Use of Pine and Cinchona Barks for Mercury Removal from Aqueous Solution

1. Use of Pine and Cinchona Barks for Mercury
Removal from Aqueous Solution
BY
KOMAL RAJPOOT
GUIDED BY
DR. S. K. PATIDAR
November , 2018
DEPARTMENT OF CIVIL ENGINEERING
NATIONAL INSTITUTE OF TECHNOLOGY KURUKSHETRA
KURUKSHETRA – 136119 (INDIA)

2. Introduction
⮚ Mercury is risk to environment and human
health.
⮚ Mercury causes chemical and physical
transformations cycles in atmosphere.
⮚ It has long retention time in soils.
⮚ Mercury occurs naturally in the environment
as well as anthropogenically.

3. Source of Mercury
⮚Burning of coal in power plants.
⮚Burning or transfer of mercury containing items.
⮚Utilization of mercury for chlorine manufacturing in the
chloro-alkali industry.
⮚ Production of zinc, steel and different metals.
⮚Cement production.
⮚Mining and product reusing.
⮚Natural phenomena (volcanic emissions, degradation of
minerals, forest fires or evaporation from mercury rich
soils).

4. Cont….

5. Mercury Removal
⮚ Several conventional techniques such as coagulation, ion
exchange, reverse osmosis, precipitation, ion exchange, lime
softening and activated carbon adsorption are available.(Febrianto
et al., 2009)
⮚Adsorption is looked upon as a superior innovation due to its
simplicity, minimization of secondary waste and high-efficiency
characteristics.(Kurniawan et al., 2006)
⮚Natural materials, agricultural waste or industrial by products
with little processing can be used as a low- cost adsorbents.
(Monier et al., 2013)
⮚A wide variety of adsorbents have been prepared from
agricultural and wood wastes such as bagasses, pinewood, sawdust,
coconut tree sawdust, bamboo.

6. Details of studies on use of low cost adsorbents for mercury removal are
summarized in following table:
Literature Review
SN. Type of
Water/
Wastewater
Adsorption
System Details
Operation
Conditions
Adsorption
Details
Observations References
1. Synthetic and
Actual industrial
WW collected
from chloro-
Alkali industry
Batch experiments
With adsorbent,
apparent,density:
1.18g/m l; surface
area: 87.8 m2/g;
porosity: 0.38
ml/g
Initial metal
conc.: 40-
400mg/L,
PTCH: 1-
10%, contact
time: 1-24 hr
Polysulphide
treated
coconut
husk(PT
CH)
Removal efficiency:
94.8% at
pH: 5.5-10
Sreedhar et al., 1999
2. Synthetic
mercuric
chloride
solution
Batch/
continuous
columns
Temperature : 27°C-
45°C, pH : 2-6, Hg
Concentration :
5000 ppm
Chemically
pretreated
bituminous
coal
Removal efficiency:
90%
Srivastava et al., 1989
3. Synthetic
solution by
HgCl2
Surface
area:1260 m2/g
Hg(II)
Concentration:
10–40 mg/l
Activated carbon
from Antibiotic
waste
Adsorption capacity:
129 mg /g at
pH: >5
Budinova et al., 2008
4. Synthetic
solution and
WW from
Battery industry
Particle size: 0.05-0.10
mm, surface area:
160 m2/g, pore
volume: 0.43cm3/g
Hg(II) concentration
in industry
WW : 5.80-
8.02 mg/l
Modified
Rice straw (MRS)
Adsorption capacity:
0.110 mmol/g at
pH: 5
Rocha et al., 2009

7. Cont.
5. Synthetic
solution by
HgCl2
Size: 180-300
µm, Biomass
concentration:
0.4-16 g/l
Hg(II) concentration
: 10-400mg/l, contact
time: 5-120
min, pH: 2-8,
temp: 20- 50°C
Moss
biomass
Adsorption
capacity: 94.4 mg
/g
pH: 5.5
Sari et al., 2009
6. Synthetic solution
Of Mercury acetate,
nitrate,
sulphate, chloride
Batch/
continuous
columns method
Ambient conditions,
5-400 PPM of
mercury
Hardwickia
binata bark
Removal
efficiency: 97%
Deshkar et al.,
1990
7. Synthetic Solution
and chloro-alkali
Industry Waste
Water
MBI-clay size: 0.096
mm; surface area:
71.3m2/g; porosity:
0.39 g/ml; density:
1.39 g/ml
Hg(II) concentration:
25–100 mg/l for
Kinetic studies and
50–1000 mg/l for
isotherm studies
MBI-Clay >99% removal at
an initial
concentration of
50 mg/l at pH:
4-8
Manohar et al.,
2002
8. Synthetic
solution and
Chloro-alkali
industry WW
Surface area: 500.5
m2/g, cation-exchange
capacity: 5.02 meq/g
Hg(II)
Concentration:
50–1000 mg/l
and contact time: 200
min- 240 min
Sulphurized and
Steam activated
bagasse
Complete
removal for
20 mg/l
Initial
concentration
Krishnan et
al., 2002
9. Synthetic
solution by
HgCl2
Batch experiments,
carbon surface
area: 1100 m2/g,
particle size: 0.2 mm
Hg(II) concentration:
10– 40 mg/l and
contact time up to 1
hr
Furfural
carbon
adsorbent
Adsorption
capacity: 174 mg
/g
pH: 5.5
Yardim et
al., 2009
10. Synthetic solution Continuous
Columns experiments
20-40 PPM of
mercury
Redwood bark,
activated sewage
sludge, chitoson,
orange peels
- Marsi et
al.,1994

8. Cinchona bark
⮚Cinchona plants belong to the family Rubiaceae and are large shrubs or
small trees with evergreen foliage, growing 5–15 m (16–49 ft) in height
and have medicinal values.
⮚ Interactions effects of cinchona was studied in one of the prior art for
the removal of lead from aqueous solution which showed antagonistic
effect on efficiency of pine. (M.M. Al-Subu et al.,2002)
⮚Cinchona has also been used as catalyst in various metal removal
processes.(George Lutz et al.,1937)

9. Pine Bark
⮚ Pine trees are evergreen, coniferous resinous trees (or, rarely,
shrubs) growing 3–80 m (10–260 ft) tall, with the majority of
species reaching 15–45 m (50–150 ft) tall.
⮚ Large quantities of pine products are produced annually
throughout the world.
⮚ Pine bark is an environmental waste which has been successfully
use for removal of heavy metals such as lead, chromium,
cadmium etc.

10. Use of Pine as Adsorbent
S
N.
Type of
Water/
Wastewater
Adsorption
System Details
Operation
Conditions
Observations References
1. As(V)
ions from aqueous
solutions
Chir pine leaves (Pinus
roxburghii)
pH : 4.0 while equilibrium was
achieved in 35 min.
Maximum adsorption
capacity of P. roxburghii was
3.27 mg/g
Umer et al.,
2012
2. Cd2+ and Zn2+ metal
ion from aqueous solution
Washed and dried pine
cones power sized 150
μm
Volume of dye solution : 50 ml,
pH: 6.16,
Temperature: 30°C, Shaker speed:
120 rpm
Variation of contact time
with different parameters
was obtained.
Tushar et al.,
2012
3. CdSO4.7H2O, pine bark, cones and
needles
cadmium concentration: 100 ppm;
sorbent concentration:
9.2 mg/ml; pH : 5
Cd removal from
pine bark : 84%
pine cones : 69%
pine needles : 65%
S. Al-Asheh et.
al., 1997
4 Pentachlorophenol (PCP) 150-450 µm size of
bark
equilibrium time of 24 h;
100mg of pine bark and 5ml of PCP
solutions with concentrations
between 0.03-5mg/l at pH: 2
Maximum adsorption
capacity :73%
Isabel et. al.,
2004
5. Synthetic Pb(II) ions
prepared from Pb(NO3)2
50mg of pine bark was
equilibrated with 10mL
of Pb(II) solution
shaker speed: 400rpm ;
optimum pH : 4, optimum time :
4hours
Efficiency reached from 64.6
to 90.7% when
the concentration of HCl
increased from 0.01 to 0.5 M
Ali et al., 2009

11. 6. Synthetic WW containing
Cu(II), Ni(II), Zn(II), and
Pb(II).
Pine bark treated with a 5%
urea solution, particle size of
0.05–4 mm.
pH range : 6-11
2 g of bark were placed into
100 cm3 of a 5% urea
solution
at 20°C
Impact of the urea solution,
pH on the adsorption, degree
of ions of Cu(II), Ni(II),
Zn(II), and Pb(II) under
conditions of the modified
pine bark and the initial
concentration of metals
equal to 200 mg/m3 was
obtained.
Oleksandr et
al., 2010
7. Dissolved phosphorus in
surface water runoff
Cationized pine bark using
polyallylamine hydrochloride
(PAA HCl).
pH range: 2.5 to 7.9 maximum adsorption
capacity is approximately
12.65 mg phosphate/g
Mandla et al.,
2004
8. Aqueous solution of Cu
and Pb ions
Natural Pinus halepensis
sawdust 1-50gm/l
Temperature: 20-60o C,
duration :5 min to 31 hours,
pH :1-12
93-95% adsorption
efficiency for contact time of
5 min
Lucy et al.,
2018
9. Aqueous solution of Cd,
Cu, Ni, Pb , Zn ions
Grounded and sieved pine
bark through a 2 mm mesh
Centrifuged at 4000 rpm for
15 min
Adsorption capacity: 98-
99% for Pb, 83-84% for Cu,
78-84% for Cd, 77-83% for
Zn, and 70-75% for Ni
L. Cutillas et.
al., 2014

12. Objective
⮚To determine adsorption capacity of pine and cinchona barks for Hg(II) ion
removal.
⮚To investigate the effects of various parameters affecting the adsorption process
such as pH, Adsorbent dose, Hg ion concentration, Contact time.
⮚Finding out the interaction effects of two adsorbents.
⮚To obtain the best possible proportions of above mentioned adsorbents in order
to have maximum metal removal.
⮚Determination of Equilibrium Adsorption Models using Freundlich and
Langmuir adsorption isotherm models.

13. ⮚Procurement of pine and cinchona barks.
⮚Preparation of Mercury stock solution.
⮚Preparation of adsorbents from the barks of adsorbents.
⮚Batch & continuous study for mercury removal.
⮚Determination of adsorption efficiency parameters.
⮚Study of interaction effects of two adsorbents.
⮚Determination of equilibrium adsorption models using
Freundlich and Langmuir adsorption isotherm models.
Methodology

14. ⮚ Procurement of pine bark has been completed.
⮚ Learning the use of Mercury Analyzer.
⮚ Study of Freundlich and Langmuir adsorption isotherm
models.
Work completed

15. The Freundlich isotherm is an experimental relation between the
concentration of a solute on the surface of an adsorbent to the concentration
of the solute in the liquid with which it is in contact.
It is given by following equation:
X/M=Kc1/n
X = mass of adsorbate (Mercury)
c = Equilibrium concentration of adsorbate in solution.
M = mass of adsorbent
n and K are constants for a given adsorbent and adsorbate (Mercury) at a
given temperature.
Freundlich Isotherm Model

16. The Langmuir model assumes that adsorbate behaves as an ideal thing at isothermal
conditions.
At these conditions the adsorbate's partial pressure pA , is related to its volume V
adsorbed onto a solid adsorbent.
The adsorbent, is assumed to behave as solid surface composed distinct sites capable
of adsorbing the adsorbate. Equation is given by :
ßA= V/Vm= Keq
ApA/(1+ Keq
ApA)
Where: Vm is the volume of the mono layer,
Keq
A is associated equilibrium,
ßA is the fractional occupancy of the adsorption sites.
Langmuir Isotherm Model

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Cont….

20. Thank You