Removal of heavy metal ions from industrial waste

water using low cost adsorbent

Presentation
by

Sudeep Asthana
(Ph.D Scholar)
Under the supervision of
Prof. Arinjay Kumar Jain

UNIVERSITY SCHOOL OF CHEMICAL TECHNOLOGY

GURU GOBIND SINGH INDRAPRASTHA UNIVERSITY
Sector 16 C, Dwarka, New Delhi – 110075
 Contents
• Overview
• Introduction
– Waste water treatment methods
– Adsorption
• Objectives
• Experimental work
– Preparation of adsorbent
– Pretreatment of adsorbent
– Adsorption with single metal ion solution
– Adsorption with binary metal ion solutions
– Adsorption with ternary metal ion solutions
• Results and discussions
– Characterization of untreated adsorbent
– Characterization of pretreated adsorbent
– Comparison of both adsorbents
 Contents
– SEM
– FTIR
– ZETA Potential
– BET Surface area
• Adsorption on untreated adsorbent
• Adsorption on Pretreated adsorbent-Optimization of Process Parameters
• Adsorption Isotherms
• Kinetic Studies
• Thermodynamics of adsorption
• Cost optimization & Design of batch reactors
• Conclusions
• List of Publications
 Preview of Adsorption Experiments

1.Feasibility of adsorption with Tea

waste

2.Pretreatments(10) of Tea
waste

3.Adsorption experiments with

pretreated Tea waste

3.1.Single metal ions

3.2.Binary mixtures 3.3.Ternary mixtures
Ni,Cu,Cd,Zn

4.Optimized Treatment Cost

& Batch Reactor Design
 Introduction
Industry is a major consumer of water for its different manufacturing & processing
operations, therefore it also produces a large amount of effluent waste water containing
toxic & hazardous heavy metals in it ,e.g. Ni,Cu,Cd,Zn,Pb,Hg etc.

This waste water effluent if not treated properly becomes dangerous source of toxic heavy
metals which may enter into the environment,causing damage to living beings &
surroundings.

Industry effluent waste water

Damage to Aquatic life & environment

Heavy metals removal from industrial effluent waste water has been the target of great
attention in the last few years because of its potential toxicity and severe ill effects to living
beings & environment.
 Waste Water treatment methods

biological treatment Chemical precipitation

coagulation/flocculation

ion exchange Water Treatment adsorption

Electrochemical
degradation membrane based separation
technology,
 Objectives
• Identifying the low cost natural adsorbent for effective
heavy metal ion removal.
• Preparation of the natural adsorbent to perform
adsorption experiments.
• Enhancement of adsorption efficiency by various
pretreatments to the adsorbent
• Investigating the effect of various process parameters
and optimization of the adsorption process.
• Characterization of fresh adsorbents and the residue
obtained after adsorption experiments.
 Objectives
• Investigation of equilibrium isotherms and kinetics for
the proposed adsorption process.
• Thermodynamic study of the adsorption process.
• Cost optimization & design of batch reactors for
adsorption process.
 Adsorbate- Heavy Metals
Four pollutant heavy metal ions Ni,Cu,Cd and Zn
were selected for experiments

Sources-Minning,petroleum refining,paints,electroplating,fertilizer,pulp &

paper,battery,steel industry,etc

Stock solutions (1000 mg/l) of Ni,Cu,Cd and Zinc ions were

prepared separately and then required dilutions & mixtures were
prepared from it.
 Natural adsorbent-Tea waste

Figure shows the actual tea production & consumption worldwide also it shows the
projected tea production for the year 2023, i.e 7140 .50 thousand tonnes

(Thousand tonnes) Actual and Projected Tea Production

(thousand tonnes)
4040 4364.7 4627 4784.5 5063.9
7140.5
6000 2916 4180.3 4449.6 4626.8 4842.1
4000
5063.9
2000
0
2009 2010 2011
2012
2013

world tea production world tea consumption

2013 2023

Official statistical data for tea waste

 Preparation of adsorbent

Steam Dried in oven

treatment in at 800C for
cooker for 20 24 h
min

Repeated
Tea waste
several Pulverized
collected from
times by grinder
GGSIPU hostel

Again dried in oven for 1 h at 700C Size 0.149 mm

& kept in air tight container ready
to use tea waste adsorbent
 Adsorption Process Flow Chart with tea waste
1.Feasibility of adsorption

Adsorption of single metal ions on tea waste

Kept in temperature
Metal ion 100 ml
controlled shaker at specific
Samples of diff conc.+ Filteration by filter
reaction conditions (pH,
adsorbent added to paper
shaking speed, reaction
sample
time,temp)

AAS analysis to determine the

unknown concentration of
Metal ion present in the
Optimization of Process Parameters sample after adsorption
• Dosage of Absorbent
• Reaction pH
• Time
• Initial metal ion Concentration
• Temperature
 2.Enhancement of adsorption efficiency
Pretreatments of adsorbent tea waste

The tea waste was subjected to 10 pretreatments with following chemicals:

S.No. Chemical S.No. Chemical

1 0.1M NaOH 6 0.1M H2C2O4

2 0.1M KOH 7 0.1M HCl

3 0.1M Na2S 8 0.1M H2SO4

4 0.1M Na2CO3 9 0.1M HNO3

5 0.1M HCHO 10 0.1M H3P04

 Pretreatment of adsorbent tea waste

Tea waste mixed

with chemical in Filtration by
beaker & kept for vacuum filter
3 h -5 h

Addition of chemical Washed

with
Tea waste powder distilled
water
Size 0.149 mm
Dried in oven
at 800C for
24 h

Kept in air tight

container ready to use
pretreated tea waste
 Adsorption Process Flow Chart with pretreated (ATTW) tea waste

2.For Enhancement of adsorption efficiency

Adsorption of single metal ions on pretreated tea waste

Kept in temperature
Metal ion 100 ml
controlled shaker at specific Filtration by filter
Samples of diff conc.+
reaction conditions (pH, paper
adsorbent added to
shaking speed, reaction
sample
time,temp)

AAS analysis to determine the

unknown concentration of
Optimization of Process Parameters Metal ion present in the
• Dosage of Absorbent sample after adsorption
• Reaction pH
• Reaction Time
• Initial metal ion Concentration
• Temperature
 Adsorption Process Flow Chart with pretreated (ATTW) tea waste

Adsorption of binary mixture of metal ions on pretreated tea waste

Binary mixtures 100 ml Kept in temperature

Samples of diff conc.+ controlled shaker at specific Filtration by filter
adsorbent added to reaction conditions (pH, paper
sample shaking speed, reaction
time,temp)

AAS analysis to determine the

unknown concentration of
Process Parameters two metal ions present in the
• Reaction Time sample after adsorption
• Initial metal ion Concentration
 Adsorption Process Flow Chart with pretreated (ATTW) tea waste

Adsorption of ternary mixture of metal ions on pretreated tea waste

ternary mixtures 100 Kept in temperature

ml samples of diff controlled shaker at specific Filtration by filter
conc.+ adsorbent reaction conditions (pH, paper
added to sample shaking speed, reaction
time,temp)

AAS analysis to determine the

unknown concentration of
Process Parameters two metal ions present in the
• Initial metal ion Concentration sample after adsorption
 Observations & Calculations :

• The amount of metal ion adsorbed qt (mg /g), at contacting

time of t (min) with initial metal ion concentration (Co) is
calculated as:
qt = (Co − Ct )V /W -----------(1)

where Ct is the residual metal concentration at time t; W (g) is

the weight of adsorbent per V (L) of the reaction mixture
• The percentage of removed metal ions ( R %) in solution is
calculated using Equation ( 2)

R (%) = (C0 - Ct) / C0 x100 ----------(2)

 Characterization of Tea waste

Characterization is done by the following:

• SEM (Scanning Electron Microscopy)

• FTIR (Fourier Transmission Infrared Spectroscopy)
• ZETA POTENTIAL
• SURFACE AREA & PORE VOLUME (BET)
 Scanning Electron Microscopy-Images

Tea Waste Alkali Treated Tea Waste

SEM image is showing irregular structure with tiny pores which seems to be increased after
the alkali treatment also confirmed by the pore volume data
 Scanning Electron Microscopy-Images

ATTW Before adsorption ATTW After Ni adsorption

 Scanning Electron Microscopy-Images

ATTW Before adsorption ATTW After Cu adsorption

 Scanning Electron Microscopy-Images

ATTW Before adsorption ATTW After Cd adsorption

 Scanning Electron Microscopy-Images

ATTW Before adsorption ATTW After Zn adsorption

 Fourier Transmission Infrared Alkali treated tea waste ATTW for Ni

Stretch shown ,Wave number (cm-1) Functional group Compounds

3435.4-3445.3 O-H Stretch Phenol,alcohols

2925.6-2940.8 C-H Stretch Alkyl

1665.1-1678.5 C=O Stretch Ketone

 Fourier Transmission Infrared Alkali treated tea waste ATTW for Cu

Stretch shown ,Wave number (cm-1) Functional group Compounds

3430.6-3441.3 O-H Stretch Phenol,alcohols

2922.3-2933.5 C-H Stretch Alkyl

2291.3-2293.4 CΞN Nitrile

 Fourier Transmission Infrared Alkali treated tea waste ATTW for Cd

Stretch shown ,Wave number (cm-1) Functional group Compounds

3431.6-3439.3 O-H Stretch Phenol,alcohols

2922.3-2932.5 C-H Stretch Alkyl

2291.3-2293.4 CΞN Nitrile

 Fourier Transmission Infrared Alkali treated tea waste ATTW for Zn

Stretch shown ,Wave number (cm-1) Functional group Compounds

3430.3-3434.1 O-H Stretch Phenol,alcohols

2921.5-2927.2.5 C-H Stretch Alkyl

2291.7-2292.3 CΞN Nitrile

 Zeta Potential
TW ATTW
15

10
Zeta potential (mV)

0
0 1 2 3 4 5 6 7 8 9
-5

-10

-15

-20
pH

Comparison of Tea waste & alkali treated Tea waste zeta potentials

The pHzpc value is slightly increased after the alkali treatment of adsorbent
 BET Surface Area

S.N. Property Tea Waste ATTW

1. Specific Surface area BET

( m2 / g ) 122.03 225.3

2. Pore Volume
( cm3 / g ) 0.132 0.175
Adsorption on untreated adsorbent-Tea waste optimum parameters

Metal Conc Eqbm time TW dose(g) pH Removal Temp

(ppm) (min) (%) (K)
Ni 20 120 2 6 75.8 293
Cu 20 90 2 6 72.1 293
Cd 20 120 2 6 68.2 293
Zn 20 90 2 5 64.3 293
 Adsorption on untreated adsorbent-Tea waste

Adsorption of Equilibrium study,

Ni,Cu,Cd,Zn on Langmuir model best fit
Tea waste Q values-
Ni(14.1),Cu(14.3),Cd(12.9),Zn(10.8)
(mg/g)

Kinetics study,
Pseudo second order
is the best fit model

Thermodynamics study,
Process spontaneous,
exothermic in nature
 Removal of Ni –Comparative study, adsorption by tea waste
and 10 pretreated tea waste
The tea waste was subjected to 10 pretreatments and the comparative % removal of
Ni with pretreated tea waste & tea waste is shown in the following bar graph:

% Removal Ni

100 92.1 92 90.03 88.8

80 64.8 65.1
60
40 24.9
20 6.9 4.5 2.9 0.6
0

Initial metal ion concentration=100ppm, Adsorbent dose=0.6g/100ml,

pH=6,Temperature=303K, ,Shaking speed = 150 rpm,Time =2h,
concentration of all above chemicals = 0.1 M
 Removal of Ni –Comparative study, adsorption by ATTW & STTW

The maximum adsorption 92.1% was found with ATTW and almost similar
92.0% adsorption was obtained with STTW.To find out the best pre-treatment
methods out of these two further investigations were made.
ATTW- 0.1 M NaOH alkali treated tea waste.
STTW- 0.1 M Na2S sodium sulphide treated tea waste. STTW ATTW
STTW ATTW
STTW ATTW

95 100
100
80
85
%R
90 60

%R
%R

75
80
40
65 20
70
55 0
0 50 100 150 200 250
0 0.4 0.8 1.2 1.6 2 2.4 0 2 4 6
Initial Ni ion concentration,ppm Adsorbent dose,g Time, h

STTW ATTW
STTW ATTW

120 20 Langmuir adsorption capacity

Zeta Potential,mV

100
80
10 Q(mg/g)-
%R

60 0 ATTW-30.31
40 0 5 10
20
-10 STTW-27.03
0 -20
pH value
0 5 10 15
pH value
Result-ATTW was found better for Ni
 Removal of Ni –Comparative study, adsorption by ATTW & STTW

1.The ATTW was found better adsorbent than STTW with a maximum removal
of Ni ion 92.1 %.
2.The experiments were performed further with 0.1 M NaOH solution alkali
treated tea waste (ATTW)

35
 Removal of Ni-Effect of contact time
120
Adsorbent(ATTW) dose=0.6 g/100 ml,
pH=6, temp=303 K, shaking speed=150
100
rpm
% Removal Ni

80

60 20 ppm

60 ppm
40
100
ppm 18
20
16

14
0
0 1 2 3 4 12

q (mg/g)
Time (h) 10

8 20 ppm

The equilibrium time= 90 min 6

60 ppm
100 ppm
4
140 ppm
2
200 ppm
0
0 1 2 3 4

Time (h)
 Removal of Ni-Effect of initial concentration
293 K 303 K 313 K 323 K 333 K

100
Adsorbent(ATTW) dose=0.6 g/100 ml,
95
pH=6, shaking speed=150 rpm contact time
90 = 90 min
% Removal

85

80 293 K 303 K 313 K 323 K 333 K

30
75

70
25
65

60
20
0 50 100 150 200 250

q ,(mg/g)
Ni ion concentration (ppm)
15

10

The maximum removal was found 5

at 20 ppm and 293 K temperature
0
0 50 100 150 200

Ni ion conc (ppm)

 Removal of Ni-Effect of adsorbent dose
100

Sample volume=100 ml, pH=6, temp=303 K,

90
shaking=150 rpm contact time = 90 min
80
% Removal Ni

70

60 20 ppm
60 ppm 40
50
100 ppm 35 20 ppm
140 ppm
40 60 ppm
30
200 ppm 100 ppm
140 ppm

q (mg/g)
30 25
200 ppm
0 0.5 1 1.5 2 2.5
20
Dose of ATTW (g)
15

10

The maximum removal was found 5

at ATTW dose of 0.6 g 0
0 0.5 1 1.5 2 2.5

Dose of ATTW (g)

 Removal of Ni-Effect of pH
100

95 Adsorbent(ATTW) dose=0.6 g/100 ml,

90
shaking speed=150 rpm contact time = 90
20 ppm min,temp=303 K
% Removal

85
60 ppm
80
100 ppm
18
75 140 ppm
16
70 200 ppm

65 14

60 12
3 5 7 9 11 20 ppm

q ,(mg/g)
pH value 10 60 ppm
100 ppm
8
140 ppm

6 200 ppm
The maximum removal was found
4
at pH = 5
2

0
0 2 4 6 8 10 12

pH value
 Removal of Ni-Effect of temperature
20 ppm 60 ppm 100 ppm 140 ppm 200 ppm
100
Adsorbent(ATTW) dose=0.6 g/100 ml,
95
pH=6, shaking speed=150 rpm contact time
90 = 90 min
% Removal

85

80

75 20 ppm 60 ppm 100 ppm 140 ppm 200 ppm

17
70

65 16
60
290 300 310 320 330 340 15

Temperature K

q (mg/g)
14

13

The maximum removal was found 12

at temperature = 293 K 11

10
290 300 310 320 330 340

Temperature K
 Removal of Ni-Optimum conditions

Metal Equilibrium time Initial ion ATTW dose (g) pH Temperature

(min) conc(ppm) (K)

Ni 90 20 0.6 5 293
 Removal of Cu –Comparative study, adsorption by tea waste and
pretreated tea waste
The tea waste was subjected to 10 pretreatments and the comparative % removal of
Cu with pretreated tea waste & tea waste is shown in the following bar graph:
% Removal Cu

100
87.3 83.5 83.4 82.3
80

62.1 50.2
60

40
22.7
20
5.2 3.3 1.3 0
0
NaOH KOH Na2S HCHO Na2CO3 H2C2O4 HCl H2SO4 H3PO4 HNO3 TW

Initial metal ion concentration = 100 ppm,Adsorbent dose = 0.6 g /100ml,

pH = 6,Temperature = 303 K,Time = 2 h, Shaking speed = 150 rpm,
concentration of all above chemicals = 0.1 M
 Removal of Cu –Comparative study, adsorption by tea waste and
pretreated tea waste
S. NO. Conc Chemical % Removal Cu
1 0.1 M NaOH 87.3
2 0.1 M KOH 83.5
3 0.1 M Na2S 83.4
4 0.1 M HCHO 82.3
5 0.1 M Na2CO3 62.1
6 0.1 M H2C2O4 22.7
7 0.1 M HCl 5.2
8 0.1 M H2SO4 3.3
9 0.1 M H3PO4 1.3
10 0.1 M HNO3 0
11 - UNTREATED TW 50.2
1.The maximum removal of Cu ion was found 87.3 % with tea waste treated
with 0.1 M NaOH solution against 50.2 % by tea waste only.
2.The experiments were performed further to find the optimum conditions &
for equilibrium, kinetics & thermodynamics study with tea waste treated
with 0.1 M NaOH solution called as alkali treated tea waste (ATTW)
 110
100 100

% Removal Cu

% Removal Cu
90 95
80 20 ppm 90
70 85 293 K
60 ppm
60 80 303 K
100 ppm 75
50 313 K
40 140 ppm 70
65 323 K
30 200 ppm
20 60 333 K
0 1 2 3 4 0 50 100 150 200 250
Time (h) Cu ion concentration (ppm)
Adsorbent(ATTW) dose=0.6 g/100 ml, pH=6, Adsorbent(ATTW)dose=0.6g/100ml, pH=6,
temp=303 K, shaking speed=150 rpm shaking speed=150 rpm contact time = 75 min
30
18 25
16

q (mg/g)
14 20 293 K
q (mg/g)

12 20 ppm
15 303 K
10 60ppm
313 K
8 100ppm 10
323 K
6 140ppm 5 333 K
4
200ppm
2 0
0 0 50 100 150 200 250
0 1 2 3 4 Cu ion concentration (ppm)
Time (h)
The maximum removal was found
The equilibrium time= 75min at 20 ppm and 293 K temperature
 120
120

% Removal Cu
% Removal Cu
100 100

80 20 ppm 80
20 ppm
60 ppm
60 60 60 ppm
100 ppm
40 140 ppm 40 100 ppm

20 200 ppm 140 ppm

20
0 200 ppm
0
0 0.5 1 1.5 2 2.5
0 2 4 6 8 10 12
ATTW Dose (g)
Sample volume=100 ml, pH=6, temp=303 K,
pH value
shaking=150 rpm contact time = 75 min
Adsorbent(ATTW) dose=0.6 g/100 ml, shaking
40 speed=150 rpm contact time = 75 min,temp=303 K
35
18
30 16
q (mg/g)

25 20 ppm 14

q (mg/g)
12 20 ppm
20 60 ppm
10 60 ppm
15 100 ppm
8 100 ppm
10 140 ppm
6
140 ppm
5 200 ppm 4
200 ppm
0 2
0 0.5 1 1.5 2 2.5 0
0 2 4 6 8 10 12
ATTW Dose (g)
pH value
The maximum removal was found at
ATTW dose of 0.4 g The maximum removal was found at pH = 5
 20 ppm 60 ppm 100 ppm
20 ppm 60 ppm 100 ppm 140 ppm 200 ppm
140 ppm 200 ppm 17
100 16
15
% Removal Cu

q (mg/g)
95
14
90 13
85 12
80 11
75 10
9
70
8
65
290 300 310 320 330 340
60
290 300 310 320 330 340 Temperature K
Temperature K
Adsorbent(ATTW) dose=0.6 g/100 ml, shaking The maximum removal was found at
speed=150 rpm contact time = 75 min, temperature = 293 K

Metal Equilibrium time Initial ion ATTW dose (g) pH Temperature (K)
(min) conc(ppm)
Cu 75 20 0.4 5 293
 Removal of Cd –Comparative study, adsorption by tea waste and
pretreated tea waste
The tea waste was subjected to 10 pretreatments and the comparative % removal of
Cd with pretreated tea waste & tea waste is shown in the following bar graph:

% Removal Cd

100 86.4 82.2 81.5 80.2

80 61.1 47.1
60
40
18.6
20 5.4 2.3 1.5 0
0

Initial metal ion concentration = 100 ppm,Adsorbent dose = 0.6 g /100 ml

pH = 6,Temperature = 303 K,Time = 2 h ,Shaking speed = 150 rpm,
concentration of all above chemicals = 0.1 M
 Removal of Cd –Comparative study, adsorption by tea waste and
pretreated tea waste
S. NO. Conc Chemical % Removal Cd
1 0.1 M NaOH 86.4
2 0.1 M KOH 82.2
3 0.1 M HCHO 81.5
4 0.1 M Na2S 80.2
5 0.1 M Na2CO3 61.1
6 0.1 M H2C2O4 18.6
7 0.1 M HCl 5.4
8 0.1 M H2SO4 2.3
9 0.1 M H3PO4 1.5
10 0.1 M HNO3 0
11 - UNTREATED TW 47.1
1.The maximum removal of Cd ion was found 86.4 % with tea waste treated with
0.1 M NaOH solution against 47.1 % by tea waste only.
2.The experiments were performed further to find the optimum conditions & for
equilibrium, kinetics & thermodynamics study with tea waste treated with 0.1 M
NaOH solution called as alkali treated tea waste (ATTW)
 100 100

90 95

% Removal Cd
% Removal Cd

80 90

70 85
293 K
20 ppm
60 80 303 K
60 ppm
50 75 313 K
100 ppm
323 K
40 140 ppm 70
333 K
200 ppm
30 65

20 60
0 0.5 1 1.5 2 2.5 3 3.5 0 50 100 150 200 250

Time (h) Cd ion concentration (ppm)

Adsorbent(ATTW) dose=0.6 g/100 ml, pH=6, Adsorbent(ATTW) dose=0.6 g/100 ml, pH=6,
temp=303 K, shaking speed=150 rpm shaking speed=150 rpm contact time = 90 min

The equilibrium time= 90min

The maximum removal was found at 20 ppm
and 293 K temperature
 120
100
90 100
80

% Removal Cd
% Removal Cd

70 80
20 ppm
60
20 ppm 60 60 ppm
50
60 ppm 100 ppm
40
100 ppm 40 140 ppm
30
140 ppm 200 ppm
20 20
200 ppm
10
0 0
0 0.5 1 1.5 2 2.5 0 2 4 6 8 10 12

ATTW Dose (g) pH value

Sample volume=100 ml, pH=6, temp=303 K, Adsorbent(ATTW) dose=0.6 g/100 ml, shaking
shaking=150 rpm contact time = 90 min speed=150 rpm contact time = 90 min,temp=303 K

The maximum removal was found at ATTW The maximum removal was found at pH = 6
dose of 0.8 g
 20 ppm
100 60 ppm 100 ppm 140 ppm 200 ppm

95
% Removal Cd

90
85
80
75
70
65
60
290 300 310 320 330 340

Temperature K
Adsorbent(ATTW) dose=0.6 g/100 ml, shaking The maximum removal was found
speed=150 rpm contact time = 90 min, at temperature = 293 K

Removal of Cd-Optimum conditions

Metal Equilibrium time Initial ion ATTW dose (g) pH Temperature (K)
(min) conc(ppm)

Cd 90 20 0.8 6 293
 Removal of Zn –Comparative study, adsorption by tea waste and
pretreated tea waste
The tea waste was subjected to 10 pretreatments and the comparative % removal of
Zn with pretreated tea waste & tea waste is shown in the following bar graph:

% Removal Zn

100
82.4 78.9 78.7 76.5
80

60
55.1 43.2

40

17.4
20
4.5 2.3 1.5 0
0
NaOH KOH HCHO Na2S Na2CO3 H2C2O4 HCl H2SO4 H3PO4 HNO3 TW

Initial metal ion concentration = 100 ppm,Adsorbent dose = 0.6 g /100 ml

pH = 6,Temperature = 303 K,Time = 2 h ,Shaking speed = 150 rpm,
concentration of all above chemicals = 0.1 M
 Removal of Zn –Comparative study, adsorption by tea waste and
pretreated tea waste
S. NO. Conc Chemical % Removal Zn
1 0.1 M NaOH 82.4
2 0.1 M KOH 78.9
3 0.1 M HCHO 78.7
4 0.1 M Na2S 76.5
5 0.1 M Na2CO3 55.1
6 0.1 M H2C2O4 17.4
7 0.1 M HCl 4.5
8 0.1 M H2SO4 2.3
9 0.1 M H3PO4 1.5
10 0.1 M HNO3 0
11 - UNTREATED TW 43.2
1.The maximum removal of Zn ion was found 82.4 % with tea waste treated with
0.1 M NaOH solution against 43.2 % by tea waste only.
2.The experiments were performed further to find the optimum conditions & for
equilibrium, kinetics & thermodynamics study with tea waste treated with 0.1 M
NaOH solution called as alkali treated tea waste (ATTW)
 293 K 303 K 313 K 323 K 333 K
100
100
90

80 95
% Removal Zn

70 90

% Removal Zn
60 20 ppm 85

50 60 ppm
80
100 ppm
40
140 ppm 75
30 200 ppm
70
20
65
10
60
0
0 50 100 150 200 250
0 1 2 3 4
Time (h) Zn ion concentration (ppm)

Adsorbent(ATTW) dose=0.6 g/100 ml, pH=6, Adsorbent(ATTW) dose=0.6 g/100 ml, pH=6,
temp=303 K, shaking speed=150 rpm shaking speed=150 rpm contact time = 60
min

The equilibrium time= 60 min The maximum removal was found at 20

ppm and 293 K temperature
 20 ppm 60 ppm 100 ppm 140 ppm 200 ppm
120
100

90 100

% Removal Zn
% Removal Zn

80
80

70
20 ppm
60
60 ppm
60
100 ppm
40
50 140 ppm
200 ppm
40 20

30 0
0 0.5 1 1.5 2 2.5 0 2 4 6 8 10 12
Dose of ATTW (g) pH value

Sample volume=100 ml, pH=6, temp=303 K, Adsorbent(ATTW) dose=0.6 g/100 ml,

shaking=150 rpm contact time = 60 min shaking speed=150 rpm,
contact time = 60 min,temp=303 K

The maximum removal was found at The maximum removal was found at pH = 5
ATTW dose of 0.6 g
 20 ppm 60 ppm 100 ppm 140 ppm 200 ppm
Adsorbent(ATTW) dose=0.6 g/100 ml, 100
shaking speed=150 rpm contact time = 60
95
min,
90

% Removal Zn
The maximum removal was found at 85
temperature = 293 K
80

75

70

65

60
290 300 310 320 330 340

Temperature K
Removal of Zn-Optimum conditions
Metal Equilibrium time Initial ion ATTW dose (g) pH Temperature (K)
(min) conc(ppm)

Zn 60 20 0.6 5 293
 Removal of Single Metals-Optimum conditions

Metal Equilibrium time Initial ion ATTW dose (g) pH Temperature (K)
(min) conc(ppm)

Ni 90 20 0.6 5 293

Cu 75 20 0.4 5 293

Cd 90 20 0.8 6 293

Zn 60 20 0.6 5 293
Overall comparison of adsorption of metals
Overall comparison of adsorption of metals
Overall comparison of adsorption of metals
Overall comparison of adsorption of metals
Overall comparison of adsorption of various metals
Heavy Metal Removal from pretreated TW
Metal Untreated tea waste Alkali treated tea waste
Removal (%) (%)
Ni 65.1 92.1

Cu 61.3 87.3

Cd 58.9 86.4

Zn 54.2 82.8
 Overall comparison of adsorption of various
metals

The alkali treated tea waste (ATTW) shows good

adsorption properties under various operating
conditions
The relative removal percentage of metals is as
follows:
Ni (98.5%) > Cu (96.6%) > Cd (94.6%) > Zn (93.5%)
Zn=20ppm
Cd=20ppm
Cu=20ppm
Zn=20ppm
Cd=20ppm
Ni=20ppm
Zn=20ppm
Cu=20ppm
Ni=20ppm
Cd=20ppm
Cu=20ppm
Ni=20ppm
 Overall comparison of adsorption of metals in
binary mixtures
The metal percentage removal reduces in case of
binary mixtures of metal ions as compared to single
of metal ion solution
The removal of Ni ions reduces up to 25.2% in its
binary mixtures.
The removal of Cu ions reduces up to 26.3% in its
binary mixtures.
The removal of Cd ions reduces up to 25.2% in its
binary mixtures.
The removal of Zn ions reduces up to 27.6 % in its
binary mixtures at room 303 K temperature
Cd,Zn=20ppm
Cu,Zn=20ppm
Cu,Cd=20ppm
Cd,Zn=20ppm
Ni,Zn=20ppm
Ni,Cd=20ppm
Cu,Zn=20ppm
Ni,Zn=20ppm
Ni,Cu=20ppm
Cu,Cd=20ppm
Ni,Cd=20ppm
Ni,Cu=20ppm
 Overall comparison of adsorption of metals in
ternary mixtures
The metal percentage removal reduces in case of
ternary mixtures of metal ions as compared to single
& binary mixtures of metal ion solution
The removal of Ni ions reduces up to 37.3% in its
ternary mixtures.
The removal of Cu ions reduces up to 44.5% in its
ternary mixtures.
The removal of Cd ions reduces up to 37.3% in its
ternary mixtures.
The removal of Zn ions reduces up to 53.4% in its
ternary mixtures at room 303 K temperature
 Langmuir Isotherm Model

Ni, T= 293 K Ni, T= 303 K Ni, T=313 K

0.18 0.35
0.18
0.16 0.3
0.16
0.14
0.14 0.25
0.12
0.12 0.1 0.2

1/qe

1/qe
0.1
1/qe

0.08
0.08 y = 0.2232x + 0.0324 0.15
y = 0.0748x + 0.0408 0.06 y = 0.3839x + 0.0354
0.06 R² = 0.996 0.1
R² = 0.9696 0.04 R² = 0.9995
0.04 0.02 0.05
0.02 0
0
0 0 0.2 0.4 0.6
0 0.2 0.4 0.6 0.8
0 0.5 1 1.5 2 1/Ce
1/Ce
1/Ce

Ni, T= 323 K Ni, T= 333 K

0.4
0.35
0.35 y = 0.5329x + 0.0381
0.3 y = 0.4709x + 0.0354
R² = 0.9907
R² = 0.9985 0.3
0.25
0.25
1/qe

0.2 0.2
1/qe

0.15 0.15
0.1 0.1
0.05 0.05
0
0
0 0.2 0.4 0.6
0 0.2 0.4 0.6 0.8
1/Ce
1/Ce
 Freundlich Isotherm Model

Ni, T=293 K,Freundlich Ni, T= 303 K, Freundlich Ni, T= 313 K,

1.6 1.6 Freundlich
2
1.4 1.4
1.2 1.2 1.5

log qe
1 1 1

log qe
log qe

0.8 0.8 y = 0.457x + 0.7589 y = 0.5545x + 0.5127

0.5
y = 0.4099x + 0.8969 0.6 R² = 0.9726 R² = 0.97
0.6
R² = 0.9857 0.4 0
0.4
0.2 0 1 2
0.2
0 log Ce
0 -1 -0.5 0 0.5 1 1.5 2
-1 0 1 2
log Ce
log Ce

Ni, T= 333 K, Freundlich

Ni,T= 323 K, Freundlich 2
2
1.5
1.5
log qe

1
log qe

1 y = 0.5802x + 0.4029
0.5
y = 0.5752x + 0.45 R² = 0.9664
0.5 0
R² = 0.9658
0 0.5 1 1.5 2
0 log Ce
0 0.5 1 1.5 2
log Ce
 Dubini Radushkevich Isotherm Model

Ni, T= 293 K,DR Ni, T= 303 K, DR Ni, T= 313 K,DR

3.5 3.5 3.5
3 y = -0.4394x + 3.1107 3 3
R² = 0.9145 y = -1.4669x + 3.0823
2.5 2.5 2.5 R² = 0.9431
2

ln qe
2
ln qe

ln qe
1.5 1.5
1.5
1 y = -0.5566x + 3.0069
1 R² = 0.8172 1
0.5 0.5
0.5
0
0 0
0 1 2 3 4
0 1 2 3 4 5 6 0 1 2
€²x1000
€²x1000 €²x1000

Ni, T= 323 K, DR Ni, T= 333 K, DR

3.5
3.5
3
3
2.5 y = -1.7252x + 3.015
2.5 y = -1.6434x + 3.0603 R² = 0.91
2
ln qe

2 R² = 0.9315
ln qe

1.5
1.5
1
1
0.5
0.5
0
0
0 0.5 1 1.5
0 0.5 1 1.5
€²x10³
€²x1000
 FREUNDLICH
LANGMUIR PARAMETERS PARAMETERS DUBININ
RADUSHKEVICH PARAMETERS

TEMP,K KL (L/g) Qc (mg/g) RL (L/mg) R2 1/n(g/L) n R2 KF(mg/g) Kd/1000 E (kJ/mol) R2 Qc (mg/g)

293 0.54 25 0.0092<R<0.085 0.969 0.409 2.45 0.985 7.87 0.439 1.067 0.914 22.42

303 0.14 31.25 0.0337<R<0.258 0.996 0.457 2.19 0.972 5.73 0.556 0.948 0.817 20.1

Ni 313 0.09 28.57 0.0519<R<0.35 0.999 0.554 1.81 0.97 3.25 1.47 0.583 0.943 21.76

0.0629<R<0.41
323 0.07 28.57 6 0.998 0.575 1.74 0.965 2.82 1.64 0.552 0.931 21.33

0.0654<R<0.41
333 0.07 26.32 2 0.99 0.58 1.73 0.966 2.52 1.725 0.538 0.91 20.39
The adsorption capacity of ATTW at room
temperature 303 K was calculated on the basis of
Langmuir isotherm and was found 31.25 mg/g for
Ni, 20.4 mg/g for Cu, 25.64 mg/g for Cd and 20.4
mg/g for Zn
 Langmuir Isotherm Model
Ni-Cu Mixture Ni-Cd
0.45 0.45
0.4 0.4
0.35 0.35
0.3 0.3
0.25
1/qe

0.25

1/qe
0.2 y = 1.8718x + 0.0639 y = 1.7113x + 0.0553
0.15 0.2
R² = 0.9932 R² = 0.9971
0.1 0.15
0.05 0.1
0 0.05
0 0.05 0.1 0.15 0.2 0
1/Ce 0 0.05 0.1 0.15 0.2 0.25
1/Ce

Ni-Zn
0.45
0.4
0.35
0.3
0.25 y = 1.4817x + 0.0485
1/qe

0.2 R² = 0.9982
0.15
0.1
0.05
0
0 0.05 0.1 0.15 0.2 0.25
1/Ce
 Freundlich Isotherm Model
Ni-Cu Ni-Cd
1.2
1.2
1
1
0.8
0.8
log qe

0.6 y = 0.6866x - 0.1119

log qe
R² = 0.9976 0.6 y = 0.6997x - 0.0788
R² = 0.9947
0.4
0.4
0.2
0.2
0
0 0.5 1 1.5 2 0
log Ce 0 0.5 1 1.5 2
log Ce
Ni-Zn
1.2

0.8
log qe

0.6 y = 0.7202x - 0.039

R² = 0.9964
0.4

0.2

0
0 0.5 1 1.5 2
log Ce
 LANGMUIR PARAMETERS FREUNDLICH PARAMETERS

Mixture KL (L/g) Qc (mg/g) R2

1/n(g/L) n R2 KF(mg/g)

Ni-Cu 0.033672 15.87302 0.993

0.686 1.457726 0.997 0.775
Ni-Cd 0.032145 18.18182 0.997
0.699 1.430615 0.994 0.836

Ni-Zn 0.032411 20.83333 0.998 0.72 1.388889 0.996 0.914

The adsorption capacity of ATTW at room temperature
303 K was calculated on the basis of Langmuir isotherm
and was found maximum 20.83 mg/g for Ni-Zn mixtures,
22.73 mg/g for Cu-Zn mixtures, 19.23 mg/g for Cd-Cu
mixtures and 17.85 mg/g for Zn-Cd mixtures
 Langmuir Isotherm Model

Ni-Cu-Cd Ni-Cu-Zn
0.6 0.6

0.5 0.5

0.4 0.4
y = 2.982x + 0.0711

1/qe
0.3 R² = 0.9903
1/qe

0.3
y = 3.1904x + 0.088 0.2
0.2 R² = 0.9829
0.1
0.1
0
0 0 0.05 0.1 0.15
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 1/Ce
1/Ce

Ni-Cd-Zn
0.5

0.4

0.3
1/qe

y = 2.8004x + 0.0551
0.2 R² = 0.9981

0.1

0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16
1/Ce
 Freundlich Isotherm Model

Ni-Cu-Cd Ni-Cu-Zn
1
1
0.9
0.9
0.8 0.8
0.7 0.7
0.6 0.6

log qe
log qe

0.5 0.5
y = 0.6719x - 0.2949 y = 0.7175x - 0.3001
0.4 0.4
R² = 0.9892 R² = 0.9976
0.3 0.3
0.2 0.2
0.1 0.1
0 0
0 0.5 1 1.5 2 0 0.5 1 1.5 2
log Ce log Ce

Ni-Cd-Zn
1.2

0.8
log qe

0.6
y = 0.74x - 0.2749
0.4 R² = 0.9949
0.2

0
0 0.5 1 1.5 2
log Ce
 LANGMUIR PARAMETERS FREUNDLICH PARAMETERS

Mixture KL (L/g) Qc (mg/g) R2 n R2 KF(mg/g)

Ni-Cu-Cd 0.027586 11.36364 0.982 1.490313 0.989 0.508

Ni-Cu-Zn 0.02381 14.08451 0.99 1.3947 0.997 0.501

Ni-Cd-Zn 0.019643 18.18182 0.998 1.351351 0.994 0.532

The adsorption capacity of ATTW at room
temperature 303 K was calculated on the basis of
Langmuir isotherm and was found maximum 18.18
mg/g for Ni-Cd-Zn mixture, 9.52 mg/g for Cu-Cd-Zn
mixture, 9.43 mg/g for Cd-Ni-Cu mixture and 7.52
mg/g for Zn-Cu-Cd mixture
 Pseudo First order

Ni = 60 PPM,Pseudo first Ni = 100 PPM,Pseudo

Ni = 20 PPM, Pseudo first
order first order
order 4
4
4 y = -0.0414x + 2.9638
y = -0.0313x + 2.6273 2 3
3 R² = 0.9843
R² = 0.9787 2 y = -0.0297x + 2.6273
2

ln(qe-qt)
0 R² = 0.9885

ln(qe-qt)
1 1
ln(qe-qt)

0 50 100 150 200

0 0
-2
-1 0 50 100 150 200 -1 0 50 100 150 200
-2 -4 -2
-3 -3
-4 -6
t,min t,min -4
t,min

Ni = 140 PPM,Pseudo first Ni = 200 PPM, Pseudo first order

order 3

4 2
y = -0.0313x + 2.8034 1 y = -0.0308x + 2.5838
R² = 0.9762
ln(qe-qt)

2 R² = 0.9831
ln(qe-qt)

0
0 0 50 100 150 200
-1
0 50 100 150 200
-2
-2
-3
-4
t,min -4
t,min
 Pseudo second order
Ni= 60 PPM,Pseudo 2nd
Ni=20 PPM,Pseudo 2nd Ni=100 PPM,Pseudo
order
order 2nd order
12 14
12 12
10
10 10
8 8
8

t/qt
t/qt

t/qt
6 6 6 y = 0.0594x + 0.8266
4 y = 0.0586x + 0.729
y = 0.0568x + 0.6595 4 R² = 0.9909 4 R² = 0.9891
2 R² = 0.9923
2 2
0
0
0 50 100 150 200 0
0 100 200
t (min) 0 50 100 150 200
t (min)
t (min)

Ni=140 PPM,Pseudo 2nd Ni=200 PPM,Pseudo 2nd

order order

15
15

10
10
t/qt
t/qt

5
5 y = 0.0688x + 1.262
y = 0.0599x + 1.1682 R² = 0.9816
R² = 0.9793 0
0
0 50 100 150 200
0 50 100 150 200
t (min)
t (min)
 Elovich Equation model

Ni= 20 PPM,Elovich Ni= 60 PPM,Elovich Ni=100 PPM,Elovich

20 20 20

15 15
15
qt (mg/g)

qt (mg/g)
10

qt (mg/g)
10 10
y = 3.344x + 0.1118 y = 3.252x - 0.0768 y = 3.1903x - 0.2602
5 5
5 R² = 0.9891 R² = 0.9865 R² = 0.9854

0 0
0 0 2 4 6
0 1 2 3 4 5 6 0 2 4 6
-5 -5
lnt lnt lnt

Ni= 140 PPM,Elovich

Ni= 200 PPM,Elovich
20
16
15 14
12
qt (mg/g)

10 10
qt (mg/g)

8
5 y = 3.1231x - 0.9079 y = 2.75x - 0.77
6
R² = 0.9679 R² = 0.9678
4
0
2
0 2 4 6
0
-5
lnt -2 0 1 2 3 4 5 6
lnt
 PSEUDO PSEUDO ELOVICH
FIRST SECOND EQUATION
ORDER ORDER

Initial conc,ppm qc (mg/g) k1 (min-1) R2 qc (mg/g) k2 (g mg-1 min-1) R2 β(g mg-1) α(mg g-1min-1) R2

20 13.83 0.071 0.978 17.86 0.059 0.992 0.299 3.46 0.989

60 19.36 0.094 0.984 17.24 0.0599 0.99 0.308 3.33 0.986

Ni 100 13.83 0.067 0.988 16.95 0.0604 0.989 0.313 3.46 0.989

140 16.5 0.071 0.983 16.95 0.0611 0.979 0.320 4.18 0.967

200 13.2 0.069 0.976 14.71 0.0714 0.981 0.364 3.64 0.967
 Pseudo First order

Ni-Cu20 Ni-Cu40
4
4
3
3
2 y = -0.0529x + 3.1723
2 y = -0.0421x + 2.8772 1 R² = 0.891
R² = 0.9599

ln(qe-qt)
0
ln(qe-qt)

1
-1 0 20 40 60 80 100 120 140
0
0 20 40 60 80 100 120 140 -2
-1 -3
-2 -4
-5
-3 t (min)
t (min)

Ni-Cu,80 Ni-Cu,100
4
4
3 3
2 y = -0.0387x + 2.8166 2
R² = 0.9058 y = -0.0394x + 2.8106
ln(qe-qt)
ln(qe-qt)

1 1
R² = 0.9005
0 0
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
-1
-1
-2
-2
-3
-3 t (min)
t (min)
 Pseudo First order

Ni-Cd,20 Ni-Cd40
4
4
3
3
2 y = -0.0507x + 3.1466
2 y = -0.0461x + 2.9798
1 R² = 0.872
1 R² = 0.9573
ln(qe-qt)

ln(qe-qt)
0
0
-1 0 20 40 60 80 100 120 140
-1 0 20 40 60 80 100 120 140
-2
-2
-3
-3
-4
-4
t (min) -5
t (min)

Ni-Cd 80 Ni-Cd 100

4
4
3
3
2 y = -0.0389x + 2.7974
y = -0.0447x + 3.0139
2 R² = 0.9223
1 R² = 0.8639
ln(qe-qt)

ln(qe-qt)

1
0
0 50 100 150 0
-1
0 20 40 60 80 100 120 140
-2 -1
-3 -2
-4
t (min) -3
t (min)
 Pseudo First order

Ni-Zn20 Ni-Zn40
4 4
3 3 y = -0.0376x + 2.8485
y = -0.039x + 2.8586
2 2 R² = 0.9258
R² = 0.9221
ln(qe-qt)

ln(qe-qt)
1 1
0 0
-1 0 20 40 60 80 100 120 140 -1 0 50 100 150

-2 -2
-3 -3
t (min) t (min)

Ni-Zn80 Ni-Zn 100

4 4

3 3
y = -0.0391x + 2.8572 y = -0.0402x + 2.8923
2 R² = 0.9266 2 R² = 0.9024

ln(qe-qt)
ln(qe-qt)

1 1

0 0
0 20 40 60 80 100 120 140 0 50 100 150
-1 -1

-2 -2

-3 -3
t (min) t (min)
 Pseudo second order

Ni-Cu20
12
Ni-Cu40
12
10
10
8
8
t/qt

t/qt
y = 0.0762x + 1.0248 6
4 R² = 0.9493 y = 0.0824x + 1.3902
4 R² = 0.9149
2
2
0
0 20 40 60 80 100 120 140 0
0 20 40 60 80 100 120 140
t (min)
t (min)
Ni-Cu80
14
Ni-Cu100
15
12
10
10
8
t/qt

y = 0.0928x + 2.263
t/qt

y = 0.089x + 1.6616
6 R² = 0.8981 R² = 0.8235
5
4
2 0
0 0 20 40 60 80 100 120 140
0 20 40 60 80 100 120 140 t (min)
t (min)
 Pseudo second order

Ni-Cd,40
Ni-Cd,20 12
12
10
10
8
8

t/qt
6 y = 0.0792x + 1.1103
t/qt

6 y = 0.074x + 0.9684 R² = 0.9474

4
R² = 0.9522
4
2
2
0
0 0 20 40 60 80 100 120 140
0 20 40 60 80 100 120 140 t (min)
t (min)

Ni-Cd,80 Ni-Cd,100
14 14
12 12
10 10

8 8
t/qt
t/qt

6 y = 0.089x + 1.7756
6 y = 0.0843x + 1.3967 R² = 0.8972
R² = 0.9277 4
4
2
2
0
0 0 20 40 60 80 100 120 140
0 20 40 60 80 100 120 140
t (min)
t (min)
 Pseudo second order

Ni-Zn20 Ni-Zn40
12 12

10 10

8 8
t/qt

t/qt
6 y = 0.0731x + 0.8409 6
y = 0.0764x + 1.0015
4 R² = 0.9618 4 R² = 0.9543

2 2

0 0
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
t (min) t (min)
Ni-Zn80 Ni-Zn100
12
14
10 12
8 10
t/qt

6 8
t/qt

y = 0.0799x + 1.1727 6
4 y = 0.0837x + 1.4784
R² = 0.9432
4 R² = 0.9193
2
2
0
0
0 20 40 60 80 100 120 140
0 20 40 60 80 100 120 140
t (min)
t (min)
 Pseudo First order
Ni-Cd
Ni-Cu

MODEL PSEUDO FIRST ORDER

MODEL PSEUDO FIRST ORDER Initial conc,ppm qc (mg/g) k1 (min-1) R2
Initial 20 19.66814 0.105938 0.957
conc,ppm qc (mg/g) k1 (min-1) R2 40 23.24291 0.11515 0.872
20 17.76091 0.096726 0.959 60 20.34835 0.101332 0.863
40 23.85515 0.119756 0.891 100 16.39539 0.087514 0.922
60 16.70988 0.087514 0.905
100 16.60992 0.089817 0.9

Ni-Zn

MODEL PSEUDO FIRST ORDER

Initial conc,ppm qc (mg/g) k1 (min-1) R2

20 17.42664 0.089817 0.922
40 17.25324 0.085211 0.925
60 17.40922 0.089817 0.926
100 18.02933 0.09212 0.902
 Pseudo second order

Ni-Cd
Ni-Cu

MODEL PSEUDO SECOND ORDER

MODEL PSEUDO SECOND ORDER

initial conc,ppm qe (mg/g) k2 (g mg-1 min-1) R2

initial conc,ppm qe (mg/g) k2 (g mg-1 min-1) R2
20 13.51351 0.005657 0.952
20 13.15789 0.005641 0.949
40 12.65823 0.005623 0.947
40 12.19512 0.004837 0.914
80 11.90476 0.005054 0.927
80 11.23596 0.004769 0.898
100 11.23596 0.004463 0.897
100 10.86957 0.00374 0.823

Ni-Zn

MODEL PSEUDO SECOND ORDER

initial conc,ppm qe (mg/g) k2 (g mg-1 min-1) R2

20 13.69863 0.006344 0.961
40 13.15789 0.00577 0.954
80 12.65823 0.005325 0.943
100 12.04819 0.004661 0.919
 VANT HOFF PLOTS

Ni=20 PPM, Ni=60 PPM Ni=100 PPM

10.5 9.5 8.2
10 8
9
9.5 7.8
9 8.5
7.6
ln KD

ln KD

ln KD
8.5 8 7.4
8 y = 6635.5x - 12.846 y = 2665.4x - 1.2351
7.5 7.2
R² = 0.8862 y = 4491.2x - 6.6311 R² = 0.8677
7.5 7
7 R² = 0.9252
7 6.8
6.5 6.5 6.6
0.0029 0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0029 0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0028 0.003 0.0032 0.0034 0.003
1/T 1/T 1/T

Ni=140 PPM Ni=200 PPM

6.8
7.8
7.6 6.6
7.4 6.4
7.2
ln KD
ln KD

6.2
7
y = 3018.6x - 2.6919 y = 2005.1x - 0.1895
6.8 R² = 0.9162 6 R² = 0.9402
6.6 5.8
6.4
5.6
6.2
0.0029 0.003 0.0031 0.0032 0.0033 0.0034 0.0035
0.0029 0.003 0.0031 0.0032 0.0033 0.0034 0.0035
1/T
1/T
 Thermodynamic Parameters

Ni
Metal conc,ppm T,K -∆G0(kJmol-1) ∆H0(kJmol-1) R2 ∆S0(kJmol-1 K-1)
293 -24.2048 -55.16339 0.886 -0.10675176
20 303 -23.4295
313 -20.1669
323 -20.2973
333 -20.6034
293 -21.7059 -37.33817 0.925 -0.055130134
60 303 -20.3589
313 -19.3982
323 -19.4084
333 -19.5513
293 -19.5819 -22.15681 0.867 -0.01026779
100 303 -18.8072
313 -18.38
323 -18.7822
333 -19.1832
293 -18.5826 -25.09165 0.916 -0.022372974
140 303 -18.6554
313 -17.458
323 -17.8472
333 -17.9163
293 -16.4302 -16.66957 0.94 -0.001571346
200 303 -16.0325
313 -15.968
323 -16.0782
333 -16.3791
The adsorption process was found feasible &
spontaneous as change in Gibb’s free energy ΔG
values are negative, & exothermic in nature
 Optimized Cost & Batch Reactor Design

Cost estimation of the treatment process

Basis

Cost of commercial grade NaOH = 50 Rs. Per kg

Calculated cost of (0.1 M NaOH alkali treatment) 1 kg of tea waste=20 paise

 Optimized Cost & Batch Reactor Design

1.Small Scale Industry

ATTW

1000 L/day or
30,000 L/ month Treated clear water
Waste water after adsorption
Containing heavy
metals Small batch
reactor

R=0.63 m,H=1 m,T= 303 K,

V= 1250 L, Stirring speed= 150 rpm

Metal Conc,ppm pH Reaction time ATTW Rs./day Rs./month

(min) (Kg/day)

Ni 20 5 90 6 1.20 36
Cu 20 5 75 4 0.80 24
Cd 20 6 90 8 1.60 48
Zn 20 5 60 6 1.20 36
 Optimized Cost & Batch Reactor Design

2.Medium Scale Industry

ATTW

10,000 L/day or
300,000 L/ Treated clear water
month after adsorption
Waste water
Containing heavy
metals Medium batch reactor

R= 2.0 m,H=1 m,T= 303 K,

V= 12,500 L, Stirring speed = 150 rpm

Metal Conc,ppm pH Reaction time ATTW Rs./day Rs./month

(min) (Kg/day)

Ni 20 5 90 60 12 360
Cu 20 5 75 40 8 240
Cd 20 6 90 80 16 480
Zn 20 5 60 60 12 360
 Optimized Cost & Batch Reactor Design

3.Large Scale Industry

ATTW

100,000 L/day or
3,000,000 L/ month
Treated clear water
Waste water
after adsorption
Containing heavy
metals
Large batch reactor

R= 3.65 m,H=3 m,T= 303 K,

V= 1,25,000 L, Stirring speed = 150 rpm

Metal Conc,ppm pH Reaction time ATTW Rs./day Rs./month

(min) (Kg/day)

Ni 20 5 90 600 120 3600

Cu 20 5 75 400 80 2400
Cd 20 6 90 800 160 4800
Zn 20 5 60 600 120 3600
 Conclusions

1.This study shows that Tea waste can be used as an

effective low cost adsorbent for the removal of Ni,Cu,Cd
and Zn heavy metals from aqeous solutions
2.The adsorption efficiency is remarkably increased by the
pretreatments of tea waste
3.The alkali treatment with 0.1 M NaOH was found to be
the best out of 10 different pretreatments applied
4.The relative removal percentage of metals by ATTW is as
follows:
Ni (99.2%) > Cu (97.3%) > Cd (94.6%) > Zn (93.8%)
 Conclusions

5.The metal percentage removal is dependant on the

pH value of the solution and the removal of Ni ions
significantly increased from 50% to 98.5% between
pH 3-6,Cu from 29.7% to 96.6% between pH 3-5,Cd
from 25% to 94.6% between pH 3-6 and Zn from
22.5% to 93.5% between pH 3-5 at room 303 K
temperature
6.The metal percentage removal reduces in case of
binary & ternary mixtures of metal ions. The
removal of Ni ions reduces up to 25.2% in its binary
& 37.3% in its ternary mixtures, The
 Conclusions

removal of Cu ions reduces up to 26.3% in its binary

& 44.5% in its ternary mixtures, The removal of Cd
ions reduces up to 25.2% in its binary & 37.3% in its
ternary mixtures, The removal of Zn ions reduces up
to 27.6 % in its binary & 53.4% in its ternary
mixtures at room 303 K temperature
7.The adsorption capacity of ATTW at room
temperature 303 K was calculated on the basis of
Langmuir isotherm and was found 31.25 mg/g for
Ni, 20.4 mg/g for Cu, 25.64 mg/g for Cd and 20.4
mg/g for Zn
 Conclusions

8. The reaction kinetics study shows that pseudo

second order model fits best for the four metal ions
9. The adsorption process was found feasible &
spontaneous as change in Gibb’s free energy ΔG values
are negative, & exothermic in nature.
10.The optimized cost of treatment was calculated and
was found pretty low & very economical in case of
small,medium & large industries
 Conclusions

11.The batch reactor design shows that adsorption

process can be applied practically & effectively for all
types of small,medium & large industries generating
polluted waste water
 Publications

1. Adsorption Study of Nickel Ni (II) Ions from Aqueous Solution on Tea Waste:
S.Asthana,A.Kedia,S.Gupta
International Journal of Advance research in Science and Engineering,IJARSE,Vol.No. 6, Issue
No.07, july 2017,ISSN No.2319-8354(UGC Listed),www.ijarse.com

2. Study of Various Pretreatment Methods for Tea Waste for the Removal of Nickel Ni (II) Ions
from Synthetic Waste Water by Adsorption, S. Asthana, S. Gupta
European Journal of Advances in Engineering and Technology, EJAET 2017, 4(9): 663-667, ISSN:
2394 - 658X, www.ejaet.com

3. Adsorption of Cd (II) Ions from Synthetic Waste Water by Tea Waste: S Asthana
International Journal of Chemical and Physical Sciences , IJCPS Vol. 6, No.5, Sep-Oct 2017
ISSN:2319-6602.,www.ijcps.org
 THANK YOU
• I am very much thankful to the following for their
help & cooperation extended for the present work:
• USCT,GGSIPU, New Delhi
• IIT Delhi
• IARI, New Delhi
• D U, Delhi
• JNU New Delhi