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GOOD MORNING

ONE &ALL
REMOVAL OF ZINC AND lead BY USING MICRO
SIZE SYZYZIUM CUMINI L. LEAVES BIOMASS:
Equilibrium And Kinetic Studies

Presenter: M.Gangadhar

Authors:
M.Gangadhara, P.Kalpanaa*, N.Rakeshb, P.Kingc , B.Niranjana Raoa

aDepartment of Chemical Engineering, GMRIT, GMR Nagar, Rajam,


Srikakulam, AP
bDepartment of Chemical Engineering, R.V.R & J.C College of Engineering,

Guntur, AP.
cDepartment of Chemical Engineering, A U College of Engineering,

Visakhapatnam, AP.
CLASSIFICATION OF WATER
POLLUTANTS
 Sewage and other oxygen demanding
wastes
 Disease causing agents
 Plant nutrients
 Synthetic Organic Compounds
 Inorganic chemicals and minerals
 Sediments
 Radioactive substances
 Thermal Discharge
Various technologies to remove toxic
metal ions from water

 Distillation  Reverse
 Ion exchange osmosis
 Filtration  Electro dialysis
 Ultra filtration  Biosorption
 Chemical
oxidation or
reduction
Merits and Demerits in These Technologies

Either
 they are of low cost, but not effective
– can’t remove trace metal of ions
Or

 effective and can be expensive


– can lower toxic metal to part per million
levels
 Biosorption
Use biomaterials to adsorb inorganic
compounds (metals) or organic compounds
from liquid phase
 Biomaterials
e.g.: microorganism, food waste, agricultural
waste etc.
 Application

- mining and metallurgical processes


- waste water treatment
ADVANTAGES

The major advantages of biosorption over


conventional treatment methods include

Low cost
High efficiency
Minimisation of chemical and biological
sludge
No additional nutrient requirement
Regeneration of biosorbent and
Possibility of metal recovery
Examples for Biomaterials
(Agricultural Waste)
Examples for Biomaterials
(Bacteria)
Examples for Biomaterials
(Algae)
Syzygium Cumini L.Leaves
Materials and Methods
Preparation of Syzygium Cumini L. Leaves adsorbent:

 The green colored Syzygium Cumini L. Leaves used in the


present study were collected in Visakhapatnam, Andhra
Pradesh, INDIA.

 The collected leaves were washed with deionised water


several times to remove dirt particles. The washing process
was continued till the wash water contains no dirt. The
washed leaves were then completely dried in sunlight for
10 days.

 The dried leaves were then cut into small pieces and
powdered using domestic mixer. In the present study the
powdered materials in the range of 75-212 m average
particle size were then directly used as adsorbents without
any pre-treatment.
Chemicals
 Metal ion solutions were prepared by diluting stock metal
ion solutions, which were obtained by dissolving weighed
quantity of ZnSO4.7H2O of analytical reagent grade
obtained from MERCK (India) in double distilled water.

Metal Solution
Preparation of zinc metal solution
 Stock solution of zinc concentration 1000 mg/L was prepared
by dissolving 4.354 g of 100% ZnSO4.7H2O in 1000 mL of
distilled water.

 The solution was prepared using standard flasks.

 The range of concentration of the prepared metal solutions


varied between 20 to 100 mg/L and they were prepared by
diluting the zinc stock solution, which were obtained by
dissolving in deionised water.
ANALYSIS

 The total metal concentration in solution was


determined with Atomic Absorption
Spectrophotometer (GBC Avanta Ver 1.32,
Australia)

 Analysis performed at a wave length of 243


nm, slit width 0.7 nm, lamp current 3 mA for
both zinc and lead
EXPERIMENTAL PROCEDURE

Batch adsorption studies  Adsorption isotherms

Effect of contact time Freundlich Isotherm


Effect of pH Langmuir Isotherm
Effect of metal ion Redlich – Peterson Isotherm
concentration Temkin Isotherm
Effect of adsorbent particle
size
Effect of adsorbent dosage
Effect of temperature
Range of variables covered in the
present study
Variable Minimum Maximum Max/Min

Time of contact (min) 0.5 240.0 360.0

Initial metal ion 20.0 100.0 5.0


concentration (mg/L)

pH 2.0 6.0 5.0


Average Size of the 75.0 212.0 2.8
adsorbent (µm)

Adsorbent dosage (g) 0.1 0.5 5.0


RESULTS AND DISCUSSION
BATCH ADSORPTION STUDIES
Effect of contact time
(Syzygium Cumini L Leaves)
 To determine the effect of contact time, 0.1 g of 75 µm adsorbent is
taken in 30 mL of aqueous solution of initial metal concentration 20
mg/L, at a known pH and the shaking was provided for 0.5 min.

 The experiment was repeated for different time intervals like 1, 2, 3


etc. up to 240 min. at constant agitation speed.

 After each interval of time the sample was filtered and was
analyzed for determination of zinc ion. This gives an opportunity
for determination of optimum contact time.

 The data obtained from the adsorption of zinc ions on the Syzygium
Cumini showed that a contact time of 10 min was sufficient to
achieve equilibrium and the adsorption did not change significantly
with further increase in contact time.
Effect of contact time

100  The data obtained from


the adsorption of zinc
ions on the Syzigium
80

Cumini L leaves
% adsorption

60

showed that a contact


time of 10 min was
40
Lead
Zinc

20 sufficient to achieve
equilibrium and the
0
0 10 20 30 40 50 60 70 adsorption did not
Time, min
Fig.1. Effect of contact time on adsorption of lead and zinc by change significantly
Syzygium Cumini L. for 20 mg/L of metal and 0.1 g/30 mL
of adsorbent concentrations.
with further increase in
contact time.
Effect of pH
(Syzygium Cumini L Leaves)
 The effect of solution pH on the equilibrium uptake of zinc
was analyzed over a pH range from 2 to 6.

 The pH was adjusted using 0.1 N NaOH and 0.1 N HCl


solutions.

 In this study, 30 mL of metal solution of concentration 20


mg/L was agitated with 0.1 g of adsorbent at room
temperature for optimum shaking time at a constant agitation
speed.

 Samples were filtered from adsorbent and they were analyzed


for concentration of metal ion.
Effect of pH
 It was observed that the
80 adsorption was very
little at the initial pH 2
60 (9.25 % Zn for 20 mg/L
% adsorption

concentration of zinc
40
metal solution). A sharp
increase in the
20
Lead
Zinc
biosorption occurred in
the pH range 3-6. It was
shown that the
0
1 2 3 4 5 6 7

pH
Fig.3. Effect of pH on lead,zinc adsorption by Syzygium Cumini L. percentage of adsorption
for 20 mg/L of metal and 0.1 g/30 mL of adsorbent concentration.
(Size 75 micro meter) increased by increasing
the pH.
Effect of metal ion concentration
Syzygium Cumini L leaves

 To study the effect of initial metal concentration, 0.1 g of


adsorbent is added to 30 mL stock solution of initial metal
concentration of 20 mg/L and is kept for shaking for
optimum time.

 Then the same procedure is repeated at pH 5 with 30 mL of


stock solution, with different initial concentrations 40 mg/L,
60 mg/L, 80 mg/L and 100 mg/L keeping the agitation speed
and room temperature constant.

 Then the samples were filtered from adsorbent and they are
analyzed for metal ion.
Effect of metal ion concentration

100 100  From the data it is observed


that the zinc metal uptake
80 80 increases and percentage
adsorption of the metals

metal uptake, mg/g


decreases with increase in the
% adsorption

60 60

Lead % Adsorption
Lead Metal Uptake
initial metal ion concentration.
40 Zinc % Adsorption
Zinc Metal Uptake
40 This increase (4.83 to 20.35
mg/g) is a result of the increase
20 20 in the driving force i.e.
concentration gradient.
0
0 20 40 60 80 100
0
120
However, the percentage
Concentration, mg/L adsorption of zinc ions on
Fig.2. Effect of metal concentration on the adsorption of lead,zinc by
Syzygium Cumini L. at 0.1 g/30 mL of adsorbent concentration.
Syzygium Cumini was
(Size 75 micro meter and pH is 6) decreased from 80.51 to 67.86%.
Effect of average particle size of the
adsorbent
(Syzygium Cumini L Leaves)

 30 mL of 20 mg/L zinc solution was added to 0.1 g of a


known size of average particle size of the adsorbent i.e. 75
m, and it was kept for shaking for the optimum time.
The sample was filtered from adsorbent and analyzed for
concentration of metal ion. This experiment was repeated
at constant agitation speed and at room temperature with
different average particle sizes of adsorbent from 75 - 212
m.
Effect of average particle size
of the adsorbent
90
 Similar trends at a lower
Lead % Adsorption
values of adsorption
85
Zinc % Adsorption
(80.51 to 68.32%) were
observed in case of
% adsorption

80

adsorption of zinc ion


75

during the studies with


70
variation of adsorbent
65
particle size (75-212 µm)
60 80 100 120 140 160 180 200 220

Adsorbent size, m
Fig.5. Effect of Syzygium Cumini L. particle size on adsorption of lead,zinc
for 20 mg/L of metal and 0.1 g/30 mL of adsorbent concentration.
(pH is 6)
Effect of adsorbent dosage
(Syzygium Cumini L leaves)

 The effect of adsorbent dosage on the amount of metal


adsorbed was obtained by agitating 30 mL of zinc solution
of concentration 20 mg/L with 0.1, 0.2, 0.3, 0.4 and 0.5 g of
adsorbent at room temperature for optimum shaking time
at a constant agitation speed.
Effect of adsorbent dosage

100  The percentage zinc


98 removal was marginally
96
increased from 80.51 to
88.95% for zinc for an
94

92
% adsorption

90 increase in adsorbent
88 dosage from 0.1 to 0.5 g.
86
This shows that very small
dosage of adsorbent i.e. 0.1
84

82 Lead

80
Zinc
g is sufficient to treat about
78
0.0 0.1 0.2 0.3 0.4 0.5 0.6
30 mL of 20 mg/L zinc
Adsorbent dosage, g concentration solutions
effectively.
Fig.4. Effect of Syzygium Cumini L. dosage on adsorption of lead,zinc
for 20 mg/L of metal concentration.
(Size 75 micro meter and pH is 6)
ADSORPTION ISOTHERMS

 Equilibrium relationships between adsorbents and


adsorbates are described by sorption isotherms which
give the capacity of a adsorbent for a adsorbate.

 In the present study, equilibrium studies were carried


out at room temperature 30310K. The equilibrium data
were analysed using four of the most commonly used
isotherm equations, Freundlich, Langmuir isotherm
models.
ADSORPTION ISOTHERMS
Freundlich isotherm
 The Freundlich expression is an empirical equation based on adsorption
onto a heterogeneous surface. The Freundlich equation is represented as,

qeq  K f C m
eq
 where K f and m are Freundlich constants characteristic of the
system. and are indicators of adsorption capacity and adsorption
intensity, respectively.

 The equation is conveniently used in the linear form by taking the


logarithm of both sides as:
log qeq = log Kf + m log Ceq
Freundlich isotherm
1.6

1.4

1.2
log qe

1.0

0.8
Lead
Zinc

0.6
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

log Ce

Fig.7. Freundlich adsorption isotherm for lead,zinc at 0.1 g/30 mL of


adsorbent concentration.
Langmuir equation
 The Langmuir model is probably the best known and
most widely applied sorption isotherm. It has produced
good agreement with a wide variety of experimental
data. The Langmuir equation has been used extensively
for dilute solutions in the following form,
Qmax bCeq
qeq 
1  bCeq

 where Qmax is the maximum amount of the metal ion


per unit weight of adsorbent (mg/g), and b is a
constant related to the affinity of the binding sites
(L/mg).
Langmuir Isotherm

1.8

1.6

1.4
Ce/qe, g/L

1.2

1.0

0.8

Lead
0.6
Zinc

0.4
0 5 10 15 20 25 30 35

Ce, mg/L

Fig.6. Langmuir adsorption isotherm for lead,zinc at 0.1 g/30 mL of


adsorbent concentration.
Redlich - Peterson equation

 The Langmuir model is probably the best known and most widely applied
sorption isotherm. It has produced good agreement with a wide variety of
experimental data. The Langmuir equation has been used extensively for
dilute solutions in the following form,

ACe
qe 
1  BC eg
 Where A(L/g) and B (L/mg) are the Redlich-Peterson isotherm constants
and g is the Redlich Peterson isotherm exponent, which lies between 0 and
1
Freundlich isotherm
1.6

1.4

1.2
log qe

1.0

0.8
Lead
Zinc

0.6
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

log Ce

Fig.7. Freundlich adsorption isotherm for lead,zinc at 0.1 g/30 mL of


adsorbent concentration.
Temkin equation
 The Temkin [16] isotherm has generally been applied in
the following form,

ln  AT C e 
RT
qe 
bT

 where AT (L/mg) and bT are Temkin isotherm


constants.
24

22

20

18

16

14
qe

12

10

6 Lead
Zinc
4

2
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

ln Ce

Fig.9. Temkin adsorption isotherm for lead,zinc at 0.1 g/30 mL


of adsorbent concentration.
30

25

20

15
qe

10

5
Experimental
Langmuir
0 Freundlich
Redlich-Peterson
Temkin

0 5 10 15 20 25 30

Ce

Fig.10. Equilibrium curves for lead onto Syzygium Cumini L.


25

20

15

10
qe

5 Experimental
Langmuir
Freundlich
Redlich-peterson
0
Temkin

0 5 10 15 20 25 30 35
Ce

Fig.11. Equilibrium curves for zinc onto Syzygium Cumini L.


Qmg / g  35.84

Langmuir bL / mg  0.0401

R2 0.9971

K f mg / g 
2.027

n
Freundlich 0.678

R2 0.9908

bT A ( L / mg ) 0.78

B L mg  56.9401

Redlich-Peterson
g -1.5644

0.3950
R2

AT L g  0.455

Temkin bT 345.95

R2
0.98709
CONCLUSIONS

 The data obtained from the adsorption of Lead


metal ions on the Syzium Cumini L Leaves showed
that a contact time of 10 min was sufficient to
achieve equilibrium.

 It was observed that the adsorption was increase in


the adsorption occurred in the pH range 2 to 6 for
zinc metal on the Syzium Cumini L Leaves.

 It was observed that the metal uptake increases


and percentage adsorption of the metals decreases
with increase in the initial metal ion concentration.
CONCLUSIONS

 It reveals that the effect of different adsorbent particle


sizes on the adsorption of zinc is significant. The
adsorption of the metal decreased with increase in
particle size for Syzium Cumini L Leaves .

 The amount of zinc and lead adsorbed increases


marginally with an increase in adsorbent dosage of
Syzium Cumini L Leaves .

 The experimental data gave good fit with Langmuir


isotherm and the adsorption coefficients agreed well
with the conditions of favourable adsorption.
THANK YOU

M.Gangadhar
GMRIT