REDUCTION OF COD FROM DAIRY WASTEWATER VIA

ADSORPTION: OPTIMIZATION OF PROCESS

PARAMETERS
A Project Report Submitted
In Partial Fulfillment of the
Requirements for the Degree
BACHELOR OF TECHNOLOGY
in
CHEMICAL ENGINEERING
By
Pankaj Kumar Verma
Rohit Singh
Yash Trivedi
Yogesh Chauhan
Balaram Singh

(20106051)
(20100011)
(20100049)
(20109030)
(20109035)

Under the supervision of

Dr. Suantak Kamsonlian

DEPARTMENT OF CHEMICAL ENGINEERING

MOTILAL NEHRU NATIONAL INSTITUTE OF TECHNOLOGY
ALLAHABAD
ALLAHABAD-211004 (INDIA)
MAY, 2014

MOTIAL NEHRU NATIONAL INSTITUTE OF

TECHNOLOGY ALLAHABAD
CANDIDATES DECLARATION
We hereby certify that the work which is being presented in the report entitled
Reduction of COD from dairy waste water via Adsorption: Optimization of process
parameters in partial fulfilment of the requirements for the degree of Bachelor of
Technology and submitted in the Department of Chemical Engineering, Motilal Nehru
National Institute of Technology, Allahabad is an authentic record of our own work carried
out during the period from 2nd January 2014 to 10th May 2014 under the supervision of Dr.
Suantak Kamsonlian, Assistant Professor, Department of Chemical Engineering, Motilal
Nehru National Institute of Technology , Allahabad.
The matter presented in this project report has not been submitted by us for the award
of any other degree of this or any other Institute.

1) Pankaj Kumar Verma (20106051) _______________________

2) Rohit Singh

(20100011) _______________________

3) Yash Trivedi

(20100049) _______________________

4) Yogesh Chauhan

(20109030) _______________________

5) Balaram Singh

(20109035) _______________________

CERTIFICATE
This is to certify that the project report entitled Reduction of COD from dairy
wastewater via adsorption: optimization of process parameters

being

submitted

by

Pankaj Kumar Verma (20106051), Rohit Singh (20100011), Yash Trivedi (20100049),
Yogesh Chauhan (20109030) and Balaram Singh (20109035) towards the fulfilment of the
curriculum of final year of degree of Bachelor of Technology in Chemical Engineering
from

Department of Chemical Engineering of Motilal Nehru National Institute Of

Technology, Allahabad is an authentic record of their own work carried out and has been
successfully completed during final year of their graduation under my supervision.
Date: _____________
Place: _____________

(Dr. SuantakKamsonlian)
Supervisor
Chemical Engineering Deptt.
MNNIT- Allahabad

ABSTRACT
Dairy industry is one of the largest food processing industry which causes severe
environmental problems due to the generation of the waste water containing high solid
concentration, high BOD and COD. The reduction of COD plays a vital role in the treatment
design. Reuse of wastewater from the dairy industry was investigated using coagulation,
adsorption and membrane separation processes. Dairy industry was chosen as it requires
huge volume of water. In the present study an attempt has been made to reduce COD from
dairy waste water using Granulated Activated Carbon (GAC).
The main objective of this project is to minimize the COD level to the required level
stipulated by the environmental standards by employing adsorption using Granulated
Activated Carbon (GAC).
After the adsorption process optimum contact time, pH and dosage were found to be
100 min, 5 and 10.5 g/L respectively. The study was performed at room temperature and at
agitation speed of 160 rpm. Adsorption isotherm has been studied and it is found that
Langmuir isotherm is best fitted. The uptake of COD onto the surface of adsorbent was also
studied using kinetic model study. It is found that Pseudo 2 nd order kinetic model is well
fitted.
Keywords: Dairy Waste Water, COD, Adsorption isotherm, Kinetic study, Activated
Charcoal

ACKNOWLEDGEMENT
We avail this opportunity to express our sincerest respect and profound appreciation
to Dr. Suantak Kamsonlian, Assistant Professor, Chemical Engineering Department, Motilal
Nehru National Institute of Technology, Allahabad for invaluable guidance which he
rendered us during the project. He is our mentor during the project and with his busy
schedule, his precious time was freely available to us always.
We would also like to acknowledge Environment Engineering Laboratory, Civil
Engineering Department, Motilal Nehru National Institute of Technology, Allahabad for
giving us permission to carry out our experiment and also providing valuable support and
suggestion during our project.
We would also like to acknowledge Dr. Sadhna Sachan, Head of Department,
Chemical Engineering, Motilal Nehru National Institute of Technology, Allahabad for
making it possible to work in Chemical Reaction Engineering Laboratory and Mass Transfer
Laboratory. We would also like to thank all the faculty members and staff members for their
support and helping us in completing our project.

1) Pankaj Kumar Verma

(20106051) ________________________________

2) Rohit Singh

(20100011) ________________________________

3) Yash Trivedi

(20100049) ________________________________

4) Yogesh Chauhan

(20109030) ________________________________

5) Balaram Singh

(20109035) ________________________________

LIST OF FIGURES
Chapter 1: Introduction
1.1 Impact of COD on human body and animals
1.2 Impact of COD on aquatic life
Chapter 3: Experimental Setup and Procedure
3.1 Experimental Program for COD Reduction from Dairy Effluent
3.2 Collection of dairy waste water from Parag dairy
3.3 pH measuring instrument used in present study
Chapter 4: Results and Discussions
4.1 SEM image of GAC surface before adsorption
4.2 SEM image of GAC surface after adsorption
4.3 %COD reduction vs treatment time graph
4.4 %COD reduction vs pH graph
4.5 %COD reduction vs dosage graph
4.6 %COD reduction vs contact time graph for equilibrium study
4.7 Langmur isotherm graph for of COD onto GAC surface
4.8 Frendulich isotherm graph for of COD onto GAC surface
4.9 Pseudo first order kinetics study
4.10 Pseudo second order kinetics study

LIST OF TABLES
Chapter 1: Introduction
1.1 Volume of waste water produced at different sources in dairy industry
1.2 Characteristics of dairy waste water of different dairies
Chapter 2: Literature Review
3

2.1 Summary of literature survey

Chapter 4: Results and Discussions
4.1 Effect of Treatment time on COD reduction
4.2 Effect of pH on COD of dairy wastewater
4.3 Effect of adsorbent dosage on COD reduction
4.4 Equilibrium study for COD reduction

CONTENTS
Abstract..

Acknowledgments .

ii

List of Figures

iii

List of Tables .

iv

Chapter 1: Introduction ..

1.1 General ...................

1.2 Effects of COD ...

1.3 Sources of COD in dairy wastewater .

1.4 Dairy Waste Water Characteristics.

1.5 Objective of the Project ..

Chapter 2: Literature Review

2.1 General

2.2 Summary .

Chapter 3: Experimental Setup and Procedure .

10

3.1 Experimental Program .

10

3.2Collection of Wastewater .

11

3.2 Estimation of Parameters .

11

Chapter 4: Results and Discussions ..

14

4.1 Characterization of adsorbents ..

14

4.2 Optimization of Parameters ...

14

4.3 Adsorption Isotherms .........

21

4.4 Adsorption Kinetics ...

24

Chapter 5: Conclusions and Recommendations

27

References ..

28

Chapter 1

INTRODUCTION
1.1 General
India is a developing country. Now a days industrialization and urbanisation is rapidly
increasing. Which is a concern for our society because of increasing pollution. Every
industry produces wastes. Dairy industry is also one of those industries. As Dairy industry is
the global industry and India is the largest milk producing country with the capacity of 137.5
million tons per year. Dairy industry involves processing of raw milk into products such as
consumer milk, butter, cheese, yogurt, condensed milk, dried milk etc, which releases waste
water having high COD content. The dairy industry is an example of food sector, in which
the cleaning silos, tanks, heat exchangers, homogenizers, pipe sand other equipment,
engenders a large amount of effluents with a high organic load. This organic load is basically
constituted by milk (raw material and dairy products), reflecting an effluent with high levels
of chemical oxygen demand (COD), biochemical oxygen demand (BOD), oils and grease,
nitrogen and phosphorus. To recycle water or before disposal of water concentration should
be on reducing impurities. Of all the impurities, COD is one of the impurities which needs to
be reduced. For reduction of COD there are many methods available like Thermal
Oxidation, Extraction, Eltrocoagulation, and Adsorption. Most of the available methods are
costly. We need to select a method for COD reduction which is easier and cheap. One such
method available is Adsorption. As adsorbents are easily available in the market and they are
cheaper than chemicals they can be used to effectively reduce COD from wastewater.
Activated carbon is a highly porous, amorphous solid consisting of microcrystallites with a
graphite lattice, usually prepared in small pellets or a powder. It is non-polar and cheap. One
of its main drawbacks is that it reacts with oxygen at moderate temperatures (over 300
C).Activated carbon is used for adsorption of organic substances and non-polar adsorbates
and it is also usually used for waste gas (and waste water) treatment. It is the most widely
used adsorbent since most of its chemical (e.g. surface groups) and physical properties (e.g.
pore size distribution and surface area) can be tuned according to what is needed. Its
usefulness also derives from its large micropore (and sometimes mesopore) volume and the
resulting high surface area.
1

In the below table 1.1, Standards Norms of Uttar Pradesh Pollution Control Board for
milk dairy effluents is presented.
Table 1.1: Standards Norms of Uttar Pradesh Pollution Control Board for milk dairy
effluents at pH ranges from 5.5 to 9.0.
Parameters

Max. Contaminated Level (MCL), mg/L

COD

250

BOD (3 days at 27 C)

50

Oil & Grease

10

Total solids

2200

Total Dissolved Solids

2100

Suspended Solids

100

Sulphates

1000

Chlorides

600

1.2. Effects of COD

Level of COD determines the quality of water. Higher amount of COD lowers the quality
of water. Therefore reducing COD is of prime concern as high level of COD inflicts damage
to humans as well as animals. The fish and other aquatic animals are killed due to high level
of COD as industrial waste and other pollutants lowers the amount of dissolved oxygen in
the water (fig. 1.2).
The excess amount of organic content present in industrial waste causes development of
bacteria and Fungi glops (fig 1.1). These bacteria and fungi changes the quality of aquatic
ecosystem and raises the pH of water which results in the death of many aquatic animals and
plants. The sediment present in the water changes the color, turbidity and also causes
erosion. Sediment also clogs up the gills of the fish and causes other harm to the animals.
This also makes the water unsuitable for drinking purposes.

Fig. 1.1: High levels of COD in water Fig. 1.2: Fish kill due to industrial pollution
often correlate with threats
and reduced dissolved oxygen from
to human health including
increased COD and BOD. (Photo
toxic algae blooms bacteria
provided by the US Fish and
from organic wastes and
Wildlife Service)
seafood contamination

1.3. Sources of COD in Dairy Industry

The dairy industry is the global industry and India is the largest milk producing
country with the capacity of 137.5 million tons. Dairy industry involves processing of raw
milk into products such as butter, cheese, yoghurt, condensed milk which all results in COD.
Generally water requirement is quite high in dairy industry as it is used in various steps
whether it is cleaning, cooling, sanitization etc. this huge amount of water must be recycled
or disposed but before that impurities must be removed. There are various methods such as
flocculation, coagulation which are being used but all these processes are very expensive. In
an alternate to these techniques adsorption is also used. This is a cost effective method for
reducing impurities in dairy waste water. Recent studies has shown that adsorption using
activated charcoal can be used to reduce the level of COD. Activated charcoal serves as a
good adsorbing agent as it is porous and surface area is quite large. Table 1.1 shows the
amount of waste water which is released in the production of various dairy products.

Table 1.1: Volume of waste water produced at different sources in dairy industry
Main Processes

Volume of wastewater(liter per liter of milk)

Production of butter

1-3

Production of cheese

2-4

Production of fresh

2.5-9

milk(Pasteurization and
Sterilization)
1.4. Dairy Waste Water Characteristics
Dairy effluents contains sugar, protein, fats and some other residues of additives. The
Source

Colour

Odour

pH

COD (mg/L)

Nagpur(Maharastra) gov. dairy

milky

unpleasant

4.06

5760

AAVIN Dairy, Coimbatore

milky

unpleasant

7.8-8.5

2850

Sangam Dairy, Andhra Pradesh

milky

unpleasant

6.23

2500

Parag Dairy, Allahabad

milky
unpleasant
8.28
1760
key parameters are biological oxygen demand (BOD), with an average ranging from 0.8 to
2.5 kilograms per metric ton of milk in the untreated effluent. Chemical oxygen demand
(COD), which is normally about 1.5 times the BOD level. So we can see that reduction of
these organic and inorganic material is of prime importance before we can dispose or recycle
the dairy waste water.
Total suspended solids, at 1001,000 mg/L; total dissolved solids: phosphorus (10
100 mg/L), and nitrogen (about 6% of the BOD level). Table 1.2 shows some characteristics
dairy waste waters of different dairies.
Table 1.2: Characteristics of dairy waste water of different dairies

1.5 Objective of the Project

Milk and milk products are very essential for mankind. Dairy industry uses huge
amount of water, hence it produces a large quantity of wastewater. If wastewater is treated
carefully then it can be recycled and used in the same process. The wastewater released from
dairy industry contains a large amount of organic matter. This may affect the death of many
aquatic animals and plants. Hence, reduction of COD level from diary wastewater is very
important to protect and prevent the environment. As per the literature survey of the past
works, we can see that less work has been done on reduction of COD from dairy wastewater
as compared to other industrial wastewater. The processes like oxidation, electrocoagulation
and combined processes were employed for COD reduction. However, very less work has
been carried out for reduction of COD level from diary wastewater using adsorption process
so far. The reduction efficiency of COD level is high in conventional process than
adsorption but they are not economical. Also, adsorbents are easily available in nature and
cheap.
In the present study, reduction of COD level from dairy wastewater by adsorption
using GAC was conducted in batch process. Characterization of the adsorbent surface was
analysed by using SEM analysis. Optimization of the process parameters such pH, dosage
and contact time were performed for COD reduction. The adsorption isotherms such as
Langmuir isotherm and Freundlich isotherm were studied to understand the mechanism of
adsorption. Moreover, kinetic studies have also been performed for Pseudo first order and
Pseudo second order.

Chapter 2

LITERATURE REVIEW
2.1.

GENERAL
This chapter presents a comprehensive review of literature on reduction of COD from

dairy wastewater using adsorption. Moreover, summary of literature is also reported here.
Halim et al. (2010) studied adsorption properties of ammoniacal nitrogen and COD in
semi-aerobic leachate from the Pulau Burung landfill site on zeolite, activated carbon and a
new composite media in terms of adsorption isotherm and kinetic. The results show that all
adsorbents fitted well with both Langmuir and Freundlich isotherms (R2>9) for ammonia
adsorption. A comparison study indicated that the adsorption capacity of composite
adsorbent towards ammoniacal nitrogen was higher than zeolite and activated carbon and
comparable to activated carbon for COD. Findings from a kinetic study indicated that the
adsorption of ammonia on new composite adsorbent and zeolite follow almost all kinetic
models such as pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion
model, although pseudo-second-order was the most dominant. COD adsorption fitted well
with the pseudo-second-order kinetic model, while activated carbon obeys the pseudo-firstorder and intra-particle models.
Devi et al. (2007) examined the assessment of reduction of chemical oxygen demand
(COD) and biological oxygen demand (BOD) of wastewater from coffee processing plant
using activated carbon made up of Avacado Peels. The complete study was done in batch
mode to investigate the effect of operating parameters. The results of the COD and BOD
concentration reduction with avocado peel carbon (APC) and commercial activated carbon
(CAC) were compared and optimum operating conditions were determined for maximum
reduction. Adsorption isotherm was also studied besides the calculation of optimum
6

treatment parameters for maximum reduction of COD and BOD concentration from effluent
of the coffee processing plant. The maximum percentage reduction of COD and BOD
concentration under optimum operating conditions using APC was 98.20% and 99.18%
respectively and with CAC this reduction was99.02% and 99.35% respectively. As the
adsorption capacity of APC is comparable with that of CAC for reduction of COD and BOD
concentration, it could be a lucrative technique for treatment of domestic wastewater
generated in decentralized sectors.
Kushwaha et al. (2010) studied the treatment of synthetic dairy wastewater (SDW) in
terms of chemical oxygen demand (COD) removal by means of adsorption onto activated
carbon-commercial grade (ACC) and bagasse fly ash (BFA). Optimum conditions for SDW
treatment were found to be: initial pH=4.8, adsorbent dose of 20 g/l for ACC and 10 g/l for
BFA and contact time8 h. Pseudo-second-order kinetic model was found to fit the kinetic
data and RedlichPeterson isotherm model was generally found to best represent the
equilibrium data for SDW treatment by ACC and BFA. The change in entropy and enthalpy
for SDW adsorption onto ACC and BFA were estimated as 125.85 kJ/mol.K and 91.53
kJ/mol; and 25.71 kJ/mol.K and 17.26 kJ/mol, respectively. The negative values of change
in Gibbs free energy indicate the feasibility and spontaneous nature of the adsorptive
treatment.
Aluyor et al. (2008) performed a batch experiment on COD reduction by adsorption
using activated carbon preparedfrom animal horns (AHC), which is both a waste and
a pollutant and a commercial activated carbon(CAC) with respect to uptake of the
organic components responsible for the chemical oxygen demand (COD) of industrial
wastewater. The adsorption process was examined in terms of its equilibria and its kinetics.
The effect of pH, contact time and adsorbent dose were investigated. The most effective pH
was found to be 5 for AHC and 6 for CAC. The equilibrium data for COD removal fitted the
Linear, Langmuir and the Freundlich models. The mechanisms of the rate of adsorption
of COD were analyzedusing the pseudo-second-order model. The model provided a
very high degree of correlation of theexperimental adsorption rate data suggesting that
this model could be used in design applications.

2.2 Summary
Table 2.1 shows the summary of the previous works that have been done in the field of
COD reduction from industrial effluent using various methods available like Coagulation,
Thermal liquid phase oxidation, Electrocoagulation, Dissolved air oxidation and Adsorption
etc.
Table 2.1: Summary of literature review
Sources of
Wastewate
r
A.P. Dairy,
Hyderabad

Method

Adsorbent

Treatment Conditions
Conc.

Coagulation
followed by
Adsorption

AAVIN
Adsorption
Dairy,
(Biosorption)
Coimbatore

Coffee
Processing
Plant

Adsorption

Molasses
based
distillery

Adsorption

Coagulantsalum and
ferric
chloride
AdsorbentActivated
charcoal

Water
Hyacinth

1001000
mg/L
0.5- 2
g/L

pH Contact Temp
time ( oC)
4-8 30-150
4-8
min
30-120
min

5-15
g/L

10-60
min

1-10 g/
Commercial 100
activated
mL
Carbon
(Avacado
Peel)
Activated
10 g/L
Carbon

10-100
min

30 min

Observations

Reference

Optimum conc. =
Baisali
Sarkar
et al.
700 mg/L, pH= 6,
(2005)
contact time= 100
min, COD
removal= 65 %
Optimum contact
time = 90 min,
pH= 6, conc.= 1.5
g/L, COD
removal= 87.5%
Optimum contact K. Murali et
time = 40 min,
al.
conc.= 15g,
(2013)
COD removal =
89.5 %
Optimum Contact Devi et al.
time= 70 min,
(2008)
conc.= 4 g/
100mL, COD
removal = 82 %
Colour removal= Y. Satyawali
58%, COD
et al. (2007)
removal = 60 %

Refinery

Adsorption +

Wastewater Dissolved air

Activated

40-

COD removal=

Carbon

100

72%, BOD

Distillery

oxidation
Adsorption +

Effluent

electrocogulation charcoal
Thermal Liquid
Phase Oxidation

mg/L
Activated

6-

30-1150

8.2

min

al.

removal= 76 %
(2007)
Colour removal= Bhise R. M.
72.78 %, COD

removal= 62 %
500 7.9- 120200- Optimum
mL
9.7 210 min 230 removal of COD
about 49.77%
Waste
was achieved at
water
optimum T=
230C, t = 120
min, pH= 7.9

Malik L. et

et al. (2012)
Kumar et al.
(2013)

Chapter 3

EXPERIMENTAL SETUP AND PROCEDURE

3.1. Experimental Program
Fig. 3.1 shows the procedure to be followed in our study. First of all we collected
wastewater from Parag dairy. The parameters of the wastewater were studied before the
adsorption. Adsorption of wastewater was carried by using GAC. After the adsorption
process, parameters again studied for the treated sample. For characterization of adsorbents,
Scanning Electron Microgaph (SEM) analysis was performed. The results obtained from the
adsorption process have been used for mathematical modelling.
Wastewater Collection

Granulated Activated
Carbon ddd(GAC)

Adsorption

Optimization of Parameters
(pH, Dosage and Contact Time)

Characterization of
Adsorbent (SEM Analysis)

Mathematical models
1.) Isotherms
2.) Kinetic Model

Fig. 3.1: Experimental Program for COD Reduction from Dairy Effluent

3.2. Collection of wastewater

10

We have collected wastewater from PARAG Dairy, Allahabad. Fig. 3.2 shows the
image of wastewater collection site. The wastewater appears to be milky in colour and
having unpleasant odour. The pH of wastewater was 8.28 and COD level 1760 mg/L.

Fig. 3.2: Photograph of diary wastewater collected from Parag Dairy, Manauri, Allahabad
3.2 Estimation of Parameters
3.2.1 pH
The pH of wastewater is calculated as 8.28 using the pH meter which was available
in our Mass Transfer laboratory. A pH meter represents the hydrogen ion concentration in
pH units [13]. A pH meter consists of a glass electrode and a read out screen. The glass
electrode is made of very thin glass that establishes and measures the electrical potential
difference between the analyte solution (the solution to be measured) and an internal
reference. The electrical potential is then converted into a pH reading for the sample [13].
The probe is a key part of a pH meter, it is a rod like structure usually made up of glass. At
the bottom of the probe there is a bulb, the bulb is a sensitive part of a probe that contains
the sensor. Never touch the bulb by hand and clean it with the help of an absorbent tissue
paper with very soft hands, being careful not to rub the tissue against the glass bulb in order
to avoid creating static [14].

11

Fig. 3.2: Photograph of pH meter used in the present work

3.2.2 COD testing method
Chemical Oxygen Demand (COD) is also referred to as the Dichromate Oxygen
consumed. COD test is used for estimation of the amount of organic matter in sewage and
industrial effluents. For determining COD, the organic matter is oxidised with the help of
sulphuric acid. A catalyst such as silver sulphate is used to help the oxidation of the organic
matter. Titration of excess dichromate is done by using ferrous ammonium sulphate solution.
COD gives the oxygen required for the complete oxidation of biodegradable and nonbiodegradable matter [4].
Apparatus Required
COD Digester, COD Vials with stand, Pipette with elongated tip, Pipette Bulb,
Conical Flask, Tissue Papers, Wash Bottle, Burette, Burette stand.
Chemicals Required

Standard Potassium Dichromate Solution (0.25 N)

Sulphuric Acid
Standard Ferrous Ammonium Sulphate (0.1 N)
Ferroin Indicator
Silver Sulphate
Mercury Sulphate Crystals
Organic free Distilled Water
The process which we used to calculate the COD of dairy waste water in our

experiment is the open reflux method. In this method a sample is refluxed in strongly acid
solution and an excess amount of potassium dichromate (K2Cr2O7). After the process of
12

oxidation, the excess amount of K2Cr2O7 is titrated using ferrous ammonium sulphate (FAS)
to determine the amount of K 2Cr2O7 consumed. Ferroin indicator is used to determine the
end point as it changes its colour from blue-green to reddish brown. The amount of FAS
used is equivalent to the amount of an excess oxidizing agent [5].
After the determination of COD of sample, activated charcoal is used as adsorbent
and then after limited time, the sample if filtered and filtrate is again titrated using the
same method as to see how much COD has been reduced.
Calculations
The formula which was used to determine the COD is [5]
COD=

( AB) N 8 1000
(3.1)
Vol. of sample taken

where,

A= Volume of ferrous ammonium sulphate for blank

B= Volume of ferrous ammonium sulphate for sample
Volume of sample V= 2.5mL
Normality of ferrous ammonium sulphate N= 0.1 N
For our collected waste water-A= 14.1, B= 8.6
Hence, COD= 1760 mg/L
For calculating the % COD reduction form wastewater, following equation is used
[5]%COD r eduction=

C iC 0
100(3.2)
Ci

where,
Ci= COD of waste water, Co= COD of sample after treatment

13

Chapter 4

RESULTS AND DISCUSSIONS

4.1. Characterization of Adsorbents
The surface of adsorbent as GAC was analysed using Scanning Electron Microgaph
(SEM) to understand its surface morphological characteristics. The fig. 4.1 shows the image
of adsorbent before the adsorption having a smooth structure and fig. 4.2 shows the SEM
analysis of adsorbent after adsorption of organis matters. It was observed that after
adsorption, the surface of the adsorbent become rough and formed a texture structure due to
the accumulation of organic matters.

Fig. 4.2: After adsorption SEM image

Fig. 4.1: Before adsorption SEM image

4.2. Optimization of Parameters

4.2.1. Effect of treatment time
For studying the effect of the treatment time 7 samples of waste water of 3.5 mL
were taken. 3 g/L of activated carbon were added to each of the samples then each of the
samples were agitated for different contact time ranging from 20 minute to 70 minute. After
filtering the solution filtrates were analyzed for the COD value.
As shown in fig. 4.3, irrespective of the amount of adsorbent and the initial organic
compounds concentration, organic compounds adsorption from aqueous solution by charcoal
was rapid during the initial period of contact and then gradually became slower with
14

increasing contact time [4]. The adsorption attained equilibrium within 2070 min of
contact, and after reaching equilibrium, the adsorption rate remained almost constant with a
very slow increment in adsorption (fig. 4.3). The adequate accessibility of vacant adsorption
sites cause rapid adsorption onto the exterior surface of the charcoal at starting of adsorption
process, as represented by the curved portions in fig. 4.3 [4]. After a drop of time, the
majority of the exterior sites of the adsorbent surface were occupied by organic compounds,
and the remaining vacant sites became unavailable due to the repulsive forces between the
solute molecules in the solid and bulk phases [6]. At this stage, organic compounds were
transported to internal sites of the adsorbent through pore diffusion, which requires a longer
contact time. As it can be seen from the fig. 4.3 that optimum contact time is reached at 50
minute. As after 50 min. there is no significant reduction of COD is obtained.
Table 4.1: Effect of Treatment time on COD removal with dosage = 3 g/L, time= 10 to 70
min, agitation speed= 160 rpm

S. No. Speed of shaking (rpm) Dosage (g/L) Time (min) COD (mg/L) % COD reduction
1

160

10

160

160

15.23

20

1492
1316

30

1118

36.48

160

40

1022

41.93

160

50

998

43.30

160

60

990

43.75

160

70

986

43.98

15

25.23

% COD Reduction Vs Time (min)

60
40
% COD Reduction

20
0
0

10

20

30

40

50

60

70

80

Time (min)

Fig. 4.3: Effect of Treatment time on COD reduction with dosage = 3 g/L, time= 10
to 70 min, agitation speed= 160 rpm
4.2.2. Effect of pH
To study the effect of pH on COD reduction we treated the sample for 50 minutes
with 3 g/L of adsorbent and varying pH between 2 to 8. The pH was maintained using
NaOH/ HCl solution. Each sample were treated at room temperature. After treatment the
sample was filtered and filtrate was observed for the COD value. Table 4.2 is showing the
variation of the COD with pH.
The initial pH of the solution is one of the most significant factors affecting the
adsorption capacity for wastewater treatment. The variation of adsorption capacity for the
adsorbent at different pH can be credited to the chemistry of both the organic compounds
and the adsorbent, specifically the surface charge of the adsorbent in aqueous solution at a
certain pH. The COD value increases as pH is increased up to the neutral pH, after that it
starts decreasing thereby increasing hindrance for the diffusion of organics. At higher acidic
medium larger number of H ions are present, which neutralizes the negatively charged
adsorbent surface. As it is clear from the fig. 4.4. At higher pH the capacity of adsorbent
decreases. Due to more OH ions present at higher pH, the hindrance to diffusion increases
[6].

16

From the fig. 4.4 it clear that we get an optimum pH of 5. So, to study further
parameters we will keep pH as 5 with varying the parameters which to be studied and other
parameters are optimized as well.
Table 4.2: Effect of pH on COD of effluent
S. No.

pH

COD
(mg/L)

% COD
reduction

1.

986

43.6

2.

972

44.7

3.

954

45.8

4.

932

47.0

5.

946

46.2

6.

948

46.1

7.

952

45.9

% COD reduction vs pH
48.00
46.00
% COD Reduction

44.00
42.00
0

10

pH

Fig. 4.4: Effect of pH on COD reduction with dosage = 3 g/L, time= 50 min and agitation
speed= 160 rpm respectively.

17

4.2.3. Effect of Dosage

The requirement to investigate the effect of adsorbent dose comes from the economic
point of view, which requires the minimum amount of adsorbent for effective COD
reduction. The COD reduction percentage increased with increasing amount of adsorbent up
to 10.5 g /L, and for higher doses, no change in reduction efficiency was observed. The
increase in the amount of adsorbent enhanced the surface area, which, increased the number
of available adsorption sites and, thus, also boost the interaction between the adsorbent and
organic compounds, leading to the rise in the extent of COD reduction. Thus, as the
adsorbent dose increased from 3 to 10.5 g /L, the amount of COD adsorbed per unit weight
of adsorbent decreased, causing a decrease in adsorption capacity [6]. This result can be
recognized to the significant unsaturation of adsorption sites at higher adsorbent dosages for
constant COD concentration and volume.
The experimental results of charcoal dosage for COD reduction in adsorption process
are verified in fig. 4.5. For experimental verification, the treatment time is taken as 50 min,
pH= 5, agitation speed= 160 rpm, adsorbent dose is varied from 3 g/L to 13.5 g/L. The
results obtained are tabulated in table 4.3 of COD reduction with respect to adsorbent dose.
The variation in % COD reduction is plotted against adsorbent dosage, which is
shown in fig. 4.5. The COD reduction increases up to the 10.5 g/L of the adsorbent dosage,
after that the reduction is not significant, which means 10.5 g/L is the optimum amount of
adsorbent for COD reduction. At the optimum dosage, the COD reduction is 60.1 %, as
shown in table 4.3.

18

Table 4.3: Effect of adsorbent Dosage on COD reduction

S. No. Speed of shaking(rpm) Time (min) Dosage (g/L) COD (mg/L) % COD reduction
1

160

50

932

47

160

50

4.5

882

49.9

160

50

820

53.4

160

50

7.5

742

57.8

160

50

722

59

160

50

10.5

702

60.1

160

50

12

696

60.5

160

50

13.5

692

60.7

% COD Reduction Vs Dosage

80
60

% COD Reduction

40
20
0
2

10

12

14

16

Dosage (g/L)
Fig 4.5: Effect of dosage on COD reduction with dosage = 3 g/L to 13.5 g/L, time= 50 min,
agitation speed= 160 rpm and pH= 5 respectively.

4.2.4. Equilibrium Study

19

After optimizing all the parameters, we taken the sample and studied it for
equilibrium to get the maximum COD removal. Taking Optimum parameters viz. pH= 5,
dosage (m) = 10.5 g/L, rotation speed= 160 rpm, we varied contact time from 20 min to 120
min, to obtain equilibrium COD reduction. The maximum COD reduction we obtained as
75.91 % at optimum contact time of 80 minutes.
Table 4.4: Equilibrium study for reduction of COD
Time (min)

COD (mg/L)

%COD Reduction

20

692

60.68

40

602

65.80

60

512

70.91

80

424

75.91

100

418

76.25

120

414

76.48

% COD Reduction Vs Time

80
60

%COD Reduction 40
20
0

20

40

60

80

100

120

140

Time(min.)

Fig 4.6: Equilibrium Study for COD reduction with dosage = 13.5 g/L, time= 20
min. to 120 min., agitation speed= 160 rpm and pH= 5.

4.3. Adsorption Isotherms

20

An isotherm is a set of equilibrium capacity (or loading) data over a range of fluidphase concentrations at a fixed temperature. Equilibrium isotherm equations are used to
describe experimental sorption data.
The equation parameters and the underlying thermodynamic assumptions of these
equilibrium models often provide some insight into both the sorption mechanism and the
surface properties and affinity of the sorbent. Many semi theoretical equations are used to fit
isotherm data and those having more parameters can account for more subtle effects. In most
cases, simpler is better.
For the monolayer adsorption, from the many of the isotherms Langmuir and
Freundlich isotherms are best suited. The Langmuir and the Freundlich isotherm were tested
for their ability to describe the experimental results. The Langmuir adsorption model is based
on the assumption that maximum adsorption corresponds to a saturated monolayer of solute
molecules on the adsorbent surface, with no lateral interaction between the adsorbed
molecules [8].
4.3.1. Langmuir Isotherm
In 1916, Irving Langmuir published an isotherm for gases adsorbed on solids,
which retained his name. It is an empirical isotherm derived from a proposed kinetic
mechanism.
It is based on five hypotheses [8] :
1.
2.
3.
4.

The surface of the adsorbent is uniform, that is, all the adsorption sites are equal.
Adsorbed molecules do not interact.
All adsorption occurs through the same mechanism.
At the maximum adsorption, only monolayer is formed: molecules of adsorbate do
not deposit on other, already adsorbed, molecules of adsorbate, only on the free

surface of the adsorbent.

5. A second order reaction.
Langmuir model assumes that surface of adsorbent is homogeneous and all active sites
are energetically symmetrical resulting monolayer coverage and constant binding energy
between surface and adsorbate i.e, only one solute molecule per site and a fixed number of
sites are available. The monolayer adsorption comes under chemical adsorption or
chemisorption. In this type of adsorptions, the force of attraction existing between
21

adsorbate and adsorbent are almost same strength as chemical bonds. In chemisorption the
force of attraction is very strong, therefore adsorption cannot be easily reversed [5].
Langmuir isotherm can be expressed by [5]
q e=

Qb C e
(4.1)
(1+ b Ce )

where,
Q = maximum adsorption capacity (mg/g)
b = Langmuir constant (L/mg)
qeq = mass of material adsorbed (at equilibrium) per mass of adsorbent (mg/g)
Ceq = equilibrium concentration in solution when amount adsorbed equals qe (mg/L).
On linearizing the equation (4.3.1) [5]
1 1
1
= +
(4.2)
qe Q Qb C e
Fig. 4.7 shows the Langmuir plot, by which value of Q and b is calculated as 112
mg/g and 0.70169 L/mg respectively. The linear regression coefficient (R 2) comes out to be
0.9857, which is the clear indication of linear fit of Langmuir isotherm.
4.3.2 Fruendlich Isotherm
Freundlich isotherm assumes that the uptakes of adsorbate occur on a heterogeneous
surface by multilayer adsorption and the amount of adsorbate adsorbed increases infinitely
with an increase in concentration. This type of adsorption comes under physical adsorption
or physiosorption. If the force of attraction existing between adsorbate and adsorbent are
Vander Waals forces, the adsorption is called physical adsorption [5]. It is also known as
Vander Waals adsorption. In physical adsorption the force of attraction between the
adsorbate and adsorbent are very weak, therefore this type of adsorption can be easily
reversed by heating or by decreasing the pressure. This type of adsorption usually takes
place at low temperature and decreases with increasing temperature [6].

The Freundlich equation is given as [5]22

1
n
e

q e= K F C (4.3)
where
KF = adsorption capacity
1/n = adsorption intensity
qeq = mass of material adsorbed (at equilibrium) per mass of adsorbent (mg/g)
Ceq = equilibrium concentration in solution when amount adsorbed equals qe (mg/L).
On linearization of equation (4.3) we get [5]
1
log q e=log K F + log C( 4.4)
n
For calculation of qe following equation will be used [5] q e= ( C0 Ce )

V
( 4.5)
W

Fig. 4.8 shows the Fruendlich plot, by which value of KF and n is calculated to be 14.392
L/mg and 1.5633 respectively with the regression coefficient (R2) of 0.96012.
As the Langmuir curve is having higher adsorption capacity it is better fit isotherm.

Fig.4.7: Langmiur isotherm for reduction

Fig.4.8: Fruendlich isotherm for reduction of

of COD from dairy waste water (Ci= 752

COD from dairy waste water(Ci= 752 mg/L, t=

mg/L, t= 80 min and 160 rpm)

80 min and 160 rpm)

Table 4.5: Parameters for Langmuir and Fruendlich models for the sorption of COD onto
23

the surface of GAC

Isotherm Study
Langmiur
Q(mg/g)
b(L/mg)
R2
112
0.70169

Fruendlich
KF(L/mg)
n
0.9857
14.392

R2
1.5633

0.96012

4.4 Adsorption Kinetics

The study of the adsorption kinetics is the main factor for designing an
appropriate adsorption system and quantifying the changes in adsorption with time
requires that an appropriate kinetic model is used. The rate of adsorption of organic
material onto the adsorbent surface can also be studied like other molecules. Adsorption
kinetics study not only allows estimation of sorption rates but it also leads to suitable rate
expression characteristics of possible reaction mechanisms. In this respect two kinetic
models, pseudo first order kinetic model and pseudo second order kinetic models have been
studied.
4.4.1 Pseudo First Order Kinetic Model
The Pseudo first order kinetic model is given by the following equation [5]ln ( q e q t )=ln ( qe ) k 1 ( t ) ( 4.5)
where,
qe = amount of COD adsorbed at equilibrium (mg/g)
qt = amount of COD adsorbed at time t (mg/g)
k1 = pseudo first order rate constant (min-1)
t = time (min)

4.4.2 Pseudo Second Order Kinetic Model

24

The second order kinetic model is given by the following equation [5]t
1
t
=
+ (4.6)
qt k 2 q 2e qe
where,
qe = amount of COD adsorbed at equilibrium (mg/g)
qt = amount of COD adsorbed at time t (mg/g)
k2 = pseudo second order rate constant (g.mg-1min-1)
t = time (min)
Fig. 4.9 shows the pseudo first order kinetics, the value of rate constant (k 1), qe,cal and R2 is
calculated to be 0.682 h-1, 19.3 mg/g and 0.92106 respectively (table 4.6). Table 4.6 also
shows the value of qe,exp= 27.1. Fig. 4.10 shows the pseudo second order kinetics, the value
of rate constant (k2), qe,cal and R2 is calculated to be 0.034 g/mg.h, 30.4 mg/g and 0.97649
respectively (table 4.6). Hence, pseudo second order is more favourable than pseudo first
order.

Fig. 4.9: Pseudo first order kinetics at

Fig. 4.10: Pseudo second order kinetics
0
25 C, 702 mg/L and dosage of 10.5
at 250C, 702 mg/L and dosage of 10.5
g/L
g/L
Table 4.6: Kinetic Model Parameters for sorption of COD onto the surface of GAC
25

Initial qe,exp
Conc. (mg/g)
(mg/L)
702

27.1

Pseudo 1st Order Kinetic Model

k1 (1/h)

qe,cal
(mg/g)

R2

0.682

19.3

0.92106

26

Pseudo 2nd Order Kinetic Model

k2
(g/mg.h)
0.034

qe,cal
(mg/g)

R2

30.4

0.97649

Chapter 5

CONCLUSIONS AND RECOMMENDATIONS

The present study on reduction of COD from diary wastewater using GAC by adsorption
process can be concluded as follows:

The maximum COD reduction was obtained as 76.25 % at Optimum contact time of
80 min, Dosage of 10.5 g/L of Activated carbon (mesh size- 300), speed of shaking
of 160 rpm, pH of 5 at room temperature.

For equilibrium studies Langmuir isotherm was found to be more favorable than
Freundlich isotherm with maximum adsorption capacity of 112 mg/g.

The uptake of COD onto the adsorbent surface was studied using kinetic model and
Pseudo 2nd order kinetic model fits very well with Linear Correlation coefficient (R 2=
0.9764) and adsorption capacity of 30.4 mg/g.

Activated charcoal is easily available and cheap than other chemical adsorbents.

The adsorbent can be reused disposed of safely after drying or burned.

It is clear that utilization of Activated carbon have effectively removed COD from
Dairy wastewater and this is a better solution for achieving a cleaner production
technology.

Recommendations and Future Scope

Parameters like particle size, agitation speed and temperature can also be studied for

higher reduction of COD level.

Thermodynamic properties can be determined to understand the spontaneity nature

of sorption process.
Further a continuous process study should be carried out.

27

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