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A SEMINAR REPORT
Submitted by
KEVIN D THOMAS
of
ERNAKULAM 682313
SEPTEMBER 2014
Toc H INSTITUTE OF SCIENCE & TECHNOLOGY
ARAKKUNNAM, ERNAKULAM-682 313
DEPARTMENT OF CIVIL ENGINEERING
CERTIFICATE
TIST TIST
i
ACKNOWLEDGEMENT
This seminar work is the product of hard work and experience and it goes a long
way in shaping a person in his respective profession. If words can be considered as
token of acknowledgement and symbols of love, then these words play a vital role in
expressing my gratitude. First of all, Im thankful to God Almighty, for his
choicest blessings for the successful completion of my seminar.
Last but not the least; Im grateful to all my friends and parents for their valuable
motivation and support.
Kevin D Thomas
S7, CE
ii
ABSTRACT
Water pollution is the contamination of water bodies. Water pollution occurs when
pollutants are directly or indirectly discharged into water bodies without adequate
treatment to remove harmful compounds. Two types of adsorbants are used to treat oily
waste water, activated carbon and activated lemon peels. This report deals with two
studies conducted by Khaled Okiel, Mona El-Sayed& Mohammed Y. El-Kady on the
topic Treatment of oil-water emulsion by adsorption on to activated carbon and A.R.
Tembhurkar, Ph. D & Radhika Deshpandeon the topic Powdered Activated Lemon Peels
as Adsorbent for Removal of Cutting Oil from Wastewater. Past literature have shown
that lemon peels performed some better properties in removal of oil. The adsorption
behavior of oil on to activated carbon was examined as a function of contact time, the
weight of adsorbent and the concentration of adsorbate. Oil removal percentage increase
with increasing contact time and the weight of adsorbents, and decrease with increasing
the concentration of adsorbate. It is seen that the adsorption process on activated carbon fit
the Freundlich isotherm model. These existing treatment technologies are mostly
expensive and many times are not so effective. Thus, this demands a search for new
alternatives for oil removal. Recent research has directed towards finding the feasibility of
using activated lemon peels. The maximum adsorption efficiency of lemon peels
depending on various parameters namely pH, dose of adsorbent, contact time, mixing
speed and initial oil concentration are discussed in detail.
iii
CONTENTS
CERTIFICATE i
ACKNOWLEDGEMENT ii
ABSTRACT iii
LIST OF TABLES vi
LIST OF ABBREVATIONS ix
LIST OF NOTTATIONS x
1. INTRODUCTION 1
iv
2.5. RESULTS OBTAINED 6
3.5.1. pH 16
5. CONCLUSION 25
REFERENCES
v
LIST OF TABLES
vi
LIST OF FIGURES
vii
Fig No. Name Page No.
viii
LIST OF ABBREVIATIONS
Abbrevation Expansion
PAC POWDERED ACTIVATED CARBON
DC DEPOSITED CARBON
ix
LIST OF NOTATIONS
Notation Expansion
qe AMOUNT OF ADSORBATE PER UNIT WEIGHT
OF ADSORBENT (mg/g)
x
1. INTRODUCTION
One of the most challenging environmental problem today is the removal of oil
from waste water. The automobile industry and other metal manufacturing facilities use
large amount of synthetic fluids and natural oil based products, resulting in large
amounts of high organic strength, oily waste waters. The oil from these sources may be
either as free oil or in the form of emulsion. This oil spills have wide variety of impacts
on the environment, with the possibility of severe economic and ecological
consequences.
The emulsified oil in the wastewater constitutes a severe problem in the different
stages of treatment. The exhausted oil from industrial activities or operational
maintenance of a machine is usually disposed of in conventional sewage treatment
plants, causing environmental damage in particular to microorganisms responsible to
biological processes. Most organic pollutants were more soluble in oil than in water.
Therefore, the removal of oil and grease would result in significant removal of these
pollutants. Oil and greases have great capacity to penetrate to the ground; hence they
constitute a very serious threat for ground water. Due to hazards of oil field effluent on
environment, treatment is necessary before disposal.
Free oil can be easily separated by mechanical methods, but there are only few
methods to remove the emulsified oil content. The important methods are variety of
filters, adsorption, reverse osmosis, gravity separation, ultra-filtration, micro filtration,
biological processes, air floatation, chemical coagulation, electro coagulation and
flocculation. One commonly used technique for removing oil dissolved in water is the
process of adsorption, because this method has high efficiency compared to other
methods. Efficiency of filtration, adsorption, biological processes, air floatation,
coagulation and flocculation are 82%, 97%, 93.6%, 77%, 94% and 95% respectively.
Adsorption is the process which involves the separation of substances from one phase to
the surface of another.
Adsorption is one of the most efficient methods for the treatment and removal of
oil contamination in waste water. This process has advantages over the other methods
because of simple design and can involve low investment in term of initial cost. The
1
adsorption process is widely used for treatment of industrial wastewater from organic
and inorganic pollutants and meets the great attention from the researchers. In recent
years, the search for low-cost adsorbents that have pollutant binding capacities has
intensified. Materials locally available such as natural materials, agricultural wastes and
industrial wastes can be utilized as low-cost adsorbents. Commonly used adsorbents are
activated carbon, bentonite, deposited carbon, clay, clay minerals, zeolite etc.
Oil adsorbents comprise a wide range of organic, inorganic and synthetic products
designed to recover oil in preference to water. Their composition and configuration are
dependent upon the material used and their intended application in the response. In order
for a material to act as an adsorbent, it should be attract oil preferentially to water, i.e.it
should be both oleophilic and hydrophobic. Emulsified oil in waste water can be removed
by adsorption on powdered activated carbon. But adsorption by activated carbon is
mostly expensive and many times are not so effective and needed some supplementary
treatment to satisfy the standards. So a new adsorbent material is invented, that is
powdered activated lemon peels. Activated lemon peels are cheap, nontoxic, easily and
locally available material also it have high efficiency.
2
the AC surface have been introduced using chemical/physical treatment, impregnation
and surface modification with surfactant. It has also been shown that chemical
modifications can improve the adsorption capabilities of activated carbons for various
molecules. Modification of the surface chemistry of activated carbons may be a possible
attractive route toward novel applications of these materials as an adsorbent for
contaminants removal.
New adsorbent was prepared from lemon peels. Then it was dried for 3-4 days
under sunlight and crush manually. Sun dried for 34 days and crushed manually. This
biomass was further digested by chemical methods.
= (1)
Where,
qe = The amount of adsorbate per unit weight of adsorbent (mg/g)
Ce = The concentration of adsorbate in solution at equilibrium after the adsorption is
complete (mg/L)
3
KL = The amount of solute adsorbed/unit weight of an adsorbent in forming a complete
monolayer on the surface (mg/g)
b = The constant related to the energy or net enthalpy of adsorption.
The linear form of Langmuir expression is
= + Ce (2)
Therefore, a plot of Ce/qe versus Ce gives a straight line of slope b/KL and intercepts 1/KL.
The essential characteristics of the Langmuir isotherm could be expressed in
terms of a dimensionless constant, separation factor or equilibrium parameter r that is
defined as follows:-
r= (3)
Where,
Co = The initial adsorbate concentration (mg/L)
b = The Langmuir constant related to the energy of adsorption (L/mg)
The value of r indicates the shape of the adsorption isotherm to know whether
adsorption is unfavorable (r >1), linear (r =1), favorable (0< r< 1), or irreversible ((r = 0).
4
Langmuir and Freundlich isotherm equations were employed to quantify the
adsorption equilibrium.
5
2.3. TREATMENT OF SAMPLES
The stabilized oilwater emulsion samples were divided into200 ml portions and
treated with different doses of adsorbents activated carbon. The adsorptive capacity of the
adsorbents was determined by aqueous phase isotherm technique. The treated samples
were stirred using a magnetic stirrer with a mixing speed of 400 rpm for different contact
time intervals of 0.5, 1.0, 2.0, 3.0 and 4.0 hours. The treated samples were filtered
through filter papers. The amount of oil removed was determined.
(Source: Khaled Okiel et. al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)
6
The initial oil concentration varies from 600 836 mg/L and final oil concentration
varies from 54 to 480 mg/L with percentage of oil removal range from 20.0 to 93.54 %.
Efficiency of adsorption of oil by activated carbon depends on different factors such that
weight of adsorbent, time of stirring and concentration of the adsorbate. Increasing the
weight of absorbent from 0.1 to0.5 g led to the increase in oil removal from 20.0% to
61.0% on treating sample of initial oil concentration of 600 mg/L and after stirring time
of 30 minutes. On treating oilwater emulsion sample of initial oil concentration 836
mg/L (ppm) with 0.5 g PAC and stirring for 2.0 hours gave oil removal of 82.78% and
with1.0 g of the adsorbent and stirring time for 4.0 hours gives 93.54%.
Table 1 shows that increasing the dosage of adsorbent led to increasing the oil
removal percentage because each adsorbent particle has to purify a certain volume of
water so that a higher dosage is required to reach the equilibrium faster than the low
dosage and consequently, enough time must be allowed for the low dosage.
In order to establish the equilibrium time for maximum uptake of oil from oilwater
emulsion, the amounts of oil adsorbed on the adsorbent ( PAC) was studied as a function
of stirring time, which varied from 0.5 to 4.0 hours, using initial oil concentration of 1000
mg/L and with dosage of 0.5 g adsorbent. The results are given in Table 2.and the
relationship between the amounts of oil adsorbed per gram of adsorbent qe as a function
of the time was shown in Fig. 2.It is clear that the amount of oil adsorbed increased with
increasing contact time. The rate of uptake of oil is rapid at the beginning and within 2.0
hour 80.6% by PAC. These data indicated that the reasonable time for adsorption
equilibrium was 2.0 hours.
7
Table 2: Effect of contact time on the amount of oil adsorbed and oil adsorbed per
unit weight of adsorbent qe, at initial oil concentration 100 mg/L
500
400
qe(mg/g)
300
200 PAC
100
0
0 1 2 3 4 5
time (hr)
Fig 2: Effect of contact time on the amount of oil adsorbed per unit
Weight of adsorbent qe
(Source: Khaled Okiel et. al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)
8
was considered as a sufficient time for the adsorption of oil from oilwater emulsion on
the PAC under the used operating conditions.
100
80
Residual oil content %
60
40 PAC
20
0
0 0.5 1 1.5 2 2.5 3 3.5 4
Time(hours)
9
Table 3: Effect of initial oil concentration on oil removal efficiency by PAC
Adsorbent Initial oil Final oil Oil Oil q e (mg/g)
concentration, concentration, removed removal
Co Ce Co Ce (%)
(mg/L) (mg/L) (mg/L)
836 145.5 690.5 82.6 276
Powdered 1012 196 816 80.6 326
activated 1210 290 920 76 368
carbon 1613 443 1170 72.5 468
(Source: Khaled Okiel et. al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)
100
95
concentration(%)
90
Adsorbed oil
85
80 PAC
75
70
700 900 1100 1300 1500 1700
Initial concentration of oil (mg/L)
The adsorption isotherm studies were performed by using samples of initial oil
concentrations of 1000 mg/L, with adsorbent dosages of 0.1, 0.3, 0.5, 0.7, 1.0, 1.5 g/200
ml, and stirring to the equilibrium time which is determined previously. The results were
given in Table 4.
10
The equilibrium experimental data for activated carbon was analyses using
Langmuir isotherm by plotting Ce/qe against Ce as shown in Fig.5. and Freundlich
isotherm by plotting log qe against log Ce as shown in Fig.6.The results of the regression
equations obtained for the Fig.5. Adsorption of oil in-water emulsions by PAC is
presented in Table 5.
The isotherms yield constants whose values express the affinity of adsorbate for the
surface of adsorbent. Appling the Langmiur isotherm model, it was observed that K L
varies from7.12 to 9.23, b (L/mg) the Langmuir constant ranges from 0.009 to 0.002, and
the values of r calculated by the above Eq. (3) are between 0 and 1 confirming that
isotherm is favorable. Consider the Freundlich model, the values of Kf corresponding to
PAC is 10.39. The higher value indicates more adsorption capacity. 1/n value for PAC is
taken as 0.66. The smaller values of 1/n, higher the affinity between adsorbate and
adsorbent hence efficiency of removal of oil also higher.
(Source: Khaled Okiel et. al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)
11
1
0.8
0.6
Ce/qe
0.4 PAC
0.2
0
0 200 400 600 800
Ce (mg/L)
3.1
2.9
2.7
2.5
Log qe
2.3
PAC
2.1
1.9
1.7
0.7 1.2 1.7 2.2 2.7 3.2
Log Ce
12
Table 5: Regression analysis for sorption of oil by PAC and the parameters
estimated using Langmuir and Freundlich models
Freundlich Y= mX c Correlatio
Adsorbent Langmiur model Y=mX c Correlation model n factor R
KL B R factor R KF 1/n
PAC 2.58 0.0021 0.323 Y=0.0008X 0.8724 10.37 0.658 Y=0.658X 0.996
+ 0.3871 +1.016
(Source: Khaled Okiel et al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)
13
a size that can be sieved through a 600 m sieve. The characteristics of powdered lemon
peel adsorbent used in this study is given in Table 6.
(Source: A.R. Tembhurkar et. Al, Powdered Activated Lemon Peels as Adsorbent for
Removal of Cutting Oil from Wastewater)
3.2. PREPARATION OF SAMPLE
Cutting oil used as a coolant in a lathe machine is taken to prepare the oil-in-water
emulsion for the study. It was prepared using a known volume of cutting oil in 1 L of
water and stirring it for at least 10 min at 150160 revolutions per minute (rpm) using a
mechanical stirrer to get oil in-water emulsion. The characteristics of the oil are given in
Table 7.
Table 7. Typical Characteristics of Cutting Oil
Sl no: Characteristics Value
1 Density (at 15C g/m3) 1.206
2 pH (2% in DW min) 9
3 Flash point (C) 150
4 Kinematic viscosity at 40C 20
(Source: A.R. Tembhurkar et. Al, Powdered Activated Lemon Peels as Adsorbent for
Removal of Cutting Oil from Wastewater)
14
dose of adsorbent, 25200 min for contact time, 1002,000 mg/L for initial oil
concentration, and 30150 rpm for speed. A multiple-paddle speed-controlled mixer (jar
test laboratory apparatus made by Scientific Engineering Corporation, Delhi, India) that
accommodates six beakers was used for stirring the content simultaneously at the same
speed. During each batch study, the beakers were filled with 1 L of oil-in-water emulsion
for each test run, and after adding powdered activated lemon peel to the suspension, the
contents of the beaker were rapidly mixed at 90 rpm for 10 min and then mixed at various
mixing times and speeds for different dosages. The clarified supernatant after a
sedimentation time of 60 min was analyzed for residual oil content. Batch isotherm
experiments were also conducted at room temperature (22 3C) to examine adsorption
isotherm.
The oil content in water was measured according to the procedure for extraction
recommended by the American Public Health Association (1992, 18th edition) using n-
hexane as the oil extraction solvent and with a spectrophotometer (Systronics,
Ahmedabad, India). A 300 mL of sample was taken to which 5 mL 1:1 HCl was added to
create an acidic condition. It is then transferred to a separating funnel to which 30 mL
hexane was added, and the resulting mixture was shaken vigorously for 5 min and then
left for 10 min to allow further separation. The solvent layer was then slowly drained
through a funnel containing filter paper having pore size of 1.5 m and 10 g anhydrous
sodium sulphate. Residual oil content was measured using a spectrophotometer at a peak
wavelength of 380 nm. A standard curve was prepared for determination of oil
concentration.
Adsorption Efficiency is the ratio of the difference in the initial oil concentration
and oil concentration after adsorption to the initial oil concentration expressed as a
percentage.
Where,
Ci = initial oil concentration, C0 = oil concentration after adsorption.
15
3.5. RESULTS OBTAINED
Adsorption efficiency of powdered activated lemon peels depends different
parameters are pH, dose of adsorbent, contact time, mixing speed and initial oil
concentration.
3.5.1. pH
The pH of the aqueous solution is a controlling factor in the adsorption process.
Thus, the role of the hydrogen ion concentration was examined at pH values of 2, 4, 6, 8,
and 10. The pH was adjusted by using dilute H2SO4 (0.5 N) and dilute NaOH (0.5 N).The
maximum adsorption was found by keeping a constant adsorbent dose at 1 g/L, contact
time at 60 min, contact speed at 30 rpm, initial concentration at 200 mg/L, and varying
pH. Tests conducted on emulsion at different pH values indicate that the adsorption
efficiency decreases with increases in the pH value Fig 7. The adsorption efficiency is
maximized at an acidic condition of 2. This may be because of breakage of emulsion at
lower pH values. Under acidic conditions, physiochemical effects apparently cause de-
emulsification and enhance the adsorption of oil, which gives better adsorption, and
greater removal is achieved at acidic pH values. However, at pH values greater than 8.0,
an increasing removal of residue oil occurred. It is known that the addition of excess
NaOH to increase the alkalinity of a suspension containing residue oil can lead to
saponification, i.e., the residue oil is hydrolyzed by NaOH to produce glycerol and a fatty
acid salt called soap. This could have been the reason for the increase in the percentage
removal of residue oil under strong alkaline conditions, i.e., the residue oil was
hydrolyzed in and not extracted by the solvent, thereby indirectly giving a higher
percentage of removal of residue oil. This leads to a conclusion that maximum adsorption
is achieved at an acidic pH condition.
16
Figure 7: Effect of pH on adsorption efficiency of powdered lemon peels
(Source: A.R. Tembhurkar et. Al, Powdered Activated Lemon Peels as Adsorbent for
Removal of Cutting Oil from Wastewater)
17
Figure 8: Effect of adsorption dose on adsorption efficiency of powdered lemon
peels
(Source: A.R. Tembhurkar et. Al, Powdered Activated Lemon Peels as Adsorbent for
Removal of Cutting Oil from Wastewater)
The powdered lemon peels before adsorption were off-white in color and after
adsorption were shining (a visual observation).The scanning electron microscope (SEM)
micrograph depicted in Fig. 9(a) shows the view of powdered lemon peels before
adsorption and Fig. 9(b) shows powdered lemon peels after adsorption of oil. The SEM
micrograph depicted the fibrous structure with heterogeneous pores. However, a
significant change in the structure of the lemon peels is depicted after oil adsorption. The
structure appeared to be surface coated with oily substances. This is due to the oil
molecules covering the surface adsorption of powdered lemon peels.
18
Figure 9: (a) Electron micrographs of powdered lemon peels before oil adsorption
(5,000 magnification); (b) electron micrographs of powdered lemon peels after
cutting oil adsorption (5,000magnification)
(Source: A.R. Tembhurkar et. Al, Powdered Activated Lemon Peels as Adsorbent for
Removal of Cutting Oil from Wastewater)
19
oil adsorption efficiency also increases because an increase in contact time increases the
chances of breakage of the oil droplets reducing the diameter of the oil droplets, which
enhances the adsorption process at a greater interfacial area.
An extended contact period does not improve efficiency further, but it slightly
decreases because it might lead to desorption of adsorbed oil at higher contact times,
thereby reducing the efficiency of adsorption. This phenomenon may be due to prolonged
agitation, which may cause the adsorbent to break up and introduce adsorbed oil back
into the system. The contact time of 70 minute at which the oil removal efficiency (97%)
is maximized which is selected as the optimum contact time for next study.
Figure 10: Effect of contact time on adsorption efficiency of powdered lemon peels
(Source: A.R. Tembhurkar et. Al, Powdered Activated Lemon Peels as Adsorbent for
Removal of Cutting Oil from Wastewater)
20
And more contact between the adsorbent and emulsified oil Fig 11.When speed is
further increased, the efficiency drops, which may be due to shearing of adsorbed oil
from adsorbent at high speed. The mixing speed of 50 rpm achieved maximum oil
adsorption is taken for further study.
Figure 11: Effect of mixing speed on adsorption efficiency of powdered lemon peels
(Source: A.R. Tembhurkar et. Al, Powdered Activated Lemon Peels as Adsorbent for
Removal of Cutting Oil from Wastewater)
21
Figure 12: Effect of initial concentration on adsorption efficiency of
powdered lemon peels
(Source: A.R. Tembhurkar et. Al, Powdered Activated Lemon Peels as Adsorbent for
Removal of Cutting Oil from Wastewater)
Where
qe = equilibrium oil concentration on the activated powdered lemon peels (mg/ g)
Ce = equilibrium oil concentration in the solution (mg/L)
KF = Freundlich adsorption isotherm constant (L /g)
n = The Freundlich adsorption isotherm constant
22
The Freundlich isotherm endorses the heterogeneity of the surface and assumes
that the adsorption occurs at sites with different energies of adsorption. The data obtained
through isotherm studies were subjected to estimation of constants using the previous
isotherm model. Among these, the data fit closely to the Freundlich isotherm. The
graphical representation for the Freundlich isotherm is shown in Fig.13. On plotting the
equilibrium data, the following Freundlich isotherm is obtained for adsorption of oil on
powdered lemon peel.
Here the value of adsorption capacity and n is taken as 8.896, 1.871 respectively.
The value of n greater than 1 indicates that changes in adsorption capacity are less
sensitive to those changes in aqueous phase concentrations.
(Source: A.R. Tembhurkar et. Al, Powdered Activated Lemon Peels as Adsorbent for
Removal of Cutting Oil from Wastewater)
23
From this study optimum values of the parameters are obtained. An adsorbent
dosage of 5 g/L, contact time of 70 min, mixing rate of 4550 rpm, and pH of 2 can
provide maximum oil removal efficiency for the powdered activated lemon peels.
24
5. CONCLUSION
Adsorption of oil on to the powdered activated carbon increases with increasing the
dosage of the adsorbent and contact time until reaches the equilibrium time of 2 hours.
Also the adsorbed amount of oil is dependent on the initial oil concentration. It decreases
as the initial oil concentration increases. The removal efficiency of activated lemon peel
is maximum at the adsorbent dosage of 5g/L, contact time of 70 minutes, mixing rate of
45-50 rpm and pH of 2. The present research reveals that the powdered activated lemon
peels can be effectively used as adsorbent than powdered activated carbon for the
removal oil from waste water. This method is more economic and material used as
adsorbent is cheap, non-toxic and easily available.
25
REFERENCES
Khaled Okiel, Mona El-Sayed and Mohamed Y. El-Kady, (2011), Treatment of oil-
water emulsions by adsorption on to activated carbon, bentonite and deposited carbon,
Egyptian Journal of Petroleum, vol.20, no.1, pp. 9- 1.
Muhammad Abbas Ahmad Zainy, MuazZakaria, Mohd-Setapar, S.H. and Che-
Yunus, M. A. (2013), Sludge adsorbents from palm oil mill effluent for methylene
blue removal, Journal of Environmental Chemical Engineering, vol.38, no.1, pp.1091
1098.
Norhusna Mohammad Nor, Lau Lee Chung, Lee Keat Teong and Abdul Rahman
Mohamed, (2013), Synthesis of activated carbon from lingo cellulosic biomass and its
applications in air pollution control a review , Journal of Environmental Chemical
Engineering, vol.10, no.1, pp. 658-666 .
Sawsan, A. M., Mohammed, Ibtihage Faisal, Maha and M. Alwan, (2011), Oily
Wastewater Treatment Using Expanded Beds of Activated Carbon and Zeolite, Iraqi
Journal of Chemical and Petroleum Engineering, vol.12, no.1, pp. 576- 589.
Tembhurkar, A. R., Ph. D and Radhika Deshpande, (2012), Powdered Activated
Lemon Peels as Adsorbent for Removal of Cutting Oil from Wastewater , Journal of
Hazardous, toxic, and Radioactive Waste, ASCE, vol.16, no.4, pp. 311 315 .
26