Treatment of Dairy Wastewater

Treatment of Dairy Wastewater implementing
Coagulation and Adsorption.
Treatment of Dairy Wastewater implementing

Coagulation and Adsorption
A Thesis submitted in partial fulfillment of the requirements for the

degree of
Master of Engineering
In
Chemical Engineering
By
Uttarini Pathak
(Roll No. 001310302007
Regn N0.-124704
Exam Roll No. M4CHE1507
Under the supervision and guidance of

Dr. Siddhartha Datta , Sri. Prasanta K. Banerjee
Department of Chemical Engineering
Jadavpur University
Kolkata 700032
CERTIFICATE
This is to certify that the thesis entiled Treatment of Dairy Wastewater
implementing Coagulation and adsorption is submitted by Uttarini Pathak
student of Chemical Engineering Department of registration year 2013- 2014 to
this institute in partial fulfillment of the requirement for the award of the degree of
Master of Engineering by Research.
This report is a bona-fide record of the work carried out by her under my
supervision and guidance at the Department of Chemical Engineering,
JADAVPUR UNIVERSITY, Kolkata-700032.It is further certified that no part of
this thesis is submitted for the award of any degree.
Sri. Prasanta K. Banerjee

Jadavpur University
Dr. Siddhartha Datta

Jadavpur University
APPROVAL
The following thesis is hereby approved as a credible study of a Engineering
subject and presented in a manner satisfactory to warrant its acceptance as a
perquisite to the degree for which it has been submitted. It is to be understood that
by this approval, the undersigned do not necessarily endorse or approve any
statement made, opinion expressed or conclusion drawn there in, but approve the
thesis only for the purpose for which it has been submitted.

Jadavpur University
HOD (Department of Chemical Engineering)
Dean (FET)
ACKNOWLEDGEMENT
I am grateful to Chemical Engineering Department, Jadavpur University, Kolkata for providing
an opportunity to undertake this Project Work.
While doing this project, I have come across many erudite personalities who had helped me a lot
in doing and finishing this project simultaneously. It is their kind help and untiring effort that has
resulted in completion of this project.
I would like to express my heartful gratitude to Prof. Dr. Siddhartha Datta and Sri. Prasanta K.
Banerjee of Chemical Engineering Department of Jadavpur University, Jadavpur for allowing
me to complete this work under their elegant supervision and guidance. Their encouragement
throughout the times of difficulties was something that cannot be expressed with mere words.I
am deeply indebted to them.
I am very grateful to Prof. Dr. Papita Das & Head of the Department, Chemical Engineering
Department, Jadavpur university and all other faculty members for their help and cooperation.
I would like to extend my thanks to our Lab assistant who has helped me a lot all throughout my
work. My sincere appreciation also extends to all my colleagues and others who have provided
assistance at various occasions; it is not possible to list all of them in this limited space.
I am grateful to my parents who encouraged and supported me all through and helped me in all
respect.
UTTARINI PATHAK
ABSTRACT
Dairy industry is one of the largest food processing industry which causes severe environmental
problems due to the generation of wastewater containing high Solid concentration, high BOD
and COD . Of all industrial activities, this food sector has one of the highest consumptions of
water and is one of the biggest producers of effluent per unit of production in addition to
generating, besides to generate a large volume of sludge in biological treatment. Effluent from
milk processing unit contains soluble organics, suspended solids, trace organics which releases
gases, causes taste and odor, impart colour and turbidity, and promote eutrophication. The casein
precipitation from waste decomposes further into highly odorous black sludge. .In this study
after determination of the preliminary parameters like pH, BOD, COD, Oil and Grease, alkanity
and many more it was subjected to coagulation using alum, lime, Ferric Chloride and Ferrous
Sulfate. It was found that efficient removal of COD as much as 92 % could be brought using a
combination of lime and Ferrous Sulfate. Moreover further studies was done to check whether
coagulation followed by adsorption process could be adopted which resulted in increased value
of COD. Thereby Adsorption Batch studies using nano composites (Graphene Oxide and
Hydroxyapatite nano particles) and plant adsorbents were performed ( Ricehusk and Sawdust).
Batch adsorption studies are carried out as a variation of adsorbent dosage solution pH, contact
time, initial COD concentration and temperature. Results obtained clarified that nano particles
would be more preferable compared to agro based adsorbents. But all four showed a same
pattern of maximum removal at conditions of Low temperature(20 -25 deg C) and Low pH (2
4). Further Fitting of Isotherms and evaluation of kinetics and thermodynamics were done which
showed that Langmuir isotherm favoured the process followed by an exothermic reaction with
second order kinetics taking place.
CONTENTS
1.0 INTRODUCTION
2.0 LITERATURE REVIEW
2.1.1 Biological oxygen demand (BOD)
2.1.2 Chemical oxygen demand (COD)
2.1.3 pH
2.2 New Technologies in the Dairy Industry Waste Water Treatment
2.2.1 Ion Exchange
2.2.2 Chemical Oxidation
2.2.3.Membrane Filtration
2.2.4 Ozonization
2.2.5 Biodegradation
2.2.5 Solvent Extraction
2.3 CHEMICAL PRECIPITATION (Coagulation and Flocculation)
2.4 ADSORPTION
2.4.1 Fundamentals of the adsorption
2.4.2 Physical Adsorption
2.4.3 Chemical Adsorption
2.4.4 Adsorption Mechanism
2.5 ADSORBENTS
2.5.1 Sawdust
2.5.2 Ricehusk
2.5.3 Graphene Oxide
2.5.4 Hap Nano-Composites
2.6 ADSORPTION ISOTHERMS
2.6.1 Langmuir Isotherm
2.6.2 Freundlich Isotherm
2.7 Adsorption Kinetics
2.8 Adsorption Thermodynamics
3.0 MATERIALS AND METHODS
3.1 Coagulation- Coagulants and Procedure
3.1.1 Preparation of Coagulant Solution
3.1.2 COD Estimation
3.2 Adsorbent preparation
3.3 Batch sorption experiments
4.0 RESULTS AND DISCUSSIONS
4.1 Characterisation of Dairy Wastewater
4.2 Results obtained after Treatment of Wastewater with Coagulants
4.3 Results obtained after Treatment of Wastewater with Coagulation followed by
Adsorption.
4.4 Rate of Settling
4.5 Batch Adsorption study using Graphene Oxide as Adsorbent

4.5.1 Effect of Adsorbent Dosage
4.5.2 Effect of pH
4.5.3 Effect of Temperature
4.6 Batch Adsorption Study Using HAP Nano-Composites As Adsorbent
4.6.2 Effect of pH
4.6.4 Effect of Concentration
4.6.5 Adsorption Isotherms
4.6.6 Adsorption Thermodynamics
4.6.7 Adsorption Kinetics
4.7 Batch Adsorption study using Ricehusk as Adsorbent
4.7.2 Effect of pH
4.8 Batch Adsorption study using Sawdust as Adsorbent
4.8.2 Effect of pH
4.8.5 Effect of Adsorbent Size
4.9 Conclusion
5.0 References
LIST OF TABLES
1.
2.
3.
4.
5.
6.
Characteristics of Dairy Wastewater

Effect of Different Coagulant Treatment on Different Parameters
Effect of Coagulation Followed By Adsorption
Percentage Removal at different Adsorbent Dosage onto Graphene Oxide
Percentage Removal at different pH onto Graphene Oxide
Percentage Removal at different Temperature For Adsorption onto
Graphene Oxide
7. Percentage Removal at different Dosage For Adsorption onto HAP
8. Percentage Removal at different pH For Adsorption onto HAP
9. Percentage Removal at different Temperature For Adsorption onto HAP
10.Percentage Removal at different Concentration For Adsorption onto HAP
11.Isotherm parameters for Adsorption onto HAP
12.Thermodynamic Parameters for adsorption onto HAP .
13.Percentage Removal at different Adsorbent Dosage For Adsorption onto
Ricehusk
14.Percentage Removal at different pH For Adsorption onto Ricehusk
15.Percentage Removal at different Temperature For Adsorption onto
Ricehusk
16.Percentage Removal at different Concentration For Adsorption onto
Ricehusk
17.Isotherm parameters for Adsorption onto Ricehusk
18.Thermodynamic Parameters for adsorption onto Ricehusk
19.Percentage Removal at different Dosage For Adsorption onto Sawdust.
20.Percentage Removal at different pH For Adsorption onto Sawdust.
21.Percentage Removal at different Temperature For Adsorption onto Sawdust.
22.Percentage Removal at different Concentration For Adsorption onto
Sawdust.
23.Percentage Removal at different Adsorbent size For Adsorption onto
Sawdust.
1.0 INTRODUCTION
Water used in domestic and industrial applications become polluted to a greater or lesser
extent. Water is also used as a transport medium to carry away waste products. As awareness of
the importance of improved standards of water treatment grows, process requirements become
increasingly exacting. The food industry contributes to a great extent to pollution, particularly as
the pollutants are of organic origin. Organic pollutants normally consist of 1/3 dissolved, 1/3
colloidal and 1/3 suspended substances, while inorganic materials are usually present mainly in
solution[1].
Large amounts of water are used during production process producing effluents containing
dissolved sugars and proteins, fats, and possibly residues of additives. Wastewater from dairies
and cheese industries contain mainly organic and biodegradable materials that can disrupt
aquatic and terrestrial ecosystems. Due to the high pollution load of dairy wastewater, the milkprocessing industries discharging untreated/partially treated wastewater cause serious
environmental problems. Moreover, the Indian government has imposed very strict rules and
regulations for the effluent discharge to protect the environment.
Dairy effluent contains soluble organics, suspended solids, trace organics. All these
components contribute largely towards their high biological oxygen demand (BOD) and
chemical oxygen demand (COD). Dairy wastes are white in colour and usually slightly alkaline
in nature and become acidic quite rapidly due to the fermentation of milk sugar to lactic acid.
The suspended matter content of milk waste is considerable mainly due to fine curd found in
cheese waste. The pollution effect of dairy waste is attributed to the immediate and high oxygen
demand. Decomposition of casein leading to the formation of heavy black sludges and strong
butyric acid odors and characterize milk waste pollution( Shete et al.,).
Coagulation is an essential process in water and industrial wastewater treatment.
Coagulation has been subject of many research, most of which has been related to wastewater
treatment, however, it may differ from depending on chemical and physical parameters of
contaminants. The particles to be removed include organic material, which can react differently
to a coagulant[Sahu et al., (2013)]. Coagulation/flocculation is a commonly used process in
water and wastewater treatment in which compounds such as lime, alum, ferric chloride and
ferrous sulfate [Parmar et al.,(2011)] are added to wastewater in order to destabilize the
colloidal materials and cause the small particles to agglomerate into larger settleable flocs
[Jopson and Hector(2004)].
Aluminum sulfate (alum), ferrous sulfate, ferric chloride and ferric chloro-sulfate were
commonly used as coagulants [Affrin et al.,]. Additionally, high COD removal capacities have
been observed during the combined action of alum and lime for the treatment of stabilized
leachates. The coagulation process with alum as the sole coagulant is capable of achieving
significant organic removal. The pH of the water during coagulation has profound influences on
effectiveness of coagulation for organic removal. Organic removal is much better in slightly
acidic condition. The optimum pH for alum coagulation is influenced by the concentration of
organic matter in the water.
Adsorption is typically used in wastewater treatment to remove toxic or recalcitrant organic

pollutants (especially halogenated but also non-halogenated), and to a lesser extent, inorganic
contaminants, from the wastewater. Adsorption finds applications in tertiary wastewater
treatment as a polishing step before final discharge. Adsorption is commonly used in the
treatment of industrial wastewaters containing organic compounds not easily biodegraded during
secondary (biological) treatment or toxic.
Many industrial wastewaters contain substances that:
are difficult to remove via conventionally secondary treatment

are toxic or hazardous
are volatile and cannot be transferred to the atmosphere.
have the potential for creating noxious vapors or odors, or for imparting color to the
wastewater.
are present is very small concentrations that make their removal via other methods
difficult.
There are various methods including chemical precipitation, membrane process, ion
exchange, liquid extraction and electrodialysis (Verma et al., 2006).. These methods are noneconomical and have many disadvantages such as incomplete metal removal, high reagent and
energy requirements, generation of toxic sludge or other waste products that require disposal or
treatment.
Biosorption, a technically feasible and economical process, has gained increased credibility
during recent years (Loukidou et al., 2004)..Plant wastes are inexpensive as they have no or very
low economic value and it is abundant in nature. Some of the advantages of using plant wastes
for wastewater treatment include simple technique, requires little processing, good adsorption
capacity, selective adsorption of heavy metal ions, low cost, free availability and easy
regeneration. The commonly used biosorbents in this study are: Rice husk, Saw dust.
However, the application of untreated plant wastes as adsorbents can also bring several
problems such as low adsorption capacity, high chemical oxygen demand (COD) and biological
chemical demand (BOD) as well as total organic carbon (TOC) due to release of soluble organic
compounds contained in the plant materials. The increase of the COD, BOD and TOC can cause
depletion of oxygen content in water and can threaten the aquatic life.
Carbon nanostructures have been extensively studied due to their excellent properties and
numerous applications [Geim and Novoselov (2007) and Saxena et al.,]. Graphene Oxide is a
single-atomic-layered material made by the oxidation of graphite crystals, which are inexpensive
and abundant. It is dispersible in water, and as a result is easy to process. Most importantly, it
can be converted into graphene. Graphene Oxide is one of the first commercial graphene
materials and one of the most popular products in the Graphene Supermarket.
Hydroxyapatite [Ca10(PO4)6(OH)2, HAP], a main inorganic constituent of the hard tissues
(bone and teeth) in human body, has marked potential in adsorption of various ions, organic
molecules and polymers (Jang et al.,(2008). HAP is also capable of establishing bonds with
organic molecules of different size. However, HAP is usually provided in powder or calcined
pellets form, which limits its industrial applications.
2.0 LITERATURE REVIEW

Wastewater from dairies and cheese industries contain mainly organic and biodegradable
materials that can disrupt aquatic and terrestrial ecosystems. Due to the high pollution load of
dairy wastewater, the milk-processing industries discharging untreated/partially treated
wastewater cause serious environmental problems. Hence the importance of carrying out a whey
treatment as a starting point in order to optimize a simple and economic method to treat the
whole dairy effluent. Moreover, the Indian government has imposed very strict rules and
regulations for the effluent discharge to protect the environment.
Industrial waste water emanates from spillage of milk and products thereof, and from cleaning of
equipment that has been in contact with milk products. The concentration and composition of the
waste depends on the production programme, operating methods and the design of the processing
plant.
2.1 Organic pollutants

2.1.1 Biological oxygen demand (BOD)
Oxygen demand is measured in terms of the quantity of oxygen consumed by micro-organisms
over a period of five days (BOD5) or seven days (BOD7 ), in decomposing the organic pollutants
in waste water at a temperature of 20C. BOD is measured in mg oxygen/l or g oxygen/m3.
2.1.2 Chemical oxygen demand (COD)

COD indicates the quantity of the pollutants in waste water that can be
oxidised by a chemical oxidant. The normal reagents used for this purpose are strongly acid
solutions (to ensure complete oxidation) of potassium dichromate or potassium permanganate at
high temperature. Consumption of oxidant provides a measure of the content of organic
substance and is converted to a corresponding quantity of oxygen, expressing the result as mg
oxygen/l or g oxygen/m3.
The COD/BOD ratio indicates how biologically degradable the effluent is.Low values, i.e. < 2,
indicate relatively easily degradable substances, while high values indicate the contrary.
However, this relationship cannot be used generally, but a typical value of COD/BOD for
municipal sewage effluent is often < 2.
2.1.3 pH
The pH of dairy effluent varies between 2 and 12 as a result of the use of acid and alkaline
detergents for plant cleaning.Both low and high pH values interfere with the activity of the
micro-organisms that break down organic pollutants in the biological treatment stage of the
sewage treatment plant, transforming them into biological sludge (cell detritus).Used detergents
are therefore normally collected in a mixing tank, often located close to the cleaning plant, and
the pH is measured and regulated to, say, pH 7.0 before it is discharged to drain.
2.2 New Technologies in the Dairy Industry Waste Water Treatment
Treatment of Dairy Industry Wastewater by Reverse Osmosis for Water Reuse

Anaerobic Filter Reactor for the Treatment of Complex Dairy Wastewater at Industrial
Scale
Use of Nanofiltration and Reverse Osmosis Membranes in Dairy Wastewater
Treatment
Anaerobic Treatment of Dairy Wastewaters
Electrochemical Technologies in Wastewater Treatment.

2.2.1 Ion Exchange
Ion exchange means the removal of an ion from aqueous solution by replacing another ionic
species. There are natural and synthetic materials available which are specially designed to
enable ion exchange operations at high levels. So ion exchangers are used to perform this ion
exchange for removal of organic and inorganic pollutants along with other heavy metals for
purification and decontamination of industrial effluents. The main disadvantages associated with
ion exchange methods are the high cost of the ion exchange resins and each resins must be
selectively removes one type of contaminant only. Further, complete removal of the contaminant
is not possible. Besides, it can be used for limited cycles only as by passing concentrated metal
solution the matrix gets easily owned out by organics and other solids in the wastewater after
several uses. Moreover ion exchange is also highly sensitive to pH of the solution [Liotta et al.,
2009 and Sapari et al., (1996)].
2.2.2 Chemical Oxidation
In this process the waste materials from the industrial waste water are removed by the help of
chemical oxidation by the use of various chemicals mainly hydrogen peroxide is widely used for
this purpose as reported [Dias-Machado et al., 2006 and Ksibi, (2006)]. There are many
disadvantages associated with this process like the high cost of the chemicals, emission of
various harmful by products, it creates hazardous constituent like secondary effluent problem
along with the production of harmful gases.
2.2.3.Membrane Filtration
Membrane filtration technique has received a significant attention for the waste water treatment.
It considers the application of hydraulic pressure to bring about the desired separation through
the semi permeable membrane [Chen et al., (2004)]. Important examples of membrane process
applicable to inorganic wastewater treatment include Ultra-filtration, Nanofiltration,
electrodialysis and Reverse osmosis reported by [Chauhan and Rekha, 2004 and Al-Rekabi et al.,
(2007)]. This process involve ionic concentration by the use of selective membrane with a
specific driving force. For reverse osmosis, pressure difference is employed to initiate the
transport of solvent across a semi-permeable membrane and electrodialysis relies on ion

migration through selective permeable membranes in response to a current applied to electrodes.
The main problem associated with this process is incomplete removal of contaminants, high
energy requirement, and high cost of the membrane and longevity of the membrane. After long
term use the membrane get clogged with the contaminants present in the waste water and is
damaged due to extra pressure on the membrane.
2.2.4 Ozonization
Chemical oxidation with ozone can be used to treat organic pollutants or act as disinfectants
agents. Ozone is a powerful oxidants that can oxidize a great number of organic and inorganic
materials Ozone based technologies research is also being focused on the catalytic ozonation
where the presence of catalyst significantly improved the oxidation rate of organic compounds
compared to non-catalytic ozonations. The ozonation processes are possibly one of the most
effective methods for the treatment of wastewater containing organic products effluents from
chemical and agrochemical industries, textile industry, paints, etc. [Guendy,(2007)]. The
disadvantages associated with the process are high operating cost. The cost of the equipment is
very high and also it requires high voltage and electricity for its operation [Gharbani et al.,
(2010)].
2.2.5 Biodegradation
Biodegradation is the process of decaying or reduction of different organic materials and toxic
metals to their non-toxic form with the help of microorganisms. In this process complete
mineralization of the starting compound to simpler ones like CO2, H2O, NO3 and other inorganic
compounds takes place[Atlas and Bartha, (1998)]. It is an eco-friendly and cost effective process
that requires low capital and operating cost. Being environmentally friendly process it produces
no harmful end products. The main disadvantage of this process is that it requires high
maintenance of various parameters like temperature, pH, source of carbon and other
microelements etc.
2.2.5 Solvent Extractions
Liquid-liquid extraction of heavy metals from solutions on a large scale is widely practiced. It
involves an organic and an aqueous phase. The aqueous solution containing the metal or metals
of interest is mixed with the appropriate organic solvent and the metal passes into organic phase.
In order to recover the extracted metal, the organic solvent is contacted with aqueous solution
whose composition is such that the metal is stripped from the organic phase and re-extracted into
stripping solution. Once the metal of interest has been removed, the organic solvent is recycled
either directly or after a fraction of it has been treated to remove the impurities .The disadvantage
associated with this process is high maintenance cost.
2.3 Chemical Precipitation (Coagulation and Flocculation)

Precipitation of metals is achieved by addition of coagulations such as alums, lime, iron
salts and other organic polymers.
In wastewater treatment, coagulation/flocculation processes are mainly used for the
removal of colloidal material, which cause color and turbidity by bringing suspended
matter together for the purpose of settling and for the preparation of the water for
filtration. Coagulation involves three specific steps which are Coagulation, Flocculation,
and Sedimentation. Coagulation can be a simple and in expensive way to improve the
quality of wastewater. Coagulation can improve the quality of water. This improves taste
and odor, makes the water safer for chlorination, and makes the water easier to treat for
domestic purposes.
Coagulation and flocculation processes are intended to form particles large enough to be
separated and removed by subsequent sedimentation, or alternative clarification
processes. The coagulation stage occurs when a coagulant, such as alum, is added to the
water to neutralize the charges on the colloidal particles in the raw water, thus bringing
the particles closer together to allow a floc to begin to form. The flocculation process,
following coagulations, allows smaller particles formed during the rapid coagulations
stage to agglomerate into larger particles to form flocculation aids, including alum
[Al2(SO4)3.18H2O], ferric chloride[FeCl3.6H2O], ferric sulphate[Fe2(SO4)2], ferrous
sulphate[FeSO4. 7H2O] and lime [Ca(OH)2]. These coagulants when used in
combinations gives better result in wastewater treatment, such as Lime +Alum, Lime +
Ferric Chloride + Alum, lime + Ferrous Sulphate, Lime + Ferrous Sulphate+ Ferric
Chloride etc.
The theoretical reaction when coagulants added to water are:
Al2SO4.14.3H2O+3Ca(HCO3)2=2Al(OH)4+3CaCO4+14.3H2O+6CO2
Ca(OH)2 + H2CO3= CaCO3 + 2 H2O
Ca(OH)2 + Ca(HCO3)2= 2 CaCO3 + 2 H2O
FeSO4 +2 HCO3- = Fe (OH) 2 +SO4 -2 +2CO2
2.4 ADSORPTION
2.4.1 Fundamentals of the adsorption
Adsorption is a process in which a substance (adsorbate), in gas or liquid phase, accumulates on
a solid surface. It is based on the capability of porous materials with large surfaces to selectively
retain compounds on the surface of the solid (adsorbent). There are two types of adsorption;
physical and chemical adsorptions.
2.4.2 Physical Adsorption
Physical adsorption is achieved by Van der Waals forces, dipole interactions, and hydrogen
binding. There is no electron exchange between adsorbent and adsorbate. Because there is no
activation energy required for physical adsorption, the time needed to reach equilibrium is very
short. Physical adsorption is a nonspecific and a reversible process.
2.4.3 Chemical Adsorption
Chemical adsorption results from the chemical link between adsorbent and adsorbate molecule,
therefore it is specific as well as irreversible and chemical as well as electronic properties of
adsorbent are changed. Binding between adsorbent and adsorbate by covalent bond is called
weak chemical adsorption, and that by ionic bonds is called strong chemical adsorption.
2.4.4 Adsorption Mechanisms
The adsorption process of the adsorbate molecules from the bulk liquid phase into the adsorbent
surface is presumed to involve the following stages :
Mass transfer of the adsorbate molecules across the external boundary layer towards the
solid particle.
Adsorbate molecules transport from the particle surface into the active sites by diffusion
within the porefilled liquid and migrate along the solid surface of the pore.
Solute molecules adsorbtion on the active sites on the interior surfaces of the pores.
Once the molecule adsorbed, it may migrate on the pore surface trough surface diffusion.
2.5 ADSORBENTS
2.5.1 SAWDUST
Sawdust is a waste by-product of the timber industry that is either used as cooking fuel or a
packing material; however, it can be used as a low-cost adsorbent of heavy metals, principally
due to its lignocellulosic composition. It is mainly composed of cellulose (4550%) and lignin
(2330%).
2.5.2 RICEHUSK
Rice husk, which is a relatively abundant and inexpensive material, is currently being investigated as an
adsorbent for the removal of various pollutants from water and wastewaters. Various pollutants, such as
dyes, phenols, organic compounds, pesticides, inorganic anions, and heavy metals can be removed very
effectively with rice husk as an adsorbent. Rice husk contains 75-90 % organic matter such as
cellulose, lignin etc. and rest mineral components such as silica, alkalis and trace elements
(Madhumita et al.,).
2.5.3 GRAPHENE OXIDE

GO has two important characteristics:(a) it can be produced using inexpensive graphite as
raw material by cost-effective chemical methods with a high yield, and (b) it is highly
hydrophilic and can form stableaqueous colloids to facilitate the assembly of macroscopic
structures by simple and cheap solution processes, both of which are important to the large-scale
uses of graphene. Graphite oxide has a similar layered structure to graphite, but the plane of
carbon atoms in graphite oxide is heavily decorated by oxygen-containing groups, which not
only expand the interlayer distance but also make the atomic-thick layers hydrophilic. As a
result, these oxidized layers can be exfoliated in water [ Shahriary and Anjali(2014)].
2.5.4 HAP NANO-COMPOSITES

Calcium hydroxyapatite (HAP), Ca10(PO4)6(OH)2, is an important inorganic material in biology
and chemistry (Elliott, 1994; LeGeros, 1991; Arends et al., 1987). Their availability structure,
ionic exchange property, adsorption affinity, and their characteristic to establish bonds with
organic molecules of different sizes have conferred to this material to attract more attention
during the last two decades. Calcium phosphates, especially apatites, are widely used for
chromatographic purposes (Kawazaki, 1991; Gorbuno_, 1984) and are suitable for a number of
biomedical applications, e.g., artificial bone and roofs of teeth, as well as a carrier for drug
delivery (Barroug and Glimcher, 2002; Cannon and Bajpai, 1995; Aoki, 1994). In addition, this
material can be a matrixes efficient of water purification.
2.6 ADSORPTION ISOTHERMS

Adsorption isotherms ,which are the presentations of the amount of the solute adsorbed per unit
of the adsorbent as a function of equilibrium concentration in bulk solution at constant
temperature .If a quantity q of adsorbate is adsorbed by a porous solid adsorbent at constant
temperature and the steady state equilibrium concentration , then the function q describes the
adsorption isotherm. The isotherm rises in the initial stages with higher slope at low Ce and qe
values.This indicates that initially there are numerous readily accessible sites.This confirms the
monolayer coverage of adsorbate onto adsorbent particles.A variety of isotherm equations have
been in use some of which have a theoretical foundation and some being of more empirical
nature.
2.6.1 Langmuir Isotherm

A basic assumption of the Langmuir theory is that the sorption takes place at specific
homogenous sites within the adsorbent . It is then assumed that once a ion or molecules occupies
a site no further sorption can take place at that site. The rate of sorption to the surface should be
proportional to a driving force multiplied by are. The driving force is the concentration in the
solution and the area is the amount of bare surface.
Ce/qe = 1/ KL Qo + Ce/ Qo
Where Ce is the equilibrium concentration , qe is the amount of ions or molecules adsorbed
(mg/g) ,Qo is qe for a complete monolayer ( mg/g) ,KL is sorption equilibrium constant . A plot of
Ce/qe versus Ce should indicate a straight line of slope 1/ Qo and an intercept of 1/ KL Qo.
2.6.2 Freundlich Isotherm

Freundlich Isotherm assumes that the uptake of ions occur on a heterogenous surface by
multilayer adsorption and that the amount of adsorbate adsorbed increases infinitely with an
increase in concentration . It is the most popular model for a single solute system, based on the
distribution of solute between the solid phase and aqueous phase at equilibrium.
Linear Equation of Freundlich Isotherm is
Log qe = log Kf + (1/n) log Ce
Where Ce is the equilibrium concentration , qe is the amount of ions or molecules adsorbed
(mg/g), Kf and n are Freundlich constants related to the adsorption capacity and adsorption
intensity ,respectively. A plot of Log qe versus log Ce gives a linear trace with a slope of 1/n and
intercept of log Kf . When 1/n > 0 , the change is adsorbed on concentration is greater than the
change in ion concentration in solution. It is often found that the Freundlich equation is fitted
well to the data at higher and intermediate concentrations , since the Freundlich equation does
not approach Henry s Law of ideal dilute solutions.
2.7 Adsorption Kinetics

Several Kinetic models are in use to explain the mechanism of the adsorption processes. A
simple pseudo second order equation was used.
t/qt = 1/K2qe2 + t/qe

qt and qe are the amount of adsorption at equilibrium and at time t respectively and K2 is
the rate constant of the pseudo second order adsorption process.
where
The rate parameters K2 and qe can be directly obtained from the intercept and slope of the plot of
t/qt versus t.The values of rate constant are obtained graphically for both adsorption models.
2.8 Adsorption Thermodynamics

The thermodynamics of an adsorption process is obtained from a study of the influence of
temperature on the process. The standard Gibbs Energy was
G = RT ln Kc
The equilibrium constants Kc was evaluated at each temperature using the following relationship
Kc = Ca/Ce
Kc = distribution coefficient for adsorption.
Ca = equilibrium concentration on the adsorbent.
Ce = equilibrium concentration in solution.
Other thermodynamic parameters such as change in standard enthalpy H and standard entropy
S were determined using the following equations.
G = H TS
G = Gibbs free energy change
H = enthalpy of reaction.
H and S were obtained from the slope and intercept of the Vant Hoff s plot of ln k eq
versus 1/T , Negative value of H indicates that the adsorption process is exothermic.The
negative values of G reflect the feasibility of the process and the values become more negative
with increase in temperature. Standard entropy determines the disorderliness of the adsorption at
solid-liquid interface. The positive value if S shows that increasing randomness at the solidliquid interface during the adsorption process.
3.0 MATERIALS AND METHODS

Wastewater sample was collected from outfall of a dairy industry at Dankuni near Durgapur
express Highway. Wastewater sample collected from the plant was placed in plastic containers to
be transported to the laboratory and stored at 4C in a refrigerator. pH, oil and grease, COD,
BOD, Chlorides, Alkalinity were analysed in the laboratory according to the methods given in
the Standard Methods. Closed reflux colorimetric method was used for COD analysis and was
analysed as dictated by Standard Methods [APHA (2005)]. All the chemicals were of analytical
reagent grades and used as received, without further purifications.
3.1 Coagulation- Coagulants and Procedure

Coagulants included lime, alum, ferric chloride and ferrous sulfate were all supplied by Merck
India. Coagulation-flocculation and precipitation studies were performed in a conventional jartest apparatus [Ayeche (2012)], equipped with
beakers of 500 mL volume. Before
coagulation/flocculation process, wastewater sample was thoroughly shaken to avoid possibility
of settling solids. The experimental process consisted of the initial rapid mixing stage that took
place for 5 min at 150 rpm, the following slow mixing stage for 30 min at 30 rpm and the final
settling step for 1 h. After 1 hour settling period, samples were withdrawn from supernatant for
analyses. Process performance was monitored by using COD values[Murali et al., (2013)].
3.1.1 Preparation of Coagulant Solution

Coagulants used for the removal of colour, COD, etc. in the experiment were Lime, Alum, Ferric
Chloride and Ferrous Sulphate. These coagulants were used in combination to enhance of COD.
The combination of the coagulants used was:
i.
ii.
iii.
iv.
v.
Lime (10%) + Alum (10%)

Lime (10%) + Ferric Chloride (10%)
Lime (10%) +Ferrous Sulfate (10%)
Lime (10%) + Ferric Chloride (10%) + Alum (10%)
Lime (10%) + Ferrous Sulfate (10%)+ Ferric Chloride (10%)
Coagulation process Followed by Adsorption

The different combination of coagulants was added to the dairy wastewater according to the
procedure mentioned below:
i.
Lime (10%) + Alum (10%)

100 ml of dairy wastewater was taken in 500 ml conical flask and the pH was
measured.
Lime (10%) solution (about 5 ml) was added to the sample to adjust the pH to
8.3.
Alum (10%) solution (about 5 ml) was added to adjust pH 7.83.
ii.
Then the flask was kept in rotary shaker at a high agitation of 150 rpm for 5
minutes and then at low agitation of 30 rpm for 30 minutes.
After that, it is allowed to settle down and the rate of settling was observed
with time.
The supernatant was collected and the parameters like COD, pH were
analysed.
The sludge volume was also measured.
Lime (10%) + Ferric Chloride (10%) + Alum (10%)
iii.
100 ml of dairy wastewater was taken in 500 ml conical flask and the pH
was measured.
Lime (10%) solution (about 5ml) was added to the sample to adjust the pH
to 8.3.
Ferric Chloride (10%) solution (about 5 ml) was added to adjust pH 7.43.
No precipitate or settling was observed, then Alum (10%) solution (5 ml)
was added until precipitate was formed.
Then the flask was kept in rotary shaker at a high agitation of 150 rpm for
5 minutes and then at low agitation of 30 rpm for 30 minutes.
with time.
analysed.
Lime (10%) + Ferrous Sulfate (10%)
was measured.
Lime (10%) solution (about 5 ml) was added to the sample to adjust the pH
above 8.3.
Ferrous Sulfate (10%) solution (5 ml) was added to adjust pH 7.31.
with time.
analysed.
iv.
Lime (10%) + Ferrous Sulfate (10%) + Ferric Chloride (10%)
was measured.
Lime (10%) solution (about 5 ml) was added to the sample to adjust the pH
to 8.3.
Ferric Chloride (10%) solution (5 ml), Ferrous Sulfate(10%) solution (5
ml), was added to bring the pH to 7.21.
Due to the addition of ferric chloride, ferrous sulfate and sulfuric acid pH
comes nearly to 5. So lime (10%) was added to adjust the pH to 7.
with time.
analysed.
After the coagulation process, the supernatant of each flask was collected and sawdust was
added to the supernatant and kept in rotary shaker for 2 hrs. for adsorption process. After 2
hours, samples were taken COD were analysed using respective instruments and procedure.
3.1.2 COD Estimation
For the estimation of COD standard procedure was followed 2.5 ml of the collected samples was
poured to the COD vials along with 1.5 ml digestion mixture and 3.5 acid mixture. Then it is
kept in COD digestor for 2 hours at 148C. After 2 hour, the COD was calculated as
( a b ) N x 8000
COD mg/l = --------------------------------ml sample
where,
a = ml Fe(NH4)2(SO4)2 used for blank
b = ml of Fe(NH4)2(SO4)2 used for sample
N = normality of Fe(NH4)2(SO4)2
3.2 Adsorbent preparation

Sawdust and Ricehusk were used for the adsorption process. Sal Sawdust was collected from a
nearby sawmill and ricehusk was collected from a local agro industry.All the adsorbents were
washed several times with hot distilled water and dried at room temperature for several days.
They were sieved using meshes to get the desired adsorbent size of <30 and stored in a air tight
container.
Graphene Oxide was synthesized by the modified hummers method[Hummers (1958)]. The
synthesis was performed by exfoliating graphite powder in the presence of potassium
permanganate (KMnO4) and concentrated sulphuric acid (H2SO4). Graphite powder (2.0 gm )
was taken and placed in a conical flask, now 50 ml of concentrated sulfuric acid was slowly
added and cool it in ice bucket and, 6.0 gm of potassium permanganate (KMnO4 ) was slowly
added over 20 min with continuous stirring in ice bucket. The mixture was stirred at 40C for
more than 2 hrs and the resulting solution was diluted by adding 100 ml of water under vigorous
stirring. To ensure the completion of reaction with KMnO4, the suspension was further treated
with 35% H2O2 solution. The resulting mixture was washed with HCl and H2O respectively,
followed by filtration and drying.
HAP Nanoparticles - In a typical synthesis,10.9 gm (1.11 M) orthophosphoric acid (H3PO4) was
dropwise added into 11.1gm (1.5 M) calcium hydroxide Ca(OH)2solution under strong magnetic
stirring at 70C for 3 h. The mixture was stirred until a clear and homogeneous solution formed,
and 2 mol of NaOH was added dropwise to this solution until pH value maintained to be 10. The
white precipitate HAP gel was precipitated after aging for 4 h. The obtained HAP solid products
were separated, washed repeatedly with de-ionized water, and dried under ambient atmosphere.
The yield of HAP nanoparticles was up to almost 100%. The solid products were then heated in
an electric furnace at 700C for 1 h in air, and final products were obtained.
3.3 Batch sorption experiments

The sorption studies were carried out at 30C. Solution pH was adjusted with HCl or NaOH
(0.1N). A known amount of adsorbent was added to samples and was agitated at 150 rpm
agitation speed, allowing sufficient time for adsorption. Then, the mixtures were filtered through
filter paper and membrane and the final concentration were determined in the filtrate using UVvis spectrophotometer The effects of various parameters on the percentage removal were
observed by varying contact time, adsorbent dosage, and initial pH of solution.
The amount of organic pollutant adsorbed (mg pollutant per g adsorbent) was calculated
according to a mass balance on the pollutant concentration using:
qe =(CO Ce)V/m
The percent removal (%) of dye was calculated using the following equation:
Removal (%)=[(Co Ce)/Co]*100
CO = Initial Pollutant Concentration
Ce = Equilibrium Pollutant Concentration
m = mass of adsorbent
4.0 RESULTS AND DISCUSSIONS

4.1 Characterisation of Dairy Wastewater
The Dairy wastewater collected from the input of an effluent treatment section has the following
characteristics :Table 1 : Characteristics of Dairy Wastewater
Initial parameters of waste water
COD
BOD
OIL AND GREASE
CHLORIDES
ALKALINITY
PH
TSS
TDS
Conductivity
468 mg/l.
210 mg/l.
240 mg/l.
136 mg/l. (less than 250 ppm).
462.5 mg/l CaCo3 equivalent
7.34-7.38
942 mg/l
680 mg/l
1200 mS/cm
4.2 Results obtained after Treatment of Wastewater with Coagulants

Effects of different coagulants on COD removal, pH, sludge produced were studied and the
results observed below. Maximum removal of 92 % was obtained using Lime and Ferrous
Sulfate combination. But the main problem behind using Iron based Coagulants was the amount
of sludge produced. So Lime and Alum was more preferable.
Coagulant
COD
Percentage
removal (COD)
pH
Sludge
produced
(mg/100ml)
Lime + Alum
Lime +Ferric Chloride
Lime+Ferrous Sulfate
72
80
26
236
84%
82.9%
92%
7.83
7.12
7.31
616.23
779.67
747.77
50%
7.21
578.47
12%
7.43
746
Lime+Ferrous Sulfate+ Ferric

Chloride
Lime + Alum+ Ferric Chloride 411.86
Table 2 : Effect of Different Coagulant Treatment on Different Parameters
Figure1: Effect of Coagulants on

Percentage Removal.
Figure2: Effect of Coagulants on

Sludge Produced.
4.3 Results obtained after Treatment of Wastewater with Coagulation

followed by Adsorption.
The supernatant obtained after Coagulation were subjected to equal amount of dosage of the
adsorbent for equal interval of time and rotation in the shaker. The results showed that
coagulation followed by adsorption could not be adopted in case of Dairy Wastewater since it
resulted in massive increase of COD of wastewater as compared to the removal using only
coagulation technique. This may be due to the due to release of soluble organic compounds
contained in the adsorbents which added up to the proteins and Casein which was already present
in the wastewater.
Table 3 : Effect of Coagulation Followed By Adsorption

After coagulation
COD value
mg/l
Lime +alum
Lime
+ferric
chloride
Lime + ferrous
sulfate
Lime + ferric
chloride+
ferrous sulfate
72
80
After coagulation +
adsorption
with
SAWDUST
COD value mg/l
392
444
After coagulation
+ adsorption with
RICEHUSK
COD value mg/l
140
440
After coagulation
+ adsorption with
GRAPHENE OXIDE
COD value mg/l
180
432
36
420
360
220
236
252
380
Not done
4.4 Rate of Settling

The rate of Settling was observed for different coagulants on treatment of the wastewater .It was
observed
18
Lime+FeCl3
Height
16
14
Lime+alum
12
Lime+FeSO4
Figure3: Rate of Settling of

Different Coagulants
10
8
6
4
2
0
0
20
40
60 Time 80
100
120
140
Figure 4: Rate of Settling of

Different Coagulants
4.5 Batch Adsorption study using Graphene Oxide as Adsorbent

4.5.1 Effect of Adsorbent Dosage :. At this stage, the experiments were done under the
conditions of constant temperature (30 C), agitation speed (150 rpm), constant pH of 2 and
variable adsorbent dose (0.5, 1, 1.5 , 2 , 2.5 g/L). The effect of adsorbent dose on the adsorption
in Fig.(5). are explained. It was observed that the percentage removal increased with an increase
in adsorbent dose. The correlation between adsorbent dose and percentage removal can be
related to an increase in the adsorbent surface area and availability of more adsorption sites.
Adsorbent Dosage in g/L
0.5
1
1.5
2
2.5
Percentage Removal ( % )
94.14
94.63
95.36
96.34
96.5
Table 4: Percentage Removal at

different Adsorbent Dosage For
Adsorption onto Graphene Oxide
Figure 5: Effect of Dosage on

Percentage Removal using
Graphene Oxide.
4.5.2 Effect of pH
The pH of the aqueous solution is clearly an important parameter that controlled the adsorption
process. The experiments of this stage were done under the conditions described above with
adsorbent dose (1.1 g/L). The experimental results of this stage are presented in Fig (6). At lower
pH there was a increase in percentage removal with time. But at pH 10 after a certain time there
was a drastic reduction in percentage removal.This suggests that the adsorption process was
favoured at lower pH.
pH
2
4
6
10
Percentage Removal ( % )
97.578
97.31
96.34
96.09

different pH For Adsorption onto
Graphene Oxide
Figure 6: Effect of pH on
Graphene Oxide.

Figure (7) displays the effect of temperature on the adsorption process keeping other parameters
same as before. As seen from the figure, the percentage removal decreased with increasing
temperature. At a temperature of 20C the percentage removal was maximum of about
98%.Thus it concluded that the process was favoured by a lower temperature. Since the sorption
capacity of the adsorbent was greater at lower temperature, it can also be said that the sorption
might be an exothermic process. The binding capacity decreases with increasing temperature
which may be due to weakening of the bonds between the molecules and the binding sites of the
adsorbent.
Temperature ( K) Percentage Removal ( % )

293
298
308
313
98.04
96.09
95.36
93.9
Table 6:Percentage Removal at

different Temperature For
Adsorption onto Graphene Oxide
Figure 7: Effect of Temperature

on Percentage Removal using
Graphene Oxide.
4.6 Batch Adsorption Study Using HAP Nano-Composites As Adsorbent

4.6.1 Effect Adsorbent Dosage : Result on the effect of adsorbent dose at temperature of
30C, Ph 7.38 and agitation 172 rpm is presented in table. The percentage removal increased
with an increase in adsorbent dose. The removal efficiency increases with increase in adsorbent
dose, as contact surface of adsorbent particles and the availability of more binding sites increase
for adsorption.
Adsorbent Dosage (g/L)
4
6
8
10
12
PERCENTAGE REMOVAL (%)

91.67
92.09
92.57
93.38
93.4

different Dosage For Adsorption onto
HAP

Hydroxyapatite Particles.
4.6.2 Effect of pH : Result on the effect of pH at temperature of 30C, adsorbent dosage of

11 gm/l and agitation 172 rpm is presented. The removal was favoured at a lower pH and there
is a sharp decrease in the removal capacity with the increase of pH.. At higher pH, the adsorbent
surface carries a net negative charge while at lower pH a net positive charge.The Casein has a
negative charge resulting in electrostatic repulsion between the molecules and the binding sites
in alkali medium.This might be due to the weakening of electrostatic force of attraction between
the oppositely charged adsorbate and adsorbent that ultimately lead to the reduction in removal.
pH
2
4
6
8
10

93.54
93.14
92.02
91.38
91.22
Table 8: Percentage Removal at different

pH For Adsorption onto HAP
4.6.3 Effect of Temperature: Figure(10) below displays the effect of temperature on the
adsorption process keeping other parameters same as before. Thus it concluded that the process
was favoured by a lower temperature and the sorption might be an exothermic process. The
binding capacity decreases with increasing temperature which may be due to weakening of the
bonds between the molecules and the binding sites of the adsorbent.
TEMPERATURE (K)
293
298
308
313

99.84
96.44
90.65
88

Adsorption onto HAP


The concentration of the wastewater was varied by the method of percent dilution keeping the
other parameters same as above. It was observed that on increasing the dilution or reducing the
concentration the percentage removal increased. It is evident from this figure that,removal
efficiency decreases with the increase in initial Concentration. In case of lower concentrations,
the ratio of the initial number of moles of ions to the available surface area of adsorbent is large
and subsequently the fractional adsorption becomes independent of initial concentration.

However, at higher concentrations, the available sites of adsorption become fewer, and hence the
percentage removal of decreases.
Concentration (mg/L)
231.8
219.6
207.4
195.4
183

90.8
92.49
93.04
93.27
93.03
Table 10: Percentage Removal

at different Concentration For
Adsorption onto HAP
Figure 11: Effect of

Concentration on Percentage
Removal using Hydroxyapatite
Particles.
4.6.5 Adsorption Isotherms : Data for Langmuir, Freundlich were plotted for adsorption of
molecules into the nano-adsorbent.It was observed that Langmuir isotherm was found
suitable.The plots are shown below.
Table 11 :Isotherm parameters for Adsorption onto HAP
Langmuir
Ce
Ce /qe
25.97
1.388
21.27
1.179
19.7
1.154
Ce/qe=1/Qob + 1/Qo Ce
Slope = 0.039
Q0=KL/aL= 25.6410
1/Qo = 0.039
Qo= 25.6410
Intercept = 0.370
1/KLQo = 0.370
KL= 0.1054
1/Qob=0.370, b=0.1054
RL =0.0866, 0< RL<1 which is favourable.
Freundlich
Log Ce
Log qe
3.256
2.929
3.057
2.892
2.98
2.836
ln qe = ln Kf+ 1/n ln Ce
1/n =0.306
n= 3.2679
lnKf= 1.935
Kf= 6.9240 which is normal.
Figure 12: Langmuir Isotherm

Plot for adsorption onto HAP
Figure 13: Freundlich Isotherm

Plot for adsorption onto HAP

The thermodynamic parameters such as Gibbs energy (G),enthalpy (H) and entropy changes
(S) for the adsorption process can be determined using Vant Hoff equation. The enthalpy
change is determined graphically by plotting ln(keq) versus 1/T which gives a straight line and the
values of G and S computed numerically. Gibbs energy values are negative and large and
increases with increase of temperature. This indicated that better removal is obtained at lower
temperature.Negative value of H indicate that the process is exothermic.The positive value of
S shows the feasibility of the adsorption and the increased randomness at the sorbent /solution
interface during the adsorption of molecules onto HAP.
Temperature (K)
G (J /mole)
293
- 4.3840
298
-104.305
308
313
H ( J/mole )
-673.2
S (J/mole K )
2.298
Table 12: Thermodynamic

Parameters for adsorption
onto HAP .
-293.969
-390.3423
Figure 14: Vant Hoff Plot for

estimation of thermodynamic
parameters for adsorption onto
HAP

Data for pseudo second order kinetic model for the adsorption of ions onto the nano- adsorbent
surface at temperature 30C , pH 7.38 and agitation 172 rpm and dosage of 11 g/L is presented.
Figure 15: Pseudo Second Order

Kinetic Model for adsorption
onto HAP
4.7 Batch Adsorption study using Ricehusk as Adsorbent

4.7.1 Effect of Adsorbent Dosage: The experiments were done under the conditions of
constant temperature (30 C), agitation speed ( >150 rpm), constant pH of 7.38 and variable
adsorbent dose (4,6,8,10 g/L).The percentage removal was found to be decreasing with increase
in dosage.This increase in COD value may be due to the release of soluble organic compounds
contained in the plant materials.
Adsorbent Dosage ( g/L)
4
6
8
10

89.95
85.6
83.49
83.47

different Adsorbent Dosage For
Adsorption onto Ricehusk

Ricehusk.
4.7.2 Effect of pH : The pH of the solution is an important monitoring parameter in

biosorption studies. It influences not only the surface charge of the biosorbent but also the degree
of ionization of the organic substance present in the solution. Result on the effect of pH at
temperature of 30C, adsorbent dosage of 5 gm/l and agitation( >150 rpm), is presented. The
removal was favoured at a lower pH. At higher pH, the adsorbent surface carries a net negative
charge while at lower pH a net positive charge. The Casein has a negative charge resulting in
electrostatic repulsion between the molecules and the binding sites in alkali medium.
pH
2
4
6
8
10

93.54
91.35
89.16
85.11
74.2

Ricehusk

Ricehusk.
4.7.3 Effect of Temperature: Figure below displays the effect of temperature on the
adsorption process keeping other parameters same as before. The percentage removal decreased
with increasing temperature. Since the sorption capacity of the adsorbent was greater at lower
temperature, it can also be said that the sorption might be an exothermic process. With regard to
the effect of temperature on the adsorption, an increasing uptake of organic molecules is
expected when the adsorption temperature decreases because adsorption is a spontaneous
process. The binding capacity decreases with increasing temperature which may be due to
weakening of the bonds between the molecules and the binding sites of the biosorbent.
TEMPERATURE (K)
293
91.49
298
88.5
308
84.05
313
83.34


Ricehusk.

The concentration of the wastewater was varied by the method of percent dilution keeping the
other parameters same as above. It was observed that on increasing the dilution or reducing the
concentration the percentage removal increased. It is evident from this figure that,removal
efficiency decreases with the increase in initial Concentration. In case of lower concentrations,
the ratio of the initial number of moles of ions to the available surface area of adsorbent is large
and subsequently the fractional adsorption becomes independent of initial concentration.
However,at higher concentrations, the available sites of adsorption become fewer, and hence the
percentage removal of decreases.
Concentration (mg/L)
231.8
219.6
91.023
91.741
207.4
195.4
183
92.458
93.8
94.011

different Concentration For

Removal using Ricehusk.

Data for Langmuir, Freundlich were plotted for adsorption of molecules into the Ricehusk.It was
observed that Langmuir isotherm was found suitable.The plots are shown below
Langmuir
Ce
25.433
23.4
21.367
17.567
16.967
Ce /qe
0.6162
0.5963
0.558
0.4944
0.501
Freundlich
Log Ce
3.2360
3.1527
3.0618
2.8660
2.8312
Log qe
3.7202
3.6696
3.616
3.5702
3.5027
Ce/qe=1/Qob + 1/Qo Ce
Slope = 0.014
Q0=KL/aL= 71.4285
1/Qo = 0.014
Qo= 71.4285
Intercept = 0.241
1/KLQo = 0.241
KL= 0.0580
RL = 0.1470 ,0< RL<1 favourable.
ln qe = ln Kf+ 1/n ln Ce
1/n =0.464
n= 2.155
lnKf= 2.207
Kf= 9.0884
Normal
Table 17 :Isotherm parameters for Adsorption onto Ricehusk
Figure 20: Langmuir Isotherm

Plot for adsorption onto ricehusk
Figure 21: Freundlich Isotherm

Plot for adsorption onto ricehusk

The thermodynamic parameters such as Gibbs energy (G), enthalpy (H) and entropy changes
(S) for the adsorption process can be determined using Vant Hoff equation. The enthalpy
change is determined graphically by plotting ln(keq) versus 1/T which gives a straight line and the
values of G and S computed numerically. Gibbs energy values are negative and large and
decreases with increase of temperature. This indicated that better removal is obtained at lower
temperature. Negative value of H indicate that the process is exothermic.The positive value of
S shows the feasibility of the adsorption and the increased randomness at the sorbent /solution
interface during the adsorption of molecules onto ricehusk.
Figure 22: Vant Hoff Plot for

estimation of thermodynamic
parameters for adsorption onto
Ricehusk
Temperature (K)
G (J /mole)
293
- 253.100
298
-354.7883
308
313
H ( J/mole )
-554.1
S (J/mole K )
1.997
Table 18: Thermodynamic

Parameters for adsorption
onto Ricehusk
-524.177
-585.253

Data for pseudo second order kinetic model for the adsorption of ions onto the Ricehusk surface
at temperature 30C , pH 7.38 and agitation >150 rpm and dosage of 5 g/L is presented.
Figure 23 : Pseudo Second Order

Kinetic Model for adsorption
onto Ricehusk
4.8 Batch Adsorption study using Sawdust as Adsorbent

4.8.1 Effect of Adsorbent Dosage: The experiments were done under the conditions of
constant temperature (30C), agitation speed ( >150 rpm), constant pH of 7.38 and variable
adsorbent dose of (5,10,15 g/L).The percentage removal was found to be decreasing with
increase in dosage.This increase in COD value may be due to the release of soluble organic
compounds contained in the plant materials.
Time (min)
Variation of Dosage in g/L

5
10
15
78.9
66
54.2
57.14
25.71
18.57
54.57
21.74
15.71
12
51.14
15.85
12.85
15
19.7
10.85
8.85

different Dosage For Adsorption
onto Sawdust.

Sawdust.
4.8.2 Effect of pH : Result on the effect of pH at temperature of 30C, adsorbent dosage of 6

gm/l and agitation >150 rpm rpm is presented. The removal was favoured at a lower pH and
there is a sharp decrease in the removal capacity with the increase of pH.. At higher pH, the
adsorbent surface carries a net negative charge while at lower pH a net positive charge.The
Casein has a negative charge resulting in electrostatic repulsion between the molecules and the
binding sites in alkali medium.Thus due to the weakening of electrostatic force of attraction
between the oppositely charged adsorbate and adsorbent that ultimately lead to the reduction in
removal.
Time
(min)
Variation of pH
2
99.14
96.42
78.28
61.14
99.71
94.62
72.85
45.42
99.04
74.6
69.42
32
12
97.14
70.2
64.57
24.57
15
98.28
53.46
47.42
15.71

Sawdust.

Sawdust.
4.8.3 Effect of Temperature: Figure below displays the effect of temperature on the
adsorption process keeping other parameters same as before. Thus it concluded that the process
is exothermic and was favoured by a lower temperature. With regard to the effect of temperature
on the adsorption, an increasing uptake of organic molecules is expected when the adsorption
temperature decreases because adsorption is a spontaneous process.
Time
(min)
Variation of Temperature (K)

293
298
308
313
74.28
68.28
63.34
60.25
56.85
51.24
46.57
42.67
46.28
43.45
38
36.58
12
44
40.56
37.14
33.14
15
41
28
22.57
20.714

Adsorption onto Sawdust.
Figure 26: Effect of temperature

Sawdust.
4.8.4 Effect of Concentration: The concentration of the wastewater was varied by the
method of percent dilution keeping the other parameters same as above. It was observed that on
increasing the dilution or reducing the concentration the percentage removal increased. It is
evident from this figure that,removal efficiency decreases with the increase in initial
Concentration. In case of lower concentrations, the ratio of the initial number of moles of ions to
the available surface area of adsorbent is large and subsequently the fractional adsorption
becomes independent of initial concentration. However,at higher concentrations, the available
sites of adsorption become fewer, and hence the percentage removal of decreases.
Time
(min)
Variation of Concentration(mg/L)
231.8
219.8
195.2
183
45.41
53.83
57.58
65.58
36.58
40.41
46.08
52.25
17.5
29.34
34.67
41.91
12
10.5
15.75
19.16
33.59
15
4.5
6.25
11
14.6

different Concentration For

Removal using Sawdust.
4.8.5 Effect of Adsorbent Size :

Data for the effect of variation of different adsorbent size keeping other parameters same as
above indicates that with increase in adsorbent size the removal efficiency decreases. These
phenomena might be due to the fact that the smaller particles offer comparatively larger surface
areas and greater numbers of adsorption sites.
Time(min)
Variation of Adsorbent Size (MIC)

<25
25- 60
>60
45.9
38.75
29.16
39.58
18.75
16.67
26.25
16
10.41
12
17.5
11.666
9.16
15
5.83

different adsorbent size For
Figure 28: Effect of adsorbent

size on Percentage Removal
using Sawdust.
4.9 Conclusion
The present study shows that Nano composites especially Hydroxyapatite particle can be
effectively used as a adsorbent for treatment of Dairy Wastewater as it could bring about a
removal upto 96 % as compared to plant based adsorbents since the application of untreated
plant wastes as adsorbents can also bring several problems. With time the percentage removal
decreases which indicates to be a time saving process. Moreover it is a cost effective process
since all the nano composites were prepared from cheaply available raw materials.Casein is the
main component of Dairy Wastewater. Decomposition of casein leading to the formation of
heavy black sludges and strong butyric acid odors and characterize milk waste pollution. It is
relatively hydrophobic, making it poorly soluble in water. The caseins in the micelles are held
together by calcium ions and hydrophobic interactions. Casein has a negative charge in milk.
The purified protein is water insoluble. While it is also insoluble in neutral salt solutions, it is
readily dispersible in dilute alkalis and in salt solutions such as sodium oxalate and sodium
acetate which makes it unavailable for adsorption. The results showed that coagulation followed
by adsorption could not be adopted in case of Dairy Wastewater since it resulted in massive
increase of COD of wastewater as compared to the removal using only coagulation technique.
Only coagulation could bring about a reduction as high as 92 % using ferrous sulfate for efficient
removal of oil and grease. But Iron based coagulants causes sludge problem and inproper
removal of colour of the wastewater. Thus lime and alum was a preferable combination.
The entire process was favoured at lower temperature and lower pH with a little adsorbent
dosage . The solution pH controls the adsorptiveadsorbent and adsorptiveadsorptive
electrostatic interactions, which can have a profound effect on the adsorption process. Thus,
solution pH determines the carbon surface charge and the dissociation or protonation of the
pollutants or ions present. The removal was favoured at a lower pH and there is a sharp decrease
in the removal capacity with the increase of pH. At higher pH, the adsorbent surface carries a net
negative charge while at lower pH a net positive charge.The Casein has a negative charge
resulting in electrostatic repulsion between the molecules and the binding sites in alkali medium.
The organic removal was favoured at lower temperature which concluded that the process is
exothermic and was favoured by a lower temperature. With regard to the effect of temperature on
the adsorption, an increasing uptake of organic molecules is expected when the adsorption
temperature decreases because adsorption is a spontaneous process. Langmuir isotherm and
pseudo second order models fitted most. It can be concluded that the developed methods can be
effectively applied for the COD removal from the effluent. The present finding can be further
exploited for the possible utilization of the selected adsorbents in the industrial sector for large
scale practical applications.
5.0 REFERENCES
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Treatment of Dairy Wastewater implementing

Coagulation and Adsorption.

Treatment of Dairy Wastewater implementing

A Thesis submitted in partial fulfillment of the requirements for the

Under the supervision and guidance of

Sri. Prasanta K. Banerjee

Department of Chemical Engineering

Dr. Siddhartha Datta

Department of Chemical Engineering

Department of Chemical Engineering

HOD (Department of Chemical Engineering)

4.5 Batch Adsorption study using Graphene Oxide as Adsorbent

Characteristics of Dairy Wastewater

Adsorption is typically used in wastewater treatment to remove toxic or recalcitrant organic

are difficult to remove via conventionally secondary treatment

2.0 LITERATURE REVIEW

2.1 Organic pollutants

2.1.2 Chemical oxygen demand (COD)

2.2 New Technologies in the Dairy Industry Waste Water Treatment

Treatment of Dairy Industry Wastewater by Reverse Osmosis for Water Reuse

Electrochemical Technologies in Wastewater Treatment.

transport of solvent across a semi-permeable membrane and electrodialysis relies on ion

2.3 Chemical Precipitation (Coagulation and Flocculation)

2.5.3 GRAPHENE OXIDE

2.5.4 HAP NANO-COMPOSITES

2.6 ADSORPTION ISOTHERMS

2.6.1 Langmuir Isotherm

2.6.2 Freundlich Isotherm

2.7 Adsorption Kinetics

t/qt = 1/K2qe2 + t/qe

2.8 Adsorption Thermodynamics

3.0 MATERIALS AND METHODS

3.1 Coagulation- Coagulants and Procedure

3.1.1 Preparation of Coagulant Solution

Lime (10%) + Alum (10%)

Coagulation process Followed by Adsorption

Lime (10%) + Alum (10%)

Lime (10%) + Ferric Chloride (10%) + Alum (10%)

Lime (10%) + Ferrous Sulfate (10%)

Lime (10%) + Ferrous Sulfate (10%) + Ferric Chloride (10%)

3.2 Adsorbent preparation

3.3 Batch sorption experiments

4.0 RESULTS AND DISCUSSIONS

4.2 Results obtained after Treatment of Wastewater with Coagulants

Lime+Ferrous Sulfate+ Ferric

Table 2 : Effect of Different Coagulant Treatment on Different Parameters

Figure1: Effect of Coagulants on

Figure2: Effect of Coagulants on

4.3 Results obtained after Treatment of Wastewater with Coagulation

Table 3 : Effect of Coagulation Followed By Adsorption

4.4 Rate of Settling

Figure3: Rate of Settling of

Figure 4: Rate of Settling of

4.5 Batch Adsorption study using Graphene Oxide as Adsorbent

Table 4: Percentage Removal at

Figure 5: Effect of Dosage on

Table 5: Percentage Removal at

4.5.3 Effect of Temperature

Temperature ( K) Percentage Removal ( % )

Table 6:Percentage Removal at

Figure 7: Effect of Temperature

4.6 Batch Adsorption Study Using HAP Nano-Composites As Adsorbent

PERCENTAGE REMOVAL (%)

Table 7: Percentage Removal at