison of the Adsorbents

Adsorbents Used ( 2g) % Oil Removal in 15 minutes

Egg Shell 32.07

Banana Peel 2.91

Rice Husk 0

10
 5. CONCLUSION

Natural Adsorbents are the alternatives for Oily Waste Water Treatment for their simplicity ,
excellent oil-removal properties, environmental friendly characteristics, easy availability,
cheap cost and feasibility.
Three natural adsorbents: Egg Shell, BananaPeel, Rice Husk were used in our project for
removing the oil from oil-water emulsion. UV-VIS Spectrophotometer was used for
determining the oil percentage removed from the emulsion.
Egg Shell is readily available low cost sorbent which can be used to remove oil from oil
polluted water. This study identifies the Egg Shell waste as a suitable sorbent to be utilized
for continuous remediation of oil from oil polluted water.

Banana Peel and Rice Husk can also be used to remove oil from oil polluted water but Egg
Shell Powder is more efficient in comparison to the other two adsorbents.

The Oil removing efficiencies of the three Adsorbents in increasing order is as follows:
Rice Husk < Banana Peel < Egg Shell.

6. REFERENCES

11
1. Pasila, A. (2004) 'A biological oil adsorption filter', Marine Pollution Bulletin, vol. 49, pp.
1006-1-12.
2. El-Nafaty, U., Muhammad, I. & Abdulsalam, S., 2013. Biosorption and Kinetic Studies on
Oil Removal from

3.Produced Water Using Banana Peel. Civil and Environmental Research (IITE), 3(7), pp.
125-135.
4. Sitea, A.D. (2001) 'Factors Affecting Sorption of Organic Compounds in Natural
Sorbent/Water Systems and Sorption
5. Coefficients for Selected Pollutants. A Review', J. Phys. Chem. Ref. Data, Vol. 30, No. 1,
october, pp. 187-439.
6. Williams, J. B., C. Clarkson, C. Mant, A. Drinkwater, and E.
May. 2012. Fat, Oil And Grease Deposits In Sewers:
Characterisation Of Deposits And Formation Mechanisms.
Water Research. 46(19): 6319-6328
7. Ibrahim, S., S. Wang, and H. M. Ang, 2010. Removal Of
Emulsified Oil From Oily Wastewater Using Agricultural Waste
Barley Straw. Biochemical Engineering Journal. 49(1): 78-83.
8. R.F. Johnson, T.G. Manjrekar, H.R. Halligan, Removal of oil from water surfaces by
sorption on unstructured fibers, Environ. Sci. Technol. 1973, 7,439.

9 .J.W. Paterson, Industrial Wastewater Treatment Technology, 2nd ed, Butterworth

Publishers, Inc, Stoneham, MA, 1985.

12