STUDIES ON THE INVESTIGATION OF CHELATING

BIOPOLYMER FOR THE COMPLEXATION OF HEAVY

METAL POLUTANTS FROM AQUEOUS SOLUTION

by
Dhruba Prasad Poudyal
Birendra Multiple Campus, Bharatpur

Supervisor: Dr. Hari Poudyal

Co-supervisor: Prof. Dr. Kedarnath Ghimire
: Dr. Achut Adhikari

Central Department of Chemistry

Institute of Science and Technology
Tribhuvan University, Kathmandu, Nepal 1
Outline of the presentation

• Abstract.
• Introduction
• Statement of the Problem
• Objectives
• Research question
• The significance of the study
• Literature review
• Methodology
• Expected outcomes
• Time frame
• References

2
Abstract

• Heavy metal pollution in the environment is one of the

burning issues in the recent years.
• The biopolymer for the decontamination of aquatic
environment polluted with hazardous heavy metals and
metalloids like Cs(I), Hg(II), Pb(II), Cr(VI) and As(III
and V) will be prepared from Bridelia retusa (Gayo) and
peels of Citrus grandis using simple and cheap methods.
• A cross-linked biosorbent of Bridelia retusa (Gayo) will be
prepared by cross-linking reaction of some crosslinker
such as sulphuric acid, epichlorohydrin, formaldehyde etc
while carboxylic acid based biopolymer obtained from
Citrus grandis will be first saponified then loaded with
high valent metal ion to prepare adsorbent for anionic
species of metal ions.

3
Abstract contd…

• The investigated biosorbent will be characterized by

using chemical and instrumental methods.
• The adsorption potential of biosorbent will be studied in
batch as well as dynamic packed column in different
adsorption-desorption regeneration cycles.
• It is expected that the biosorbent investigated in this
research work will be effectively capable of removing
heavy metal pollutants from aqueous solution.

4
Introduction

• Water containing toxic metallic ions has adverse effect in

human health.

• A huge mass of metallic ions are released in to the

environment due to industrial manufacturing processes,
smelting , refining, electricity generation, agricultural
fertilization, waste water treatment, and fuel combustion.

• There are number of reports about to remove metallic ions

to ensure the safety of water for human consumption and
to preserve the aquatic ecosystem.

5
Introduction

• Reduction followed by chemical precipitation

• ion exchange,
• membrane separation,
• reverse osmosis,
• coagulation,
• solvent extraction,
• activated carbon,
• electrodialysis,
• catalytic oxidation etc

6
Introduction…..

• A Cost effective alternative technologies to conventional

methods are essential for the removal of ions from aqueous
solutions.

• Biosorption uses biomaterials to environmental ions from

aqueous solution by wide range of physicochemical mechanism,
including ion-exchange, chelation, complexation, physical
adsorption, and surface micro-precipitation.

• The major advantages of biosorption over other conventional

treatment methods include low cost, high efficiency,
minimization of chemical and biological sludge and regeneration
of biopolymer by desorption technique and possibility of metals
recovery 7
Introduction…..

• Biosorption is a physical - chemical process, simply defined as

the removal of substances from solution by biological materials.

• This is a property of both living and dead organisms (and their

components) and has been heralded as a promising
biotechnology becomes of its simplicity, analogous operation to
conventional ion-exchange technology, apparent efficiency and
availability of biomass and waste byproducts

Daphne papyracea
8
 Introduction…..

The biomass usually are composed of cellulose, pectin,

hemicellulose and lignin as major constituents and may also include
other polar functional groups of lignin, which includes alcohols,
aldehydes, ketones, carboxylic, phenolic and ether groups. These
groups have possible binding sites for metals and have the ability to
some extent to bind heavy metals by donation of an electron pair
from these groups to form complexes with metal ions in solution.

9
 Statement of problem

Toxic heavy metals are being serious problem for human being and
aquatic animals.
In Nepal peoples from Kathmandu valley and 25 districts from
Terai have been using ground water for drinking purpose.
Many studies have shown that ground water of Nepal contain
heavy metal like arsenic, chromium, lead which is a serious health
hazard.
Uncontrolled growth of industries and dumping of electronic
garbage have also increased the water contamination by heavy
metals.
There are many synthetic ion exchange resigns to remove heavy
metals from water, but they are expensive, non-biodegradable and
required a lot of chemicals to synthesize.
10
 Research questions

• Can bio-polymer obtained from Bridelia retusa and Citrus

grandis be used as adsorbent for metal ions?

• Can the adsorbent capacity of natural polymers improved by

chemical modification?

• Can the biopolymer based adsorbent be reused?

11
 Objectives

The broad/general objective of the proposed research is to

develop the natural bio-polymer based chelating adsorbent for
metal ions.

12
The specific objectives

To collect plant materials and pre-treatment.

To test the sorbent capacity of biopolymer by batch method.

To test adsorbent capacity in different variables such as temp,

time,pH, dose etc.

To modify the biopolymer by chemical methods such as cross

linking, saponification, amination, sulfonation, metal
immobilization etc

13
The specific objectives…

To characterize the biosorbent by EDX, FTIR, SEM, XRD and

chemical analysis.

To test the chelating capacity of modified biosorbent.

To evaluate the thermodynamic parameter for the sorption.

To study the regeneration test of modified bio-polymer.

To perform the continuous adsorption test by using column in

different variables.

14
 Significance of the study

This research work will provide method to develop cheap,

effective, and biodegradable adsorbent which will be prepared
from indigenous material.

15
 Literature review

Several research articles were published by different research

groups reporting the successful use of different kinds of biomass
materials in the removal of metal ions from aqueous solution, a
short summary on some of the important studies is made.

•The direct uses of natural bio-polymer of garden grass (GG) was

studied by Hossain et al, (2012) and reports 58.34 mg/g of maximum
Removal of Cu(II)
In another study, Aloma et. al., (2012) studies the adsorption ability
of sugarcane baggase for Ni(II) and report maximum adsorption
capacity of 2 mg/g from aqueous solution.
The preparation of activated carbon from coconut husk was done by
Buah and Dankwah (2016) for the removal of metal ions such as Cu
(II), Cd (II) and Pb (II) 16
•Parajuli et. al., (2007) studied the adsorption behavior of cross
linked lingo phenol gel for precious as well as base metals
removal from hydrochloric acidic media.
•Study on the removal of adsorption of uranium, throrium and
lutetium was made by Inoue et al. (2006) by using polyphenol
rich persimmon waste after cross-linking with formaldehyde.
•Investigations of adsorption ability of polyphenol enrich
biopolymers of green tea leaf was made by Pangeni et. al.
(2014) by sulphuric acid cross linking for Cs(I) ion removal. It
was shown that maximum adsorption capacity of Cs(I) was 1.22
mmol/g by cross-linked tea leaves. The adsorption property of
this biopolymer was significantly improved by cross-linking
reaction.
17
•Paudyal et. al., (2014) reported the use of chemically modified
orange juice residue (SOJR) as biosorbent for the removal of
strontium Sr(II) ion from aqueous solution with the maximum
adsorption capacity of this biosorbent was reported to be 833.4
mmol/kg.
•Study on the removal of arsenic using biopolymer derived from
orange waste was made by Biswas et. al. (2008) and reported
that base hydrolysis followed by Zr(IV) loading effectively
developed the ion exchange sites anionic species of As(III) and
As(V).

18
 Methodology

The locally available biopolymer such as Bridelia retusa (Gayo) and

peels of Citrus grandis (Vogate) rich in polyphenolic and
polysaccharides will be employed as a feed material to prepare
bioadsorbents for the removal of toxic heavy metal from aqueous
solution

19
Methodology

Biopolymer obtained from these biomass will be chemically

modified to get different functional moiety for the purpose of
selective binding targeted ions from water.

20
Chemical modification of the biopolymer

The biopolymer of Bridelia retusa containing polyphenolics

will be chemically modified by cross-linking with
formaldehyde, sulphuric acid and epichlorohydrin

21
Chemical modification of the biopolymer..

•The pectin rich biopolymer of Citrus grandis will be first

saponified to convert ester part of pectin into carboxylic
acid by lime water or caustic soda.
•In the case of metal ions existing in their oxo-
anionic form in aqueous solution such as As(III) and
As(V) anion exchange sites will be developed by
loading high valent metal ions such as Fe(III), Zr(IV)
and La(III).
• In the case of loading metal ion with high oxidation
state, some positive charge of loaded metal ion will
be neutralized by acidic functional groups of
saponified Citrus grandis and rest will be neutralized
by hydroxyl ion in water, hydroxyl ion will be
exchange with oxoanionic species of targeted metal
ions. 22
Chemical modification of the biopolymer..

Ester part

23
Characterization of the biosorbents

Characterization will be carried out by various chemical

and instrumental techniques as follows.

• FTIR (Fourier Transform Infrared Spectroscopy

• Scanning Electron Microscopy (SEM)

• Energy Dispersive X-ray (EDX) analysis

• X-ray diffraction (XRD) studies

• Boehm titration
• Analysis of total phenolic content
• Determination of total exchangeable proton
24
Analysis of metal ions

• The concentration of metal ions before and after adsorption

using investigated sorbent will be performed by UV visible
spectrophotometer or/and atomic absorption spectrometer.

25
 Application of investigated biosorbents for
toxic metal removal

• Batch wise adsorption

• Dynamic adsorption test using packed column

26
 Kinetics studies

The sorption of metal ion will be carried out by varying pH,

contact time, metal ion concentration, sorbent dosage, and
selectivity test in mixed system by following standard batch
adsorption procedure. In a typical batch experiment, 25 mg of
sorbent and 15 mL of metal solution were mixed in sealed glass
bottle and shaken together for 24 h. The solid-liquid mixture will
be separated by filtration and the filtrate will be analyzed by
using UV spectrophotometer or AAS. The adsorption percentage
and capacity were evaluated by using following mass balance
relationship.

27
 Kinetics studies

%A = (Ci -Ce)100/ Ci …………..1

q =(Ci - Ce)v/W ……….....…...2

Where, Ci and Ce are initial and equilibrium concentration
(mmol/L) respectively. W is weight of the adsorbent (g) and v is
volume of solution (L).

28
 Kinetics studies

Pseudo-first order Kinetics

• ln(qe – qt) = lnqe –k1 t……………….(3)

• where qe (mmol/g) and k1 (h-1) are the equilibrium uptake

capacity of metal ion and pseudo-first order rate constant,
respectively. The value of k1 and qe can be evaluated from the
slope and intercept of ln(qe – qt) versus t plot. A straight line
plot ln(qe – qt) versus t with high correlation coefficient
suggests the applicability of this model to the adsorption system

29
 Kinetics studies..

Pseudo-second order Kinetics

• where where qt and qe are the amount of adsorbed metal ion

(mmol/g) at time t and at equilibrium time respectively. k2 is
pseudo second order rate constants and t is contact time.

• The kinetic parameters for the pseudo-second order reaction

were estimated by plotting t/qt vs t
30
 Adsorption isotherm studies

The experimental data obtained from concentration variation will be

analyzed by using different isotherm models namely Freundlich and
Langmuir

Langmuir Adsorption isotherm:

Ce 1 Ce
 
qe qmax b qmax

• where Ce (mmol/L) is the equilibrium concentration of metal ion

tested. qmax (mmoL/g ) is the theoretical capacity of maximum
monolayer formation by metal ion adsorption, and b (L/mmoL)
is the Langmuir isotherm coefficients related to the binding
energy and adsorption equilibrium constant.
31
 Adsorption isotherm studies..

Freundlich Adsorption isotherm:

log qe = log KF + ( 1/n ) log Ce

• where KF and n are the adsorption constants of Freundlich

isotherm model. The values of KF and 1/n were determined
from the intercept and slope of the linear plot of experimental
data of log (qe) versus log (Ce), respectively.

32
Investigation of thermodynamic parameters

• The three fundamental thermodynamic parameters for the

adsorption system, such as Gibbs free energy, enthalpy and
entropy are useful for assessing the overall heat and energies
associated with complex multipath biosorption processes.
• The value of ΔGo will be calculated from the following
mathematical expression;
∆G˚ = -RT lnKc
Where
• R is the universal gas constant
• T is the temperature in Kelvin and
• Kc is the distribution coefficient (qe/Ce).

33
Investigation of thermodynamic parameters..

• The standard Gibbs free energy change (∆G˚) can be

also expressed in terms of Langmuir equilibrium
constant, b (L/mmol). Langmuir equilibrium constant is
equivalent to the distribution coefficient.

G o   RT ln( b)

34
Investigation of thermodynamic parameters..

• The change in heat of sorption (ΔHo) and entropy (ΔSo)

are related with standard Gibbs free energy change
(ΔGo), according to the following equations

G o  H o  TS o

 RT ln( b)  H  TS
o o

H S
o o
ln( b)   
RT R
35
 Adsorption test using packed column

• Dynamic adsorption behavior of metal ions such as Cr,

As etc will be carried out in a glass column using
packed column of investigated biosorbent
• The effect of various parameters such as pH, influent
concentration of metal ion, bed depth, and flow rates
will be investigated
• The dynamic adsorption data obtained using packed
column will be analyzed by using different models such
as Thomas model, Bed depth service time model as,

36
 Adsorption test using packed column..

Thomas model

 Ci  q0 M
ln   1  kTh - k Th C i t
 Ce  Q

Where M, Q, q0 are the mass of sorbent, flow rate and maximum

adsorption capacity of the bed for the metal ions respectively.

The plot of ln(Ci/Ce – 1) vs time (t) yields straight lines with slopes
of kThCi and intercept values of (M×q0×kTh/Q).

37
Expected Outcomes

• This research will help to investigate a new natural

chelating biosorbent for the treatment of toxic metal
ions from aqueous solution as a low cost
• biodegradable and environmentally friendly material
that can be used for the treatment of water and waste
water.
• Two international and three national papers will be
published after the successful completion of this
research work.

38
 Time frame

Work Duration
1st and 2nd semester classes 6 months each

Stem collection Second semester

Extraction of raw fiber Second semester
Literature survey Second semester

Isolation of pure cellulose fiber and Chemical 6 months

Characterization
Measurement of Mechanical properties 6 months

Composite preparation and characterization 6 months

Thesis writing 6 months

Total duration 3 years 39

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