ACTIVATED CARBON AND LEMON PEELS AS ADSORBENT FOR

REMOVING OIL FROM WASTE WATER

A SEMINAR REPORT

Submitted by

KEVIN D THOMAS

In partial fulfillment of the requirement for the award of the degree

of

BACHELOR OF TECHNOLOGY in CIVIL ENGINEERING

Guided by

Asst. Prof. ANNIE JOY

DEPARTMENT OF CIVIL ENGINEERING

Toc H INSTITUTE OF SCIENCE & TECHNOLOGY

ERNAKULAM 682313

SEPTEMBER 2014
 Toc H INSTITUTE OF SCIENCE & TECHNOLOGY
ARAKKUNNAM, ERNAKULAM-682 313
DEPARTMENT OF CIVIL ENGINEERING

CERTIFICATE

This is to certify that the seminar entitled ACTIVATED CARBON AND

LEMON PEELS AS ADSORBENT FOR REMOVING OIL FROM WASTE
WATER is the bonafide work done by KEVIN D THOMAS (Reg no: 11123033) under
our supervision and guidance. This seminar report is submitted to Toc H Institute of
Science & Technology in partial fulfillment of the requirements for the award of the
degree of BACHELOR OF TECHNOLOGY in CIVIL ENGINEERING.

Guided by: Head of the department:

Asst. Prof. Annie Joy Asso. Prof. Vasudev R

Department of Civil Engineering Department of Civil Engineering

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.

I would like to express my gratitude to the Management, Toc H Institute of

Science and Technology, Arakkunnam for their whole hearted support and for providing
with a greater infrastructure necessary for the completion of my seminar. I also like to
express my sincere thanks to Dr. D Vincent H Wilson, (Principal, TIST) for his kind
support throughout the completion of this venture.

I would also like to extend my heartfelt thanks to Dr. Rajeev Kumar P

(Professor In-charge, PG Studies) for his continued support and encouragement.

With a greater respect, I express my sincere thanks to our Head of the

Department Asso. Prof. Vasudev R (HOD, CE) for all the proper guidance and
encouragement that helped me to complete this seminar.

I express my sincere gratitude to my seminar guide Asst. Prof. Annie Joy,

Department of Civil Engineering, TIST, for her valuable guidance and support.

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.

KEYWORDS : Waste Water, Activated Carbon, Lemon Peels

iii
 CONTENTS

Title Page no.

CERTIFICATE i

ACKNOWLEDGEMENT ii

ABSTRACT iii

LIST OF TABLES vi

LIST OF FIGURES vii

LIST OF ABBREVATIONS ix

LIST OF NOTTATIONS x

1. INTRODUCTION 1

1.1. ADSORPTION AND ADSORBING MATERIAL 2

1.2. ADSORPTION ISOTHERM 3

1.2.1. THE LANGMIUR ISOTHERM 3

1.2.2. THE FREUNDLICH ISOTHERM 4

2. TREATMENT USING ACTIVATED CARBON 5

2.1. PREPARATION OF ADSORBENT 5

2.2. PREPARATION OF SAMPLES 5

2.3. TREATMENTS OF SAMPLES 6

2.4. DETERMINATION OF OIL CONTENT 6

iv
 2.5. RESULTS OBTAINED 6

2.5.1. CONTACT TIME 7

2.5.2. INITIAL CONCENTRATION OF ADSORBATE 9

2.5.3. ADSORPTION ISOTHERM 10

3. TREATMENT USING ACTIVATED LEMON PEELS 13

3.1. PREPARATION OF ADSORBENT 13

3.2. PREPARATION OF SAMPLE 14

3.3. TREATMENT OF SAMPLE 14

3.4. DETERMINATION OF OIL CONTENT 15

3.5. RESULTS OBTAINED 16

3.5.1. pH 16

3.5.2. ADSORBENT DOSAGE 17

3.5.3. CONTACT TIME 19

3.5.4. EFFECT OF MIXING SPEED 20

3.5.5. EFFECT OF INITIAL OIL CONCENTRATION 21

3.5.6. ISOTHERM STUDIES 22

4. COMPARISON OF TWO RESULTS 24

5. CONCLUSION 25

REFERENCES

v
 LIST OF TABLES

Table No. Name Page No.

1. OIL REMOVAL EFFICIENCY FROM 6

THE OIL-WATER EMULSION SAMPLES
BY ADSORPTION ON PAC
2. EFFECT OF CONTACT TIME ON THE 8
AMOUNT OF OIL ADSORBED AND OIL
ADSORBED PER UNIT WEIGHT OF
ADSORBENT QE, AT INITIAL OIL
CONCENTRATION 100 MG/L.
3. EFFECT OF INITIAL OIL CONCENTRATION 10
ON OIL REMOVAL EFFICIENCY BY PAC
4. APPLICATION OF LANGMIUR AND 11
FREUNDLICH MODELS
5. REGRESSION ANALYSIS FOR SORPTION 13
OF OIL BY PAC AND THE PARAMETERS
ESTIMATED USING LANGMUIR AND
FREUNDLICH MODELS
6. CHARACTERISTICS OF POWDERED 14
LEMON PEELS
7. TYPICAL CHARACTERISTICS OF 14
CUTTING OIL
8. COMPARISON OF TWO RESULTS 24

vi
 LIST OF FIGURES

Fig No. Name Page No.

1. SURFACE MORPHOLOGY OF COMMERCIAL 5

ACTIVATED CARBON
2. EFFECT OF CONTACT TIME ON THE 8
AMOUNT OF OIL ADSORBED PER UNIT
WEIGHT OF ADSORBENT QE
3. EFFECT OF CONTACT TIME ON THE 9
RESIDUAL OIL CONTENT
4. EFFECT OF THE INITIAL CONCENTRATION 10
OF OIL ON THE ADSORPTION OF OIL
UNDEROPTIMIZED CONDITION
5. LANGMUIR ADSORPTION ISOTHERM OF 12
OIL ON BENTONITEPAC, AND DC
6. FREUNDLICH ADSORPTION ISOTHERM 12
OF OIL ON BENTONITE, PAC, AND DC
7. EFFECT OF PH ON ADSORPTION EFFICIENCY 17
OF POWDERED LEMON PEELS
8. EFFECT OF ADSORPTION DOSE ON 18
ADSORPTION EFFICIENCY OF
POWDERED LEMON PEELS
9. (A) ELECTRON MICROGRAPHS OF POWDERED 19
LEMON PEELS BEFORE OIL ADSORPTION
(B) ELECTRON MICROGRAPHSOF POWDERED 19
LEMON PEELS AFTER CUTTING
OIL ADSORPTION
10. EFFECT OF CONTACT TIME ON 20
ADSORPTION EFFICIENCY OF
POWDERED LEMON PEELS

vii
Fig No. Name Page No.

11. EFFECT OF MIXING SPEED ON 21

ADSORPTION EFFICIENCY OF
POWDERED LEMON PEELS
12. EFFECT OF INITIAL CONCENTRATION 22
ON ADSORPTION EFFICIENCY OF
POWDEREDLEMON PEELS
13. FREUNDLICH ISOTHERM FOR 23
ADSORPTION OF CUTTING OIL BY
POWDERED LEMON PEELS

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)

Ce CONCENTRATION OF ADSORBATE IN SOLUTION

AT EQUILIBRIUM AFTER THE ADSORPTION
IS COMPLETE (mg/L)

KL AMOUNT OF SOLUTE ADSORBED/UNIT WEIGHT

OF AN ADSORBENT IN FORMING A COMPLETE
MONOLAYER ON THE SURFACE (mg/g)

b LANGMUIR CONSTANT RELATED TO THE

ENERGY OF ADSORPTION (L/mg)

r R VALUE INDICATES THE SHAPE OF THE

ADSORPTION ISOTHERM

Co INITIAL ADSORBATE CONCENTRATION (mg/L)

Ci INITIAL OIL CONCENTRATION (mg/L)

Kf FREUNDLICH EQUILIBRIUM CONSTANT WHICH

INDICATE THE ADSORPTIVE CAPACITY

N FREUNDLICH CONSTANT INDICATIVE OF THE

AFFINITY OF THE ADSORBATE FOR THE
SURFACE OF ADSORBENT

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.

1.1 ADSORPTION AND ADSORBING MATERIALS

Adsorption is a separation process in which gas or liquid molecules are adsorbed on

the surface of an adsorption solid. There is a variety of adsorbents. The most common are
activated carbon (AC), clay, silica, alumina and zeolite. AC is an effective adsorbent, has
a high surface area, an extensively developed pore structure, a high crystalline form and
mechanical strength. In addition, AC possesses good porous texture allowing the high
adsorption capacity in the removal of a wide variety of organic compounds including oil
from water and has proven to be technically feasible. Removal of petroleum hydrocarbon
polluted ground-water using of AC was investigated, and it was recommended that
powder activated carbon is more effective in the treatment of ground water than granular
activated carbon. The surface chemistry of carbon materials is basically determined by
the acidic and basic character of their surface, and can be changed by modifying them
with oxidizing agents either in the gas phase or in solution. Many methods of modifying

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.

1.2. ADSORPTION ISOTHERM

The adsorption of a substance from a liquid phase to the surface of a solid phase in
a system leads to a thermodynamically defined distribution of that substance between the
two phases when the system reaches equilibrium; that is when the rate of adsorption of
solute onto the surface of the adsorbent is the same as the rate of its desorption from the
surface of the adsorbent. Therefore, there is no further net adsorption occurs.
Several mathematical relationships have been developed to describe the equilibrium
distribution of solute between the solid and the liquid phases at a constant temperature
and thus aid in the interpretation of the adsorption processes. The most widely used
models are the Langmuir and the Freundlich isotherms. They are useful for describing the
adsorption capacity of a specific adsorbent.

1.2.1. THE LANGMIUR ISOTHERM

The Langmiur equation for solidliquid system is commonly written as:

= (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).

1.2.2. THE FREUNDLICH ISOTHERM

The Freundlich isotherm can be applied to non-ideal adsorption on heterogeneous
surfaces as well as multilayer sorption and is expressed by the following equations:
qe= Kf Ce(1/n) (4)
A linear form of this expression is
Log qe = log KF +1/n * log Ce
Where,
Kf = The Freundlich equilibrium constant which indicate the adsorptive capacity
N = The Freundlich constant indicative of the affinity of the adsorbate for the surface of
adsorbent,
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).

4
 Langmuir and Freundlich isotherm equations were employed to quantify the
adsorption equilibrium.

2. TREATMENT USING ACTIVATED CARBON

In a study reported by Khaled Okiel, Mona El-Sayed and Mohamed Y. El-Kady the
performance effectiveness of treatment using activated carbon was described, the details
of which are given in the following sections.

2.1. PREPARATION OF ADSORBENT

Powdered activated carbon was obtained from ADWIC CO. Egypt, of mesh size
300 and density of 0.32 g/Cm3. Then it was washed several times with distilled water,
then dried in a hot air oven at 105110 0C for 4 hours and stored in a desiccators at room
temperature. Surface morphology of activated carbon is shown in Fig 1.

Fig 1: Surface morphology of commercial activated carbon

(Source: Muhammad Abbas Ahmad Zainy et al, Sludge adsorbents from palm
oil mill effluent for methylene blue removal)

2.2. PREPARATION OF SAMPLES

The oilfield produced waste water samples from Gammas Petroleum Company, oil
treatment facilities, eastern desert, Egypt were collected from the effluent (main) waste
water pipeline before waste water treatment unit. The samples were collected in glass
containers and transported to the laboratory. The samples were poured in 2 L separating
funnel and left for 24 hours to stabilize and separate any oil.

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.

2.4. DETERMINATION OF OIL CONTENT

Oils were extracted from the untreated and treated samples as initial oil
concentration. Then final oil concentration was determined according to the standard
method (ASTM-D 3921, 1992) using1, 1,2-trichloro-1,2,2-trifluoroethane as a solvent.
The extracted oils were diluted and examined by infrared spectroscopy (PerkinElmer
Spectrum One) to measure the amount of oil removed.

2.5. RESULTS OBTAINED

The extracted oils from the studied oil-water emulsion samples were determined
before and after treatment at different conditions and results are given in Table 1.
Table 1: Oil removal efficiency from the oil-water emulsion samples
by adsorption on PAC
Weight g/200ml Time of Initial oil Final oil Oil
Adsorbent Oil-water stirring(h) concentration concentration removal
emulsion 400 rpm (mg/L) (mg/L) (%)
0.1 0.5 600 480 20.0
Powdered 0.5 0.5 600 160 61.0
activated 0.5 2.0 836 144 82.78
carbon 1.0 4.0 836 54 93.54

(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.

2.5.1. CONTACT TIME

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

Adsorbent Time of Residual oil Adsorbed Weight of qe

stirring(h) concentration(mg/L) oil (Co-Ce) adsorbed (mg/g)
Ce (%) oil (mg)

0.5 625 37.5 75 150

Powdered 1.0 418 58.2 116.4 232.8
activated 2.0 194 80.6 161.2 322.8
carbon 3.0 180 82.0 164 328.0
4.0 165 83.5 167 334.0
(Source: Khaled Okiel et. al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)

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)

The relationship between the amounts of residual oil% as a function of stirring

time was shown in Fig. 3. It is obvious that the residual concentration decreases with
increasing the stirring time until 2.0 hours for the activated carbon. Therefore, 2.0 hours

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)

Fig 3: Effect of contact time on the residual oil content

(Source: Khaled Okiel et. al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)

2.5.2. INITIAL CONCENTRATION OF ADSORBATE

The effect of the initial concentration of oil on the adsorption under optimized
conditions (stirring time 2.0 h, and 0.5 g adsorbent) was studied. The adsorbed oil
concentration% was studied as a function of initial oil concentration. The initial
concentration of oil of 836, 1012, 1210, and 1613 mg/L were used for the evaluation of
their effects on adsorption. The results obtained are represented in Table 3 and Figure 4.
It is clear that although the amount of oil adsorbed per unit weight of adsorbents qe
increases by increasing the adsorbate concentration yet the oil removal% decreases as the
initial oil concentration, Co (mg/L) increases.
The oil removal percentage by powdered activated carbon at the initial oil
concentrations from 836 to 1613 mg/L were about 82.6% and 72.5%.Increasingthe initial
oil concentration led to increasing the amount of oil adsorbed per unit weight of
adsorbents and consequently the remaining surface area decreases.

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)

Fig 4: Effect of the initial concentration of oil on the adsorption of oil

Under optimized condition (contact time 2.0 h, and 0.5 g adsorbent)
(Source: Khaled Okiel et al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)

2.5.3. ADSORPTION ISOTHERM

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.

Table 4: Application of Langmiur and Freundlich models

Adsorbent Weight Residual Adsorbed Weight Adsorbed Ce/qe log qe log Ce

of oil(mg/L) oil(mg/L) of oil qe
adsorbent Ce Co- Ce adsorbed (mg)
oil (mg)
0.10 622 378 75.6 756 0.82 2.88 2.79
Powdered 0.30 320 680 136 453.3 0.71 2.66 2.51
activated 0.50 194 806 161.2 322.4 0.60 2.51 2.29
carbon 0.70 132 868 173.6 248 0.53 2.39 2.12
1.00 75.4 924 184.92 184.9 0.41 2.27 1.88
1.50 43.5 956 191.3 127.5 0.34 2.11 1.64

(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)

Fig 5: Langmuir adsorption isotherm of oil on PAC

(Source: Khaled Okiel et. al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)

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

Fig 6: Freundlich adsorption isotherm of oil on PAC

(Source: Khaled Okiel et. al, Treatment of oil- water emulsions by adsorption on to
activated carbon, bentonite and deposited carbon)

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)

The adsorption data obtained by Langmuir isotherms model with lower

correlation coefficients (R =0.8724) while the adsorption data analyzed by the Freundlich
isotherms model conform best to following Freundlich equation with good correlation
coefficients (R= 0.996). So Freundlich isotherm is best to describe the sorption of oils
from oilwater emulsion by PAC

3. TREATMENT USING ACTIVATED LEMON PEELS

In a study reported by A. R. Tembhurkar and Radhika Deshpande the performance
effectiveness of treatment using powdered activated lemon peels was described, the
details of which are given in the following sections.

3.1. PREPARATION OF ADSORBENT

Adsorbent was prepared from lemon peels, sun dried for 34 days and crushed
manually. This biomass was further digested by chemical methods, viz., acid and alkali
treatment. A 40 g crushed biomass and 400 mL of 1 N HNO3 (nitric acid) were taken in a
1,000 mL beaker and heated on a hot plate for 20 min. After boiling, the treated biomass
was washed with distilled water until the maximum amount of color was removed and
clear water was obtained. After acid treatment, the content was further subjected to alkali
treatment. A 400 mL 1 N NaOH is mixed with the content of the biomass and heated on a
hot plate for up to 20 min after boiling. The biomass was then allowed to cool and then
washed with distilled water until the maximum amount of color was removed and clear
water was obtained. The treated biomass was then sun dried for 45 days, then ground to

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.

Table 6: Characteristics of Powdered Lemon Peels

Sl no: Characteristics Value
1 Particle size (m) 600
2 Moisture content (%) 6.22
3 pH in distilled water 6.7- 7
4 Specific gravity 0.8 0.9

(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)

3.3. TREATMENT OF SAMPLE

Experiment studies were conducted using 1 L oil-in-water emulsion and the effects
of varying values of parameters, viz., pH, adsorbent dosage; contact time, influent oil
concentration, and mixing speed, on adsorption by powdered activated lemon peels were
studied. The ranges of values used in the present study were 210 for pH, 0.29 g/L for

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.

3.4. DETERMINATION OF OIL CONTENT

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.

Adsorption efficiency = * 100

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)

3.5.2. ADSORBENT DOSAGE

The adsorbent dosages were varying in this study from 0.2 to 9 g/L and keeping the
pH value 2. The other parameters such as mixing speed, contact time, and initial oil
concentration were kept the same as the previous study. As shown in Fig 8, the greater
the dosage of powdered lemon peels, the more effective the adsorption of oil because
more surface area is available for the adsorption. Higher rates of adsorption were
observed up to a dose of 5 g/L thereafter, the percentage of oil removal remains more or
less constant. A dose of 5 g/L; was selected as the optimum dose for the next study. The
adsorption takes place due to binding and bridging of residual oil with powdered and
flaky lemon peels. The positively charged biopolymer is capable of adsorbing residual oil
as well as destabilizing negatively charged colloids of residual oil and emulsion by a
mechanism of charge neutralization.

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)

3.5.3. CONTACT TIME

Studies on the effect of contact time on adsorption efficiency were performed by
varying contact time between 25 and 200 min with the pH at 2, the adsorbent dose at
5g/L, and other parameters such as mixing speed and initial oil concentration the same as
the previous study .The efficiency of adsorption increases with increases in contact time
from 25 to 70 min Fig 10. A low percentage of oil removal is observed up to a contact
time of 50 minutes due to decreasing the chances of contact between the oil molecules
and adsorbent particles at less contact time. However, as the contact time increases, the

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)

3.5.4. EFFECT OF MIXING SPEED

Studies on the effect of mixing speed were carried out by varying the speed from 30
to 150 rpm and using 5.0 g/L of powdered lemon peels mixed for a contact time of 70
min at a pH of 2 and an initial concentration of 200 mg/L. Initially, the oil adsorption
efficiency increases with speed up to 50 rpm as it facilitates more uniform mixing and
provides more

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)

3.5.5. EFFECT OF INITIAL OIL CONCENTRATION

Studies on the effect of initial oil concentration on adsorption efficiency were
carried out by varying the initial concentration from100 to 2000 mg/L with a pH of 2 and
adsorbent dose of 5 g/L and at a contact time of 70 min and mixing speed of 50 rpm. The
variation of adsorption efficiency with the initial concentration is given in Fig 12. The
efficiency of oil removal is high at lower initial oil concentrations below 500 mg/L, and
thereafter the efficiency drops and remains constant with an increase in initial
concentration.

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)

3.5.6. ISOTHERM STUDIES

The powdered activated lemon peels are an excellent medium for treating oily
wastewater. Significant information about the adsorption capacity of this adsorbent could
be obtained through the sorption isotherm. The Langmuir, and the Freundlich are the
commonly used isotherms.
The Freundlich isotherm is used for non-ideal adsorption on heterogeneous
surfaces. The heterogeneity arises from the presence of different functional groups on the
surface and the various adsorbentadsorbate interactions. The Freundlich isotherm can be
linearly expressed as

Log qe = log KF + loge

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.

Freundlich isotherm (x/m) = 8.896Ce(1/1.871)

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.

Figure 13: Freundlich isotherm for adsorption of cutting oil by

powdered lemon peel

(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.

4. COMPARISON OF TWO RESULTS

This 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 was
compared. It is found that lemon peels performed some better properties in removal of
oil.

Table 8: Comparison of two results

Parameters Activated lemon peels Activated carbon

pH Highly acidic or highly alkaline Not specified

condition

Adsorbent dosage 5 g/L Adsorbent dosage increases

efficiency But value is not
specified

Contact time 70 minutes 2 hours

Mixing speed 50 rpm 400 rpm

Initial oil concentration 500 mg/L As Initial oil concentration

decreases efficiency
increases

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 .

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