Final Project Report Nayana

REMOVAL OF COPPER FROM INDUSTRIAL
WASTEWATER USING NATURAL ADSORBENTS

PROJECT REPORT
Submitted By,
NAYANA P BABU
Reg No: SNG16CE066
to
The APJ Abdul Kalam Technological University
in partial fulfillment of the requirements for the award of the Degree
of
Bachelor of Technology
in
Civil Engineering
Department of Civil Engineering
Sree Narayana Gurukulam College of Engineering

Kadayiruppu
2019-20
SREE NARAYANA GURUKULAM COLLGE OF ENGINEERING
KADAYIRUPPU
DEPARTMENT OF CIVIL ENGINEERING
Certificate
This is to certify that Project Report entitled ‘Removal of Copper from Industrial
Wastewater using Natural Adsorbents’ submitted by Nayana P Babu to the APJ Abdul
Kalam Technological University in partial fulfillment of the requirements for the award of
B.Tech Degree in Civil Engineering is a bonafide record of the work done by him/her under my
guidance and supervision
Guide: Coordinator: Coordinator:
Mr. Ajith AV Ms. Anila PV Ms. Ananya John

Assoc. Prof. Asst. Prof. Asst. Prof.
Dept. of Civil Engg Dept. of Civil Engg Dept. of Civil Engg
SNGCE SNGCE SNGCE
Prof. Dr. S Usha

Professor & Head of Department
Dept. of Civil Engg.
SNGCE
ACKNOWLEDGEMENT
First and foremost, we wish to thank omnipotent God for his blessings.
We are grateful to Prof. Dr. S Usha (Head of Civil Engineering Department) for her
support during this project.
We wish to express our indebtedness to our guide Mr. Ajith A.V (Associate
Professor, Civil Engineering Department) for his valuable guidance in bringing out
this project.
We would also like to record our indebt gratitude to our project coordinators Ms.
Anila P.V (Assistant professor, Civil Engineering Department) Ms. Ananya John
(Assistant professor, Civil Engineering Department) for all the direction and
guidance.
At last not the least we are grateful to all the faculty of the Civil Engineer Department
and our friends for the support and feedback.
i
ABSTRACT
As the current global trend towards more stringent environmental norms, technical
application, and cost effectiveness became key factors in the selections of adsorbents
for water and waste water treatment. Recently, various low cost adsorbents derived
from agricultural material, industrial waste material and by products or natural
materials, have been intensively investigated. In the present work, the potential of
using coconut pith and eggshell powder as adsorbents for removal of copper from
wastewater is investigated. A batch scale experiment for different amount of
adsorbents is carried out. The adsorption characteristic of the adsorbent will be
studied under various experimental conditions, such as pH, contact time, adsorption
dose. The studies revealed that the eggshell is having maximum adsorption capacity
than coconut pith. Eggshell powder contains calcium carbonate, magnesium carbonate
and calcium phosphate as main constituents, which have good adsorption capacity.
The optimum pH for maximum uptake of Copper was at pH 6.5 and optimum
eggshell concentration was 4g for 1 litre of industrial waste water. Also a method is
devised to retrieve the copper from the adsorbent after the treatment.
ii
CONTENTS
DESCRIPTION PAGE No:
ACKNOWLEDGEMENT i
ABSTRACT ii
CONTENTS iii
LIST OF FIGURES v
LIST OF TABLES vi
CHAPTER 1: INTRODUCTION 1
1.1 GENERAL 1
1.1.1 Copper removal methods 3
1.1.1.2 Removal by Ion Exchange 3
1.1.1.3 Precipitation 4
1.1.1.3 Membrane Filtration 5
1.1.1.4 Biosorption 6
1.2 SCOPE OF PROJECT 6
1.3 OBJECTIVES OF PROJECT 6
CHAPTER 2: LITERATURE REVIEW 7
2.1 GENERAL 7
2.2 PREVIOUS STUDIES 7
CHAPTER 3: METHODOLOGY 11
3.1 ADSORPTION 11
3.2 IODOMETRY 13
3.3. EXPERIMENTAL PROGRAM 13
3.3.1 Materials 15
3.3.1.1 Industrial Wastewater 15
3.3.1.2 Copper Sulphate Stock Standard Solution 17
3.3.1.3 Adsorbents 17
3.3.2 Experiment 20
3.3.2.1 Copper Removal using Eggshell 20
3.3.2.2 Removal of Copper using Coconut Pith 21
3.3.2.3 Comparison of Eggshell and Coconut pith 21
iii
CONTENTS
DESCRIPTION PAGE No:
3.3.2.4 Testing of wastewater 21
3.4 RETRIEVAL METHOD FOR COPPER AFTER 21
……………………….ADSORPTION FROM ADSORBENT
CHAPTER 4: RESULTS AND DISCUSSION 22
4.1 ADSORPTION USING EGGSHELL 22

4.1.1 Optimum Eggshell dosage and Contact time 22
4.1.2 Optimum pH 23
4.2 COMPARISON OF EGGSHELL AND COCONUT 25
MM PITH
4.3 TESTING OF WASTEWATER 26
CHAPTER 5: RETRIEVAL METHOD FOR COPPER 27
5.1 METHODOLOGY 27
5.2 IDENTIFICATION OF COPPER SALT OBTAINED 28
5.2.1 Test for Copper 28
5.2.2 Test for Chloride 28
5.2.3 Test for Nitrate 28
5.2.4 Test for Sulphate 28
.5.3 TESTING OF WASTEWATER AFTER RETRIEVAL 29
CHAPTER 6 : CONCLUSION 30
REFERENCES 31
iv
LIST OF FIGURES
Fig No : TITLE PAGE No:
1.1 Effluent from industries 2
1.2 Ion exchange process in waste water treatment 4
1.3 Chemical Precipitation 5
3.1 Adsorption process 11
3.2 Adsorption process 12
3.3 Flowchart showing methodology 14
3.4 Collected waste water 15
3.5 Collected eggshells 17
3.6 Preparation of egg shells 18
3.7 Powdered Eggshells prepared 18
3.8 Collected coconut pith 19
3.9 (a) Untreated coconut pith (b) Treated coconut 20
pith, prepared
4.1 Copper content after adsorption v/s eggshell 23
concentration
4.2 Concentration of copper after adsorption v/s 24
pH
4.3 Flow chart for retrieval of copper from 1L of 27
industrial wastewater
v
LIST OF TABLES
TABLE NO : TITLE PAGE NO:
3.1 Composition of industrial wastewater 16
4.1 Remaining concentration of copper after 22
adsorption
4.2 Titration readings after varying pH 23
4.3 Concentration of copper after adsorption at 24

different pH
4.4 Concentration and contact time of untreated 25
coconut pith
4.5 Concentration of coconut pith and contact 26
time of treated coconut pith
vi
Project report 2019-2020 Removal Of Copper From Industrial Wastewater
Using Natural Adsorbents
CHAPTER 1
INTRODUCTION
1.1 GENERAL
Environmental pollution is currently one of the most important issues faced by

humanity. Pollution has increased exponentially in the past few years and reached
alarming levels in terms of its effects on living creatures. Toxic heavy metals are
considered one of the pollutants that have direct effect on man and animals. Whether
it’s the food we eat, the beverages we drink, the clothes we wear, or the paper and
chemical products we use, water is required for nearly every step of production across
a multitude of different industries. The resulting wastewater must be carefully
managed. Regardless of how wastewater is treated, the “end product” is called
effluent. Waste water contamination is ever increasing problem which the whole
world is now facing. Waste water comprises liquid waste discharged by domestic,
industrial waste, agricultural activity and commercial properties. Industrial waste
constitutes the major source of metal pollution in natural water. Toxic heavy metals
(Cd, Zn, Pb , Cu and Ni) are major pollutant of waste water which is very hazardous.
Industrial wastewater containing lead, copper, cadmium, chromium, etc., for example
can contaminate groundwater resources and thus lead to a serious groundwater
pollution problem. Water of high quality is essential to human life and water of
acceptable quality is essential for agriculture, industrial, domestic and commercial
uses. All these activities are also responsible for polluting the water. Billions of
gallons of waste from all these sources are thrown to freshwater bodies every day as
shown in figure 1.1. The requirement for water is increasing while slowly all the
water resources are becoming unfit for use due to improper waste disposal. To comply
with environmental protection laws, certain things must be removed from the
wastewater. The treated wastewater can then be safely discharged into water bodies,
applied to land, or even reused in plant operations. The task of providing proper
treatment facility for all polluting sources is difficult and also expensive, hence there
is pressing demand for innovative technologies which are low cost, require low
maintenance and are energy efficient. On-site treatment can help the plant remain
Department of Civil Engg 1 SNGCE, Kadayiruppu

environmentally compliant and save money, while facilitating production and

recovering valuable resources.
The release of toxic substances in the wastewater from industrial activities such as
mining, metal processing, pharmaceuticals, pesticides, organic chemicals, rubber and
plastics, etc. may cause serious effects on the environment and human health. It is
because the toxic substances have a tendency to accumulate in the soil, sea water,
fresh water and sediments due to their high dispersion from where they enter into the
food-chain.
Figure 1.1: Effluent from industries

(Source: www.google.co.in)
Industrial wastewater treatment describes the processes used for treating wastewater
that is produced by industries as an undesirable by-product. After treatment, the
treated industrial wastewater (or effluent) may be reused or released to a sanitary
sewer or to surface water in the environment.
Copper is one of the toxic heavy metals discharged into the environment due to
industrial operations, anthropogenic activities and natural source of copper exposure.
In order to have a pollution-free environment, the toxic heavy metals should be

removed from wastewater before its disposal. Removal of toxic heavy metals from
industrial wastewater has been practiced for several decades by the conventional
physico-chemical removal methods, such as chemical precipitation, chemical
oxidation and reductions, Electro dialysis, Electro precipitation, extraction of liquid,
microfiltration, membrane separation, evaporation and resin ionic exchange.
However, these methods are usually are found to be inefficient and expensive,
especially when treating wastewater with low concentration of heavy metals.
Therefore, alternative method has been attempted using low cost materials to remove
heavy metals by adsorption process. Adsorption technique is an economically
favourable and technically easy method to separate pollutants from wastewater.
Biosorption is potentially an attractive technology for treatment of waste water for
retaining heavy metal form dilute solution. Biosorption has been suggested as
cheaper, more effective and minimization of chemical and biological sludge
Researchers have worked on inexpensive materials, such as coconut shell, sawdust,
mango leaves, chitosan, egg shell, and other adsorbents, which have high adsorption
capacity and are locally available.
1.1.1 Copper Removal Methods
Various treatment technologies have been developed for heavy metal removal like
copper from water including ion exchange, precipitation, membrane filtration and
adsorption.
1.1.1.2 Removal by Ion Exchange
Ion-exchange processes have been widely used to remove heavy metals from water
due to their many advantages, such as high treatment capacity, high removal
efficiency and fast kinetics. Ion exchange resin, either synthetic or natural solid resin,
has the specific ability to exchange its cations with the metals in the wastewater.
Among the materials used in ion-exchange processes, synthetic resins are commonly
preferred as they are effective to nearly remove the copper from the solution. Ion
exchangers get quickly polluted, which considerably reduces their exchange capacity.
Another disadvantage is the relatively high operational costs.

Figure 1.2: Ion exchange process in waste water treatment

1.1.1.3 Precipitation
The simple precipitation of metals as insoluble hydroxides, carbonates, or sulphides is

used in about 75% of electroplating facilities to treat wastewater. In conventional
treatment, precipitation is the technique of choice for the removal of dissolved heavy
metals. Precipitation of heavy metals lowers the concentrations of all metals. The
solubility of precipitated metal compounds is the key to the success of this method. If
a metal can form an insoluble compound, then the compound can be removed via
clarification and filtration. Of the few precipitation methods, hydroxide and sulfide
are the two main methods currently used, and hydroxide precipitation is by far the
most widely used method. In this method a large quantity of reagent is generally
needed for the removal of heavy metal, which is often very expensive. Another
disadvantage is that large quantity of silt is produced. Few problems are encountered
if the silt could be precipitated as a useful by-product. For example, the silt which
contains heavy metals in it will be regarded as a dangerous waste and will be
accompanied by high processing costs.

Figure 1.3: Chemical Precipitation

1.1.1.3 Membrane Filtration
Membrane filtration is the pressure driven separation process that employs a

membrane for both mechanical and chemical sieving of particles and
macromolecules. The concentration of larger samples on a membrane filter is a key
benefit of the technique. However, expensive cleaning and regeneration schemes may
be necessary. The high flow rates used in cross flow feed can damage shear sensitive
materials. If the membrane manufacturing process is not precisely controlled, the
membranes with wide pore size distribution may result, giving poor separation
performance.
Figure 1.4: Membrane separation


1.1.1.4 Biosorption
Biosorption is another method that can use to remove heavy metals from wastewater.
Sorption process is transfer of ions from solution phase to the solid phase, actually
describes a group of processes, which includes adsorption and precipitation reactions.
Adsorption has become one of the alternative treatment techniques for wastewater.
Basically, adsorption is a mass transfer process and substances bound by physical and
or chemical interactions to solid surface [3]. Various low-cost adsorbents, derived
from agricultural waste, industrial by-product, natural material, or modified
biopolymers, have been recently developed and applied for the removal of heavy
metals from metal-contaminated water.
1.2 SCOPE OF PROJECT
As the current global trend towards more stringent environmental norms, technical
application, and cost effectiveness became key factors in the selections of adsorbents
for water and waste water treatment. Recently, various low cost adsorbents derived
from agricultural material, industrial waste material and by products or natural
materials, have been intensively investigated.
An electroplating industry near karingachira produced around 1 lakh litres of

wastewater per day having copper concentration of 85 mg/L. As per IS 10500: 2012,
the permissible limit of copper in drinking water is 0.5mg/l. The maximum allowable
concentration limit in industrial is 3.0mg/l. And the maximum permissible limit of
copper in inland surface water is 1.5mg/l. The usage of highly copper concentrated
water will affect growth of plants. It also affects laboratory animals, aquatic life,
terrestrial plants and livestock. In plants this will affect cellular process like
photosynthesis and respiration. The main objective of this project is to reduce the
concentration of copper in industrial wastewater below the permissible limit.
1.3 OBJECTIVES OF PROJECT
The main objectives of this project are
1. To devise an efficient method to remove copper from industrial waste water.

2. To compare the adsorption capacities of egg shell and coconut pith.
3. To develop a method to recovery copper from adsorbents.

CHAPTER 2
LITERATURE REVIEW
2.1 GENERAL
In modern societies proper management of wastewater is a necessity, not an option.

Historically, the practice of collecting and treating wastewater prior to disposal is a
relatively recent undertaking. Excessive release of copper into the environment has
posed a great problem worldwide. The copper in industrial water do not degrade into
harmless end products.
2.2 PREVIOUS STUDIES
Madhu et al. (2017). This journal is based on the removal of heavy metal from
aqueous solutions by using various adsorbents. In this study both commercial
adsorbents and bio -adsorbents are used for the removal of heavy metals from
wastewater, with high removal capacity. This review article aims to compile scattered
information on the different adsorbents that are used for heavy metal removal and to
provide information on the commercially available and natural bio-adsorbents used
for removal of chromium, cadmium and copper, in particular. A number of types of
adsorbents are used for the efficient removal of heavy metal removal from wastewater
that is both commercial and/or bio-adsorbents. This review shows the potential of
commercial and agricultural adsorbents for the removal of chromium, cadmium and
copper from wastewater. And the adsorption data have been found to fit the Langmuir
and Freundlich models, which indicate single and multilayer adsorption behaviour.
Further, the cost of both commercial adsorbents and bio-adsorbents was compared.
The cost of commercial activated carbon is Rs. 500/kg; however, the cost of bio-
adsorbents is in the range of Rs. 4.4–36.89/kg, which is much less compared to the
commercial adsorbents. And they concluded that the bio-adsorbents used for removal
of chromium, cadmium and copper are low cost adsorbents and are beneficial
replacements for commercially available adsorbents.
Monser et al. (2002). This journal is based on the removal of copper, zinc, chromium
and cyanide from wastewater by modified activated carbon. They investigated the
adsorption of toxic ions, copper, zinc, chromium and cyanide on these adsorbents that

they undergo surface modification with tetra butyl ammonium (TBA) and SDDC in
wastewater applications. The modification techniques enhance the removal capacity
of carbon and therefore decrease cost effective removal of copper, zinc, CN from
metal finishing wastewater. The TBA-carbon adsorbent was found to have an
effective removal capacity of approximately five times that of plain carbon.
Range et al. (2012). This journal is based on the removal of heavy metal from
wastewater using low cost adsorbents. The study was to contribute in the search for
less expensive adsorbents and their utilization possibilities for various agricultural
waste by-products such as seaweed, algae, chitosan, egg shell and saw dust etc. for
elimination of heavy metals from wastewater. He found out that egg shell can be used
in treatment process of heavy metals and efficiency can be increased as high as 100%
of the amount of adsorbent is precise.
Heung et al. (2007). They focused on the removal capacity of toxic heavy metal
using calcinated and normal egg shell. After calcination, the major inorganic
composition was identified as Ca (lime, 99.63%) and K, P and Sr were identified as
minor components. When calcined eggshell was applied in the treatment of synthetic
wastewater containing heavy metals, a complete removal of Cd as well as above 99%
removal of Cr was observed after 10 min. Although the natural eggshell had some
removal capacity of Cd and Cr, a complete removal was not accomplished even after
60 min due to quite slower removal rate. However, in contrast to Cd and Cr, an
efficient removal of Pb was observed with the natural eggshell rather than the
calcined eggshell. From the application of the calcined eggshell in the treatment of
real electroplating wastewater, the calcined eggshell showed a promising removal
capacity of heavy metal ions as well as had a good neutralization capacity in the
treatment of strong acidic wastewater. He found that no removal of Cd and Cr in
synthetic wastewater was much enhanced in the presence of calcinated eggshell,
however removal of Pb was rather favourable with natural egg shell. Calcinated
eggshell is a good neutraliser and effective reactant for treatment of acidic water and
wastewater containing metal ion.
Ahmad et al. (2010). They studied the adsorption of Cu2+ onto iron oxide coated
eggshell powder. The effect of various operational parameters such as pH, contact,
initial adsorbate concentration of Cu2+ ions are investigated using batch adsorption.

The optimum pH for Cu2+ adsorption was found to be 6. The result shows that the
IOESP exhibited a remarkably enhanced adsorption capacity for Cu2+.
Agarwal et al. (2014). They studied the adsorption efficiency of Cu and Fe. The
research is a batch scale experiment using adsorbent at five different concentrations of
(5, 10, 20, 40, 100 mg/L) both metals and is mixed combination. About 85% to 95%
Fe removal was achieved by using 0.5 to 1.5 g adsorbent for solution having
concentration of 5 and 10 mg/L of Fe. Two main things comes out of the above study,
first, the adsorption efficiency depends on the amount of adsorbent as the adsorption
efficiency of Cu was increased from 80% to 95% in the same solution (5 mg/L).
Second, it also found that adsorption efficiency was decreased by about 7 % and 3%
of Fe and Cu to mixed metal solution. The analysis shows that eggshell powder, like
the most other natural adsorbents, can be used in the treatment process of heavy
metals and the treatment efficiency may be as high as 100% by precise selection of
adsorbent quantity. It was also observed that the concentration of heavy metals has an
important effect on the result of this treatment. Eggshell powder is a waste material
and conveniently used for the treatment of industrial wastewater containing Cu and Fe
heavy metals. The most important finding of the study shows that in the mixture of
metal ions the percentage adsorption decreased. It clearly indicate that heavy metals
need to be removed from the industrial waste before the discharge in to the rivers as
study shows that the presence of one more metal will decrease the adsorption
efficiency of adsorbent.
Abd Ali et al. (2016). In their study they investigated adsorption of Cu (II) and Cd
(II) ions onto eggshell. The effects of contact time, initial pH of solution, adsorbent
dosage, initial metal concentration, agitation speed, and temperature were studied in
batch experiments. The maximum adsorption capacities for Cu(II) and Cd(II) were
8.4 and 7.01 mg/g, respectively. Thermodynamic parameters such as Gibbs free
energy change, Enthalpy change and Entropy change have been calculated. These
thermodynamic parameters indicated that the adsorption process was
thermodynamically spontaneous under natural conditions and the adsorption was
endothermic in nature. Experimental data were also tested in terms of adsorption
kinetics, the results illustrated that the adsorption process was following pseudo
second- order kinetics. In addition Fourier transfer infrared spectroscopy (FTIR)

analysis suggests that Cu (II) and Cd (II) interact with metal oxides and –OH
functional group present in eggshell powder. They found out that maximum
adsorption capacity of Cu is 8.4mg/g. The percentage removal was strongly
dependent on the contact time, initial pH of solution, adsorbent dosage and agitation
speed. His study on thermodynamic parameters indicated that adsorption process was
thermodynamically spontaneous under natural conditions and adsorption is
endothermic.
On the banks of the Saigon river in Viet Nam, Dr. Kohler et.al. completed tests on a
new way to combat water pollution that could save millions of lives in coastal cities in
the developing world. Toxic metals like cadmium, zinc, lead and iron were cleaned
using seashells. They found that pouring metal and acid-laden water over a bed of
crushed clam or mussel shells provides an easy fix. The shells are made of aragonite,
a form of calcium atoms in favour of heavy metals, locking them into a solid form.
The shells are alkaline-a pH of 8.3 when dissolved – and needs to be maintained so by
adding more shells.

CHAPTER 3
METHODOLOGY
Adsorption is the methodology here we used for removal of copper from wastewater.
In this project the copper concentration in the waste water is determined using
iodometry and various parameters such as pH, concentration of adsorbent and contact
is optimized in the copper sulphate solution prepared in the same concentration of
copper in the wastewater. And the wastewater is treated on these optimized
parameters. Then we also designed an industrial process for removal and retrieval of
copper from wastewater.
3.1 ADSORPTION
The method used for the removal of copper from wastewater is adsorption.
Adsorption is a process that occur when a gas or liquid solute accumulates on the
surface of a solid or a liquid forming a molecular or atomic film. Adsorption is the
adhesion of atoms ions or molecular from a gas, liquid or dissolved solid to a surface.
This process creates a film of the adsorbate on the surface of the adsorbent. This
process differs from absorption, in which a fluid (the absorbate) permeates or is
dissolved by a liquid or solid (the absorbent). Adsorption is a surface-based process
while absorption involves the whole volume of the material. The term sorption
encompasses both processes, while desorption is the reverse of it. Adsorption is a
surface phenomenon.
Fig 3.1 : adsorption process


Adsorption has become one of the alternative treatment techniques for wastewater.
Basically, adsorption is a mass transfer process and substances bound by physical and
or chemical interactions to solid surface [3]. Various low-cost adsorbents, derived
from agricultural waste, industrial by-product, natural material, or modified
biopolymers, have been recently developed and applied for the removal of heavy
metals from metal-contaminated water.
Adsorption is operative in most natural physical, biological, and chemical systems,

and is widely used in industrial applications such as activated charcoal, synthetic
resins and water purification. Similar to surface tension, adsorption is a consequence
of surface energy. Adsorption is usually described through isotherms, that is,
functions which connect the amount of adsorbate on the adsorbent, with its pressure
(if gas) or concentration (if liquid). When wastewater is treated with chicken egg
shell, copper in water get adsorbed on the surface of the egg shell.
Fig 3.2 : Adsorption process


Adsorption
Adsorbate ₊ Adsobent ⇌ Adsorption
Desorption
A + B ⇌ AB
The adsorption percentage is to be calculated using the following equation:
Adsorption percentage = (Co-Cf) / Co*100
Where,
Co – liquid phase concentration of at Cu 2+ initial
Cf – liquid phase concentration of Cu 2+ at equilibrium
3.2 IODOMETRY
Iodometry is used to determine the concentration of copper in wastewater. Amount of

iodine liberated from iodide is equivalent to the quantity of oxidizing agent (CuSO4)
present.
In this method 20 ml of sample is pipet out into a conical flask. To this 15 ml of 5%

potassium iodide solution is added. The sample turns dark yellow. Then titrate against
standard 0.001N sodium thiosulphate. When solution becomes pale yellow 1 ml of
starch solution is added to it. The titration is continued until the blue colour
disappears.
From the volume of sodium thiosulphate used the remaining concentration of copper
in wastewater can be calculated using the following equation.
Copper concentration in water = (V*0.001*63.54)/20
Where,
V- Volume of sodium thiosulphate solution used
3.3. EXPERIMENTAL PROGRAM
One of the major objectives of the project was to devise a method to remove copper
from the wastewater created during an industrial process. The details of the
experimental program conducted are described in this chapter.

Identification of Industry
Selection of Adsorbents
Preparation of Adsorbents
Collection of Waste water
Estimation of Copper content in the

waste water through Iodometry
Preparation of std. Copper sulphate solution with same

concentration of copper in waste water
Copper Removal
Copper Removal using Copper Removal using

Egg shell Coconut pith
Comparison of Adsorption capacities of Egg shells and

Coconut pith
Treatment of Industrial waste water using

the adsorbent
Retrieval of Copper from Adsorbent
Design of Industrial process for removal

and Retrieval of copper
Fig 3.3: Flowchart showing methodology

Adsorption is the methodology used for removal of copper from wastewater. In this
project various parameters such as pH, concentration of adsorbent and contact is
optimized in the copper sulphate solution prepared in the same concentration of
wastewater. And the wastewater is treated on these optimized parameters. Then also
design an industrial process for removal and retrieval of copper from wastewater.
3.3.1 Materials
3.3.1.1 Industrial Wastewater
Industrial waste water is collected from an electroplating industry near Muttakuzhi in

Ernakulam district. This water contains high amount of copper. The amount of waste
water generated per day is 1 lakh litres. Copper concentration in industrial wastewater
is estimated to be 84.15 mg/L.
Fig 3.4: Collected waste water

As per the data given from the electroplating Industry the following table shows the
heavy metal composition present in the wastewater.
Table 3.1 Composition of industrial wastewater
Heavy Metal Concentration (mg/l)
Au -0.002
Ni 11.26
Cu 84.15
Cr 0.000
Pb 0.250
Zn 0.129
Sn 26.88
Co 0.015
Pd 0.022
Fe 0.048

3.3.1.2 Copper Sulphate Stock Standard Solution
To conduct the experiments, Copper sulphate (CuSO4) is used for the preparation of
stock standard solutions of Copper in distilled water. The copper sulphate solution is
to be prepared with the same concentration of copper as present in wastewater.
3.3.1.3 Adsorbents
(i) Egg shells
Egg shell is largely-crystalline calcium carbonate. The calcium comes partly from the
hen’s bones and when necessary the hen can mobilize 10 percent of her bone for the
purpose. Eggshell is mainly composed of calcium carbonate (94.03%) and it also
contains calcite and calcareous soil. Eggshell has a cellulosic structure and contains
amino acids; thus, it is expected to be a good biosorbent and it was reported that large
amounts of eggshells are produced in some countries, as waste products and disposed
in landfills annually. Eggshells are used as simple, effective and low cost method for
removing copper from industrial wastewater.
Fig 3.5 Collected eggshells

The chicken eggshell is collected from kitchen waste and is washed by deionized
water for several times to remove the dirt particles and inner layers are removed. The
eggshells are dried for 1 hour in oven at 100℃. The eggshells are heated to increase
the size of pores which will increase adsorption. The dried eggshells is ground into
small particles and stored in an airtight container for future use. Powdering of egg
shells will increase the fineness of adsorbent and thus improves adsorption. The
preparation method and the egg shells to be prepared are shown in Fig 3.3 and Fig 3.4
respectively.
Collection of eggshells
Oven drying of eggshells at 100℃ for

1 hour
Keep it at 40 ℃ for 24 hours
Ground into small powder
Fig 3.6: Preparation of egg shells
Fig 3.7 Powdered Eggshells prepared

(ii) Coconut pith
It is an organic by-product which is obtained from coconut husk while separating

fibre from husk. It is also known as “Cocopeat”. The availability of coconut pith is
approximately 0.15million tonnes in India especially from states like Kerala,
Karnataka, Tamil Nadu, Goa etc.
Cocopeat is a good biosorbent for removal of heavy metals from wastewater. Here
treated and untreated coconut piths are tried as adsorbents. Untreated coconut piths
are coconut pith which is cleaned and sieved through 300 micron sieve and retained
on 150 micron sieve. Treated coconut piths are untreated coconut piths which are
washed and oven dried. Fig 3.5 shows a sample of coconut pith.
Fig 3.8 Collected coconut pith

(a) (b)
Fig 3.9 (a) Untreated coconut pith (b) Treated coconut pith, prepared
3.3.2 Experiment
3.3.2.1 Copper Removal using Eggshell
(i) Optimization of contact time and eggshell dosage
To optimize the amount of egg shell and contact time, a series of experiments are
conducted with different concentration of egg shell and contact time. The eggshell
concentrations to be taken are 0.1, 0.2, 0.3, 0.4 and 0.5 in 100ml copper sulphate
solution. The contact times to be taken are 10, 15, 20 and 25 minutes. Agitation is to
be done using magnetic stirrer at constant rpm (350).
The remaining copper concentration was determined by iodometry.
(ii) Optimization of PH
To optimize PH, optimum gm of eggshell is added to 100ml of the copper solution at

different PH values (3, 5, 7, 9, and 11) and is to be stirred in a magnetic stirrer for the
optimum contact time. The PH is adjusted with 0.1 M NaOH or 0.1 M HCl solutions
and is measured by PH meter. The solution is filtered using filter paper. The remaining
copper concentration is determined by iodometry.

3.3.2.2 Removal of Copper using Coconut Pith
(i) Optimization of contact time and coconut pith dosage
Optimization of coconut pith concentration and contact time is to be determined for

different combinations of coconut pith dosage and contact time. The cocopeat
concentrations to be taken are 0.1, 0.2, 0.3, 0.4 and 0.5 in 100ml copper sulphate
solution. The contact time is to be taken are 10, 15, 20 and 25 minutes. The remaining
copper in solution is determined using iodometry.
3.3.2.3 Comparison of Eggshell and Coconut pith
The concentration of copper after adsorption in coconut pith determined at various

coconut pith concentrations and contact time and the concentration of copper after
adsorption at different concentrations of untreated and treated coconut pith at different
contact time is compared. And the one with maximum adsorption capacity is taken as
the adsorbent for the removal of copper from industrial wastewater.
3.3.2.4 Testing of wastewater
The adsorbent used for treating of wastewater is decided. Wastewater is treated at the
above obtained PH at an optimum concentration of selected adsorbent and contact
time.
3.4 RETRIEVAL METHOD FOR COPPER AFTER ADSORPTION FROM

ADSORBENT
An attempt is made to device a method to retrieve the copper from the adsorbent after
the treatment.

CHAPTER 4
RESULTS AND DISCUSSION

This chapter present the results obtained from the experiments conducted.
4.1 ADSORPTION USING EGGSHELL
4.1.1 Optimum Eggshell dosage and Contact time
At different contact time and eggshell dosages the remaining concentration of copper
after adsorption was determined. Table 4.1 shows the remaining concentration of
copper after adsorption at different concentration of eggshells and at different contact
time.
Table 4.1.Remaining concentration of copper after adsorption
Concentration of eggshell in gm in 100 ml
Contact time (minute) 0.1 0.2 0.3 0.4 0.5
10 56 55.2 54.6 43.2 42.2
15 49.5 44.4 35 25 20.6
20 48.6 44.1 32.7 30.9 12.3
25 41.3 22.2 24.4 1.68 1.6

Copper content after adsorption v/s Eggshell

concentration
60
50
10 Minutes
40 15 Minutes
20 Minutes
30
25 Minutes
20
10
0
0.1 0.2 0.3 0.4 0.5
Fig 4.1.Copper content after adsorption v/s eggshell concentration
It is observed from Figure 4.1 adsorption increases with increase in contact time.
Also, adsorption increases with increase in the concentration of eggshell. Maximum
removal of copper is taking place at an eggshell concentration of 0.4g in 100ml
copper solution and at 25 minutes contact time.
4.1.2 Optimum pH
The concentration of copper in copper sulphate solution after adsorption at optimum

eggshell dosage and contact time at different pH was determined. Table 4.2 shows the
concentration of copper after adsorption at different pH.
Table 4.2 Titration readings after varying pH
Volume of sodium Concentration of copper (in

pH thiosulphate used percentage) after adsorption
3 17.5 55.2
5 7.1 30.96
7 6.7 0.25
9 - -
11 - -

Concentration of copper after adsorption v/s pH
60
50
40
30
20
10
0
3 5 7 9 11
Fig 4.2 Concentration of copper after adsorption v/s pH
Table 4.3 shows the concentration of copper when the pH is varied from 5 to 7. The
adsorption is calculated for these values.
Table 4.3 Concentration of copper after adsorption at different pH
Concentration of copper after

pH
adsorption(mg/l)
5.5 12.7
6 9.05
6.5 0.25
It is observed that the maximum adsorption takes place at a pH of 6.5. Therefore the
optimum pH is taken as 6.5.

4.2 COMPARISON OF EGGSHELL AND COCONUT PITH
The concentration of copper after adsorption in coconut pith was determined at

various coconut pith concentrations and contact time.
Table 4.4 shows the concentration of copper after adsorption at different

concentrations of untreated coconut pith and at different contact time.
Table 4.4 Concentration and contact time of untreated coconut pith
Concentration of coconut pith in gm in 100 ml
10 72 62.23 60.32 50.16 42.8
15 65.4 63.5 61.27 58.42 56.5
20 66.04 62.9 60.3 57.82 55.2
25 63.54 59.4 60.04 57.18 54
From the observed results it is clear that adsorption increases with increasing the
coconut pith concentration and contact time. But the efficiency of coconut pith is less
compared to eggshell. Again the coconut is treated and compared the results. Table
4.5 shows the concentration of copper after adsorption at different concentrations of
treated coconut pith and at different contact time.

Table 4.5 Concentration of coconut pith and contact time of treated coconut pith
Concentration of coconut pith in gm in 100 ml
10 67.03 41.3 36.5 23.82 12.07
15 54.64 38.44 24.46 17.15 13.97
20 54 40.34 25.41 16.8 12.39
25 63.54 57.8 54 41.3 30.49
The heated coconut pith is more efficient in adsorption of copper from water. Again
heated coconut pith does not attain adsorption capacity of eggshells. There for here
eggshells are taken as the adsorbent for the removal of copper from industrial
wastewater.
4.3 TESTING OF WASTEWATER
Here the adsorbent used for treating of wastewater was powdered eggshells.
Wastewater was treated at the above obtained pH (6.5) at an optimum concentration
of eggshell (0.4g/100ml) and contact time (25 minutes). Almost complete removal of
copper was obtained when wastewater was treated at the optimum values. The
remaining concentration of copper in waste water is estimated as 0.25mg/l.

CHAPTER 5
RETRIEVAL METHOD FOR COPPER
5.1 METHODOLOGY
An attempt is made to device a method to retrieve the copper from the eggshells after
the treatment. For this, 1L of waste water is taken in a beaker and 90 ml of 0.02N
NaOH is added for adjusting pH. Then 4g of adsorbent is added to it. The sample is
stirred in a magnetic stirrer for 25 minutes. 90ml of 0.02N NaOH is added to
wastewater and the sample is heated till it boils. 90ml/l of 0.02N H2SO4 is added on
boiling. The sample is allowed to settle down. Adsorbent stays at bottom followed by
copper salt in colloidal form over it and water at the top. Filter and oven dry the
sample and separate copper salt. The salt obtained was tested for copper, sulphates,
chlorides and nitrates as the industrial waste water had copper chloride and copper
nitrate in it and due to treatment process there could be sulphate. Figure 4.3 shows
process of retrieval of copper salt.
Adjusting Remove
1 litre of pH using Add Stir for 900ml
waste NaOH to 4gm/l of 25 of waste
water 6.5 eggshell minutes water
Separate Add Add 90ml Remaining

the 90ml/l of NaOH waste
colloidal H SO stir and heat it water is
salt and 2 4
upto 90°C moved to
wastewater for 10mins heater
Oven dry and Wastewater

obtain copper tank
salt
Fig 4.3 Flow chart for retrieval of copper from 1L of industrial wastewater

The following reactions occur:
2+ 2+
Cu + 2 NaOH Cu(OH) + 2 Na
2
Cu(OH) + H SO CuSO . 2 H O
2 2 4 4 2
5.2 IDENTIFICATION OF COPPER SALT OBTAINED
The industrial wastewater contains copper nitrate and copper chloride in it. Due to the
various processes carried out for the retrieval of copper, the copper salt could also be
copper sulphate. Therefore test for copper, chloride, sulphate and nitrate will be done
in order to fix the copper salt obtained after the retrieval process.
5.2.1 Test for Copper
Take 20 ml of sample and add 15 ml of 5% potassium iodide, the sample turned deep
yellow indicating presence of copper.
5.2.2 Test for Chloride
About 0.5 ml of concentrated sulphuric acid is added to about 5 mg of sodium

chloride taken in a semi micro test tube. A glass rod moistened with concentrated
ammonia solution is introduced into the above gas. If change is observed indicates the
presence of chloride
5.2.3 Test for Nitrate
The brown ring test is used for detecting the presence of nitrate ion. The solution is
taken in a test tube and iron sulphate is added to it. Then concentrated sulphuric acid
is slowly added along the sides of test tube. If ring is formed on test tube indicates the
presence of nitrate.
5.2.4 Test for Sulphate
About 10 mg of the sulphate is dissolved in about 0.5 ml of water. Acidified with

dilute hydrochloric acid and add excess of barium chloride solution. A white
precipitate, insoluble in both hot dilute hydrochloric acid and nitric acid is obtained.
This indicates the presence of sulphate.

5.3 TESTING OF WASTEWATER AFTER RETRIEVAL
The waste water is tested again for the copper content after the process of retrieval of
copper. The remaining copper concentration is determined using iodometry. The pH
of the waste water is also noted.

CHAPTER 6
CONCLUSION
The removal of Cu (II) from wastewater by using chicken eggshells and coconut pith
has been experimented under several conditions such as at different pH, contact time
and adsorption dose. The egg shells with maximum adsorption capacity is used for
removing copper from industrial waste water. The optimum pH for copper adsorption
was found at pH 6.5. The optimum contact time was found to be 25 minutes. The
maximum adsorption is taking place at 4g/l eggshell concentration. The copper
removal capacity strongly depends on the concentration of adsorbents, contact time
and initial pH of the water. Adsorption capacity increases with increase in contact
time and concentration of adsorbents. This study shows that chicken eggshells and
coconut pith have high potential to be used as low-cost adsorbent for the removal of
copper from wastewater.

REFERENCES
[1]AnimeshAgarwal, Puneet Kumar Gupta(2014), “Removal of Cu and Fe from

aqueous solution by using eggshell powder as low cost adsorbent”, Advances in
Applied Science Research, Vol 5(2), page no: 75-79
[2] K.Ravindhranath,(2012), “Simple method for spectrophotometric determination

of traces of copper”, RASSAYAN J .Chem. vol.5
[3] LotfiMonser ,NafaaAdhoum,(2002), “Modified activated carbon for the removal

of copper, zinc, chromium and cyanide from wastewater”, Separation and
Purification Technology, Vol 26, page no: 137–146
[4] Mayur A. Chavan, Sachin Mane (2013), “Removal of Copper and Zinc from
Aqueous Solutions by Using Low Cost Adsorbents”, International Journal of Science
and Research (IJSR)
[5] PARK Heung Jai1, JEONG Seong Wook1, YANG Jae Kyu2, KIM Boo Gil,
LEE SeungMok ,(2007), “Removal of heavy metals using waste eggshell”, Journal
of Environmental Sciences, Vol 19, page no: 1436–1441
[6] Rais Ahmad, Rajeev Kumar, ShaziyaHaseeb,(2015), “Adsorption of Cu2+ from

aqueous solution onto iron oxide coated eggshell powder: Evaluation of equilibrium,
isotherms, kinetic and regeneration capacity”, Arabian Journal of Chemistry, King
Sauds University, Vol 5, page no: 353-359
[7] Renu, Madhu Agarwal and K. Singh,(2017), “Heavy metal removal from waste
water using various adsorbents; a review”, Journal of Water Reuse and Desalination,
Vol 4, page: 387-419
[8] Sajeda A. Al-Saydeh (2017) “Copper removal from industrial wastewater: A

comprehensive review” Journal of Industrial and Engineering Chemistry 56 (2017)
35-44
[9] V.C Range, S.V Khedkar, Shraddha V Pande,(2012), “Removal of heavy

metals from waste water using low cost adsorbents: a review”, Scientific reviews and
Chemical communications, Vol 2(4), page no: 580-584, ISSN 2277-2669

[10] ZiadTarkAbd Ali, Mohammed A. Ibrahim, Huda M. Madhloom ,(2016),

“Eggshell Powder as An Adsorbent for Removal of Cu (II) and Cd (II) from Aqueous
Solution: Equilibrium, Kinetic and Thermodynamic Studies”, NUCEJ, Vol 91, page
no: 2

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REMOVAL OF COPPER FROM INDUSTRIAL

WASTEWATER USING NATURAL ADSORBENTS

Department of Civil Engineering

Sree Narayana Gurukulam College of Engineering

DEPARTMENT OF CIVIL ENGINEERING

Guide: Coordinator: Coordinator:

Mr. Ajith AV Ms. Anila PV Ms. Ananya John

Prof. Dr. S Usha

CHAPTER 2: LITERATURE REVIEW 7

CHAPTER 4: RESULTS AND DISCUSSION 22

4.1 ADSORPTION USING EGGSHELL 22

CHAPTER 5: RETRIEVAL METHOD FOR COPPER 27

4.3 Concentration of copper after adsorption at 24

Environmental pollution is currently one of the most important issues faced by

Department of Civil Engg 1 SNGCE, Kadayiruppu

environmentally compliant and save money, while facilitating production and

Figure 1.1: Effluent from industries

Department of Civil Engg 2 SNGCE, Kadayiruppu

1.1.1 Copper Removal Methods

1.1.1.2 Removal by Ion Exchange

Department of Civil Engg 3 SNGCE, Kadayiruppu

Figure 1.2: Ion exchange process in waste water treatment

The simple precipitation of metals as insoluble hydroxides, carbonates, or sulphides is

Department of Civil Engg 4 SNGCE, Kadayiruppu

Figure 1.3: Chemical Precipitation

1.1.1.3 Membrane Filtration

Membrane filtration is the pressure driven separation process that employs a

Figure 1.4: Membrane separation

Department of Civil Engg 5 SNGCE, Kadayiruppu

1.2 SCOPE OF PROJECT

An electroplating industry near karingachira produced around 1 lakh litres of

1.3 OBJECTIVES OF PROJECT

The main objectives of this project are

1. To devise an efficient method to remove copper from industrial waste water.

Department of Civil Engg 6 SNGCE, Kadayiruppu

In modern societies proper management of wastewater is a necessity, not an option.

2.2 PREVIOUS STUDIES

Department of Civil Engg 7 SNGCE, Kadayiruppu

Department of Civil Engg 8 SNGCE, Kadayiruppu

Department of Civil Engg 9 SNGCE, Kadayiruppu

Department of Civil Engg 10 SNGCE, Kadayiruppu

Fig 3.1 : adsorption process

Department of Civil Engg 11 SNGCE, Kadayiruppu

Adsorption is operative in most natural physical, biological, and chemical systems,

Fig 3.2 : Adsorption process

Department of Civil Engg 12 SNGCE, Kadayiruppu

The adsorption percentage is to be calculated using the following equation:

Adsorption percentage = (Co-Cf) / Co*100

Iodometry is used to determine the concentration of copper in wastewater. Amount of

In this method 20 ml of sample is pipet out into a conical flask. To this 15 ml of 5%

Copper concentration in water = (V*0.001*63.54)/20

V- Volume of sodium thiosulphate solution used

3.3. EXPERIMENTAL PROGRAM

Department of Civil Engg 13 SNGCE, Kadayiruppu

Collection of Waste water

Estimation of Copper content in the

Preparation of std. Copper sulphate solution with same

Copper Removal using Copper Removal using

Comparison of Adsorption capacities of Egg shells and

Treatment of Industrial waste water using

Retrieval of Copper from Adsorbent

Design of Industrial process for removal

Fig 3.3: Flowchart showing methodology

Copper concentration in water = (V0.00163.54)/20