Final

REMOVAL OF COPPER FROM
INDUSTRIAL WASTE WATER

USING NATURAL ADSORBENTS
PRESENTED BY : GUIDED BY :
Navaneethakannan M [16] Ajith AV
Nayana P Babu [17] Associate Prof
Neethu K Avira [19] Civil Engg , SNGCE
Rohn Jose [27]
1. Introduction
2. Scope of project
3. Literature review
CONTENTS 4. Objectives of project
5. Materials required
6. Experimental program
7. Conclusion
8. References
2
Removal of copper from industrial wastewater using natural adsorbents
INTRODUCTION
• Industrial wastewater is a by-product of
industrial or commercial activities.
• To comply with environmental protection You can simply impress your audience
and add a unique zing and appeal to
your Presentations.
laws, certain substances must be removed
from the wastewater.
Fig.1: Egg shells
(Source: https://in.google.com)
• The permissible limit of copper in industrial
waste water is 3mg/L by USEPA (1998).
Removal of copper from industrial wastewater using natural adsorbents 3

SCOPE
• If the concentration of copper in water is more than the permissible
limit then it causes health issues in humans .
• If the concentration of copper in surface water is more there will be
bio magnification.
• The usage of highly copper concentrated water will affect growth of

plants and this will affect cellular process like photosynthesis.

LITERATURE REVIEW
S.No. 1
JOURNAL NAME: Heavy metal removal from wastewater using various absorbents: a
review, Journal of water reuse and desalination.
JOURNAL AUTHOR: Madhu et al. (2017)
DETAILS CONCLUSION
• A wide range of absorbents has been • The optimum values for parameters
studied for removal of heavy metals from such as pH, contact time, dosage of
wastewater . absorbent were compared and they
• For removal of copper bio-absorbents concluded that bio-adsorbents are
like: beneficial replacements for commercially
i. fungal biomass available adsorbents.
ii. yeast
iii. algal biomass
iv. bacteria , were used.
LITERATURE REVIEW
S.No. 2
JOURNAL NAME: Modiﬁed activated carbon for the removal of copper, zinc,
chromium and cyanide from wastewater
JOURNAL AUTHOR: Monser et al. (2002)
DETAILS CONCLUSION
• Investigated the adsorption of toxic • The modified TBA-carbon adsorbent was

ions like copper, zinc, chromium and found to have an effective removal
cyanide on the modified activated carbon capacity of approximately five times that of
adsorbents. plain carbon.
• Modification technique enhance the
removal capacity of carbon and therefore
cost effective.
6
LITERATURE REVIEW
S.No. 3
JOURNAL NAME: Removal of heavy metals from wastewater using low cost adsorbents :
A review, Scientific reviews and Chemical communications.
JOURNAL AUTHOR: Renge et al. (2012)
DETAILS CONCLUSION
• The search for less expensive • Egg shell can be used in treatment
adsorbents & their utilization possibilities process of heavy metals and efficiency
for the various agricultural waste by- can be increased as high as 100% of the
products such as seaweed, algae, chitosan, amount of adsorbent is precise.
eggshell and saw dust etc. for elimination o
f heavy metals from wastewater.
7
LITERATURE REVIEW
S.No. 4
JOURNAL NAME: Removal of heavy metals using waste eggshell, Journal of
Environmental Sciences.
JOURNAL AUTHOR: Heung et al. (2007)
DETAILS CONCLUSION
• When calcined eggshell was applied in the treat • Calcined eggshell showed a
ment of synthetic wastewater containing heavy m promising removal capacity
etals, a complete removal of Cd as well as above 9 of heavy metal ions.
9% removal of Cr was observed after 10 min. • An efficient removal of Pb
• Although the natural eggshell had some removal c was observed with the natural
apacity of Cd and Cr, a complete removal was not eggshells rather than the calcine
accomplished even after 60 min due to quite slow d eggshell.
er removal rate.
8
LITERATURE REVIEW
S.No. 5
JOURNAL NAME: Removal of Cu and Fe from aqueous solution by using eggshell powder as
low cost adsorbent, Advances in Applied Science Research
JOURNAL AUTHOR: Agarwal et al. (2014)
DETAILS CONCLUSION
• They studied the adsorption effi • Analysis shows that eggshell powder can be us
ciency of Cu and Fe. ed in the treatment process of heavy metals a
• It is a batch scale experiment nd the treatment efficiency may be as high as
using adsorbent at 5 different 100% .
concentrations of (5, 10, 20, 40, • It was also observed that the concentration of
100 mg/L) both metals and its mi heavy metals has an important effect on the
xed combination. result of this treatment.

LITERATURE REVIEW
S.No. 6
JOURNAL NAME: Adsorption of Cu2+ from aqueous solution onto iron oxide coated egg
shell powder: Evaluation of equilibrium, isotherms, kinetic and
Regeneration capacity, Arabian Journal of Chemistry
JOURNAL AUTHOR: Ahmad et al. (2010)
DETAILS CONCLUSION
• Studied the adsorption of Cu2+ onto iro • The result shows that the IOESP (iron
n oxide coated eggshell powder. oxide coated eggshell powder) exhibite
• Effect of various operational parameters d a remarkably enhanced adsorption
such as the pH, contact, initial adsorbate capacity for Cu2+.
concentration of Cu2+ ions are investigat
ed.

LITERATURE REVIEW
S.No. 7
JOURNAL NAME: Eggshell Powder as An Adsorbent for Removal of Cu (II) and Cd (II)
from Aqueous Solution,NUCEJ Vol.91 No.2
JOURNAL AUTHOR: Abd Ali et al. (2016)
DETAILS CONCLUSION
• Investigated the adsorption of Cu (II) and Cd • Maximum adsorption capacities for
(II) ions onto eggshell. Cu(II) and Cd(II) were 8.4 and 7.01
• The effects of contact time, initial pH of mg/g respectively.
solution, adsorbent dosage, initial metal
concentration, agitation speed, and tempera
ture were studied in batch experiments.

OBJECTIVES
• To remove copper from industrial wastewater using egg shell and

coconut pith.
• To compare the adsorption capacities of egg shell and coconut pith.
• Recovery of copper from adsorbents.
• Design of industrial process for removal and retrieval of copper.

MATERIALS REQUIRED
CuSO4 Stock Standard Solution Industrial Wastewater
To conduct the experiments, Collected from an electroplating

Copper sulphate (CuSO4) was industry in Ernakulam district
used for the preparation of stock
standard solutions of Copper in
distilled water.
Coconut pith Egg shells

Coconut pith is used as adsorbent. Egg shells are used as adsorbents

MATERIALS REQUIRED
1.Industrial Wastewater
• The sample waste water taken is from an electroplating

industry situated in Ernakulam district.
• This water contains high amount of copper.
• The amount of waste water generated per day is 1 lakh
liters.
Fig.2: collected waste water

MATERIALS REQUIRED
2. Egg shells
• Egg shell is largely-crystalline calcium carbonate.

• 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 bio-adsorbent.
• Eggshells are used as simple, effective and low cost method
for removing copper from industrial wastewater.
Fig.3: Egg shells
15
MATERIALS REQUIRED
3. Coconut pith
• It is an organic by-product which is obtained from
coconut husk while separating fibre from husk.
• Coconut pith is a good bio-adsorbent for removal of
heavy metals from wastewater.
• Here treated and untreated coconut piths are tried as
adsorbents.
Fig.4: Coconut pith

EXPERIMENTAL PROGRAM
Phase I
Identification of industry
Collection of waste water
Estimation of copper content in

waste water
Selection of adsorbents

Phase II
Collection of adsorbents Comparison of adsorption capacities of

egg shells and coconut pith
Preparation of adsorbents
Treatment of industrial wastewater
using adsorbent
Estimation of copper content in
waste water
Retrieval of copper
Copper removal using egg shells
and coconut pith Design of industrial process
18
1. Selection and Preparation of adsorbents
Selection of adsorbents
• Adsorption was chosen as the method for separation of heavy metal as it

allows adhesion of heavy metal dissolved in water to a surface.
• There are various natural adsorbents to remove heavy metals like coconut
pith , egg shells , activated carbon , fly ash etc.
• Out of this we choose egg shell and coconut pith as our adsorbent for removal
of copper from waste water as they are cheap and a waste material.

Egg shells
• Egg shells are washed and removed inner layers
• Dried 1 hour in oven at 100℃
• Keep it at 40℃ for 24 hours.
• Crushed into fine powder.
• Fineness improves the adsorption ability of egg shell.
• Heated egg shells have more adsorption capacity.
20
Continued…
Fig.5: Egg shells prepared

Coconut pith
• 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 sieved
through 300 micron sieve and retained on 150 micron sieve and are oven dried.

(a) (b)
Fig.6: (a) Untreated (b) Treated coconut pith, prepared

2.Estimation of copper content in waste water
Iodometry
• In this method 20 ml of sample is pipetted 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.

2.Estimation of copper content in waste water
Iodometry
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. Copper removal using egg shell and coconut pith
3.1 Copper removal using egg shell
3.1.1 Optimization of egg shell dosage and contact time
• Concentration of copper after adsorption is determined at different combinations

of egg shell dosage and contact time.
• The egg shell dosages taken are 0.1,0.2,0.3,0.4 and 0.5g in 100ml copper solution
prepared in the same concentration of copper that of waste water.
• Contact time taken are10,15,20 and 25minutes.
• Agitation is done using magnetic stirrer at constant rpm.

27
3.1 Copper removal using egg shell
3.1.2 Optimization of pH
• At the optimum contact time and egg shell dosage pH is varied (3,5,7,9,11 etc.)
• pH is adjusted using NaOH and Sulphuric acid.
• Stirred in magnetic stirrer at a constant rpm.
• pH value at which the maximum adsorption taking place is noted.

OBSERVATIONS
Table 1: Conc. of eggshells and contact time
Concentration of egg shell in gm. in 100ml

Contact 0.1 0.2 0.3 0.4 0.5
time
(minutes)
10 56 55.2 54.6 43.2 42.2
15 49.5 44.4 35 25 30.6
20 48.6 44.1 32.7 20.9 12.3
25 41.3 22.2 24.4 1.68 3.36

OBSERVATIONS
Copper content after adsorption (%)

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
Egg shell concentration (g/100 ml copper solution )
Fig. 7: Copper Content After Adsorption V/s Egg Shell Concentration

OBSERVATIONS
pH Volume of sodium Concentration of copper (in
thiosulphate percentage) after adsorption
3 17.5 55.2
5 6.7 30.96
7 - 0
9 - 0
11 - 0
Table.2: Conc. of copper at varying pH

OBSERVATIONS
Concentration of copper after adsorption

Concentration of copper after adsorption v/s pH
60
50
40
(g/100ml copper solution) 30
20
10
0
3 5 7 9 11
Concentration of copper v/s pH
Fig.8: Concentration of copper v/s pH

OBSERVATIONS
Fixation of pH
• At the optimum contact time (25mins) and eggshell concentration (.4g/100ml) pH
is varied between 5 and 7.
• Different pH values taken are 5.5, 6, 6.5.
• pH is adjusted using NaOH and sulphuric acid and stirred in magnetic stirrer at
constant rpm.
• pH value at maximum adsorption is noted.

OBSERVATIONS
Fixation of pH
Table.3: Concentration of copper after adsorption at different pH
pH Concentration of copper after

adsorption
5.5 12.7mg/l
6 9.4mg/l
6.5 0.25mg/l
Result
The maximum adsorption of copper taking place at a pH 6.5.
RESULT
• Adsorption increases with increase in contact time.

• Adsorption increases with increase in concentration of egg shell.
• Complete adsorption taking place at an egg shell concentration of
0.4g/100ml solution and at 25 minutes contact time.
• Optimum contact time =25minutes
• Optimum concentration of egg shell =0.4gm
• Optimum pH =6.5
3.2 Copper removal using coconut pith
3.2.1 Optimization of coconut pith dosage and contact time
• Concentration of copper after adsorption determined at different combinations of

coconut pith dosage and contact time.
• The coconut pith dosages taken are 0.1,0.2,0.3,0.4 and 0.5g in 100ml copper solution
prepared in the same concentration of copper that of waste water.
• Contact time taken are 10,15,20 and 25minutes.
• Agitation is done using magnetic stirrer at constant rpm.

36
3.2 Copper removal using coconut pith
3.2.2 Optimization of pH
• At the optimum contact time and coconut pith dosage pH is varied (3,5,7,9,11 etc.)
• pH is to be adjusted using NaOH and Sulphuric acid.
• Stirred in magnetic stirrer at a constant rpm.
• pH value at which the maximum adsorption taking place is to be noted.

OBSERVATIONS
Table 4: Conc. Of coconut pith and contact time
Concentration of egg shell in gm. in 100ml

Contact t 0.1 0.2 0.3 0.4 0.5
ime
(minute)
10 72 62.23 60.32 50.16 42.8
15 65.4 63.5 61.28 58.42 56.5
20 66.08 62.9 60.3 57.82 55.2
25 63.54 59.4 60.04 57.18 54

OBSERVATIONS
Table 5: Conc. Of coconut pith (treated) and contact time
Concentration of coconut pith in gm. in 100ml

Contact 0.1 0.2 0.3 0.4 0.5
time
(minute)
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

RESULT
• Maximum absorption for untreated cocopeat was at 0.5 g concentration of coconut

pith and 25 minutes contact time.
• The maximum adsorption for treated cocopeat was at 0.5 g conc. of cocopeat and
10minutes contact time.
• The treated coconut pith has more adsorption capacity compared to untreated.

4.Comparison of adsorption capacities of egg shells and coconut pith
• The concentration of copper after adsorption in egg shell and treated, untreated
coconut pith determined at various concentrations and contact time is
compared.
• The egg shells with maximum adsorption capacity is taken as the adsorbent for
the removal of copper from industrial wastewater.

5. Treatment of industrial wastewater using adsorbent
• 100ml of waste water is taken in a beaker.

• pH of water is adjusted to 6.5.
• 0.4g of eggshell is added.
• Stirred in a magnetic stirrer for 25 minutes.
• Remaining copper content is determined by iodometry.
• Copper content in wastewater is estimated as 0.25mg/l after adsorption was
achieved.

6. Retrieval of copper
• 1L of waste water is taken in a beaker.
• Add 90 ml of 0.02N NaOH for adjusting pH.
• 4g adsorbent is added to it.
• Stir the sample in a magnetic stirrer for 25 minutes.
• Heat the sample till it boils.
• Add 90ml/l of 0.02N H2SO4 on boiling.
• Allowed to settle down.
43
• Filter the solution.
• Oven dry the sample contained in the filter paper.
• Separate copper salt from the filter paper.
• The salt obtained was identified to be copper by testing it.
• The industrial waste water had copper chloride and copper nitrate in it and due to
treatment process there could be sulphate.
• So we tested waste water for chlorides, sulphates and nitrates and found that the
salt obtained is copper sulphate.
44
Retrieval Method For Copper After Adsorption From Eggshells
Adjusting Remove
1 litre of Add Stir for
pH using 900ml of
waste 4gm/l of 25
NaOH to wastewater
water eggshell minutes
6.5
Separate the Add 9ml of Remaining

Add 90ml/l waste
colloidal salt NaOH and
H2SO4 stir water is
and heat it upto
for 10mins moved to
wastewater 90°C
heater
Oven dry
Wastewater
and obtain
tank
copper
sulphate
45
OBSERVATIONS
Reaction of Copper Colloid Formation
Cu2+ + 2 NaOH Cu(OH)2 + 2 Na2+
Cu(OH)2 + H2SO4 CuSO4. 2 H2O

RESULT
• Copper was completely removed from waste water and this process have 100%
efficiency.

7. Design of Industrial Process
48
Industrial setup
• Main tank of 1,10,000 L capacity is 7m high and has a hopper bottom of top radius
of 2.4 m and bottom radius of 1.1m.
• Heater of 15,000 L capacity is 4m high and has a hopper bottom of top radius
1.13m and bottom radius of 0.83m.
• Eggshell and copper salt is collected in cylindrical tanks of height 1m and radius of
0.5m.

Industrial setup
• Treated waste water tank of 1,27,000 L capacity is 7m high and has a radius of
2.4m.
• NaOH is stored in a tank of 1.5m height and 0.62m radius.
• Sulphuric acid is stored in tank of 1m height and radius 0.54m
50
Procedure for 1 Lakh litres
• Waste water flows to the main tank and 0.4kg of egg shells are added to it. 900 l
of NaOH is added to it.
• Stir the mix for 25 minutes.
• Main tank with a hopper bottom allows egg shells with copper adsorbed to it to
settle at bottom and waste water at top.
• A part of waste water without copper in it moves to waste water tank and
remaining waste water along with egg shell moves to boiler.
51
Procedure for 1 Lakh litres
• Heater takes 10000 l of water per day and rest of the 90000 l of water moves to
the waste water tank.
• Add 900 l of NaOH to the sample in heater and heat it. On boiling add 900 l of
H2SO4 .
• Allow the sample to settle down. Egg shell settles at bottom over which a colloid of
copper sulphate is formed. Waste water without copper lies over it.
52
CONCLUSION
• Toxic heavy metals are considered one of the pollutants that have direct effect on
man and animals which when released to water bodies without any treatment.
• Process of adsorption is used for removing heavy metals from water.
• Bio-adsorbents like egg shell and coconut pith are used.
• Comparative study of both is carried out by varying their parameters like dosage,
contact time, pH etc., from which the eggshells with maximum adsorption is used to
remove copper from the industrial waste water.

CONCLUSION
• 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.
• The maximum adsorption is taking place at 4g/l eggshell concentration and 25
minutes contact time and the maximum adsorption is at a pH of 6.5.
• The copper can be retrieved successfully using the adopted retrieval technique.
• The industrial process is also designed.
54
REFERENCES
[1] Animesh Agarwal, 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,5(2):75-79
[2] Rais Ahmad, Rajeev Kumar, Shaziya Haseeb,(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, (5)
[3] Renu, Madhu Agarwal and K. Singh,(2017) Heavy metal removal from waste water
using various adsorbents; a review, Jounal of Water Reuse and Desalination (4): 387-419

REFERENCES
[4] 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, 580-584 ISSN 2277-2669
[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 19, 1436–1441
[6] LotfiMonser ,NafaaAdhoum,(2002) “Modified activated carbon for the removal
of copper, zinc, chromium and cyanide from wastewater”, Separation and Purification
Technology 26 , 137–146

REFERENCES
[7] 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 No.2
[8] K.Ravindhranath,(2012) “Simple method for spectrophotometric determination of
traces of copper”,RASSAYAN J .Chem. vol.5

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REMOVAL OF COPPER FROM

INDUSTRIAL WASTE WATER

Removal of copper from industrial wastewater using natural adsorbents 3

• The usage of highly copper concentrated water will affect growth of

Removal of copper from industrial wastewater using natural adsorbents 4

• Investigated the adsorption of toxic • The modified TBA-carbon adsorbent was

Removal of copper from industrial wastewater using natural adsorbents 9

Removal of copper from industrial wastewater using natural adsorbents 10

Removal of copper from industrial wastewater using natural adsorbents 11

• To remove copper from industrial wastewater using egg shell and

• To compare the adsorption capacities of egg shell and coconut pith.

• Recovery of copper from adsorbents.

• Design of industrial process for removal and retrieval of copper.

Removal of copper from industrial wastewater using natural adsorbents 12

CuSO4 Stock Standard Solution Industrial Wastewater

To conduct the experiments, Collected from an electroplating

Coconut pith Egg shells

Removal of copper from industrial wastewater using natural adsorbents 13

• The sample waste water taken is from an electroplating

Removal of copper from industrial wastewater using natural adsorbents 14

• Egg shell is largely-crystalline calcium carbonate.

Removal of copper from industrial wastewater using natural adsorbents 16

Collection of waste water

Estimation of copper content in

Removal of copper from industrial wastewater using natural adsorbents 17

Collection of adsorbents Comparison of adsorption capacities of

• Adsorption was chosen as the method for separation of heavy metal as it

Removal of copper from industrial wastewater using natural adsorbents 19

Fig.5: Egg shells prepared

Removal of copper from industrial wastewater using natural adsorbents 21

• Here treated and untreated coconut piths are tried as adsorbents.

Removal of copper from industrial wastewater using natural adsorbents 22

Fig.6: (a) Untreated (b) Treated coconut pith, prepared

Removal of copper from industrial wastewater using natural adsorbents 23

• In this method 20 ml of sample is pipetted out into a conical flask.

Removal of copper from industrial wastewater using natural adsorbents 24

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

Removal of copper from industrial wastewater using natural adsorbents 25

• Concentration of copper after adsorption is determined at different combinations

• Contact time taken are10,15,20 and 25minutes.

• Agitation is done using magnetic stirrer at constant rpm.

• pH is adjusted using NaOH and Sulphuric acid.

• Stirred in magnetic stirrer at a constant rpm.

• pH value at which the maximum adsorption taking place is noted.

Removal of copper from industrial wastewater using natural adsorbents 28

Concentration of egg shell in gm. in 100ml

Removal of copper from industrial wastewater using natural adsorbents 29

Copper content after adsorption (%)

Egg shell concentration (g/100 ml copper solution )

Fig. 7: Copper Content After Adsorption V/s Egg Shell Concentration

Removal of copper from industrial wastewater using natural adsorbents 30

Table.2: Conc. of copper at varying pH

Removal of copper from industrial wastewater using natural adsorbents 31

Concentration of copper after adsorption

(g/100ml copper solution) 30

Concentration of copper v/s pH

Fig.8: Concentration of copper v/s pH

Removal of copper from industrial wastewater using natural adsorbents 33

pH Concentration of copper after

• Adsorption increases with increase in contact time.

• Concentration of copper after adsorption determined at different combinations of

• Contact time taken are 10,15,20 and 25minutes.

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