PERFORMANCE OF LOW COST ADSORBENTS-

STUDIES ON REMOVAL
OF CADMIUM, CHROMIUM AND LEAD IN
WASTEWATER

SYNOPSIS

Submitted by

SENTHILNATHAN U

in partial fulfilment for the requirement of award of the degree

of

DOCTOR OF PHILOSOPHY

FACULTY OF CIVIL ENGINEERING

ANNA UNIVERSITY
CHENNAI 600 025

AUGUST 2013
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Introduction

Water pollution is the introduction of physical, chemical and biological

matter into the water bodies that affect the quality of life that lives in it and consumes
it. The tremendous increase in the use of heavy metals over the past few decades has
resulted in an increased flux of metallic substances into the environment. Industrial
waste constitutes the major source of various types of metal pollution in natural water.
These toxic heavy metals enter the water bodies through wastewater from metal
plating industries, phosphate fertilizer, mining, pigments, batteries, alloys etc.
Generally, water bodies are major sites of heavy metal deposits due to the fact that
streams and rivers flow through agricultural areas where pesticides and fungicides
may have been used, through industrial districts where there may have been many
metal deposits and direct discharge of effluents into these water bodies (1,2).

Heavy metals usually form compounds that can be toxic, carcinogenic or

mutagenic even in low concentrations. Presence of heavy metals even in traces is toxic
and detrimental both to flora and fauna (3).Heavy metal ions are reported as priority
pollutants , and due to their mobility in natural water ecosystems and due to their
toxicity, they require remediation. Keeping these environmental, ecological and
societal health issues in view, it is considered necessary to attempt and provide an
easy, feasible, economical and reliable method for the removal of heavy metals

The current physicochemical process for heavy metal removal like

chemical oxidation and reduction, membrane separation, liquid extraction,
electrolytic treatment, electro precipitation, coagulation, flotation, evaporation,
crystallization, ultra filtration, electrodialysis etc are expensive and inefficient in
treating large quantities. These techniques also have certain
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disadvantages like incomplete metal removal , high reagent and energy requirements,
generation of toxic sludge or other waste products that require disposal and they are
inefficient when contaminants are present in trace concentration(4).

More stringent rules by the government and media, public pressure

regarding effluent discharges have necessitated the search for newer treatment(5). In
order to solve heavy metal pollution in the environment, it is important to bring
applicable solutions. Therefore, there is a requirement for newer and effective
methods which is also cost effective (6) and there is a continuing interest in the
development of more economic and environmentally - benign processes of selective
removal of heavy metals from dilute waste streams.

Of all the recovery techniques, adsorption at solid substrate is preferred

because of its high efficiency, easy handling and cost effectiveness .The phenomenon
of higher concentration of any molecular species at the surface than in the bulk of
solid (or liquid) is known as adsorption. Adsorption is a mass transfer operation in
that a constituent in the liquid phase is transferred to the solid phase. The adsorbate is
the substance that is being removed from the liquid phase at the interface. The
adsorbent is the solid, liquid or gas phase onto which the adsorbate accumulates. The
phenomenon of adsorption also know as surface phenomenon has been know since
1773 when Scheele discovered the uptake of gases by charcoal.

Activated carbons (7) exhibit a great adsorption capacity owing to their

highly developed pore structures characterized by large surface areas. International
growing demand of this adsorbent, mainly because of their use in mitigation has led
to search for new, available materials of renewable character. The adsorption process
for the treatment of wastewaters also uses solids of natural origin that are cheap and
effective, or their derivatives to
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retain heavy metals and this source of adsorbent has a great potential to achieve this
objective. Compared wt conventional methods for removing toxic metals from
effluents, the sorption process has the advantages of low operating cost, minimization
of volume of chemicals and biological sludge to be disposed off and high efficiency
in detoxifying very dilute effluents .To obtain cost - efficient processes, low cast
sorbents based on agricultural wastes or cheap biomasses are used as a promising
alternative .

The main objective of this thesis is in the finding of a new adsorbent for
treating wastewaters. There is no literature report on the study of the adsorption
behaviour of metals by Derris indica, Acacia nilotica and Hybrid eucalyptus.
Motivated by economic and environmental considerations, this study aims at the
removal of cadmium, chromium and lead from aqueous solution from the wood of
Derrris indica, Acacia nilotica and Hybrid eucalyptus.

Organization of the thesis

The thesis comprises six chapters.

The introductory unit, chapter 1 starts with the statement of pollution

problem, toxicological aspects of metals, effects of heavy metals on human health,
effects on heavy metals on aquatic organisms, need for the removal of heavy metals,
conventional methods for the treatment of metals, chemical precipitation, chemical
reduction, membrane process, evaporators, cementation, ion exchange, electro
deposition, adsorption. It also includes the advantages of conventional methods for
treatment of wastewater containing heavy metals and gives details of the various types
of adsorption.

Chapter 2 delves into the literature study of the proposed work .

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Chapter 3 gives the Adsorption principles and practices .A general study

of types of adsorption , mechanism of adsorption and types of adsorption was
illustrated.

Chapter 4 focuses on materials and experimental methods regarding the

preparation of the adsorbent, pH and effect of adsorbent at different initial metal
concentration, determination of optimum dosage, optimum contact time Langmuir
isotherm constant and Freundlich isotherm constant. In column studies amount of
wastewater that can be treated using 2.1 cm diameter column with bed depth of 5 cm
and 2.5 cm diameter column with 7 cm bed depth was explained.

Chapter 5 presents the observations and analyses of the results and

discussion of the research findings. The results showed that wood of Derris indica,
Acacia nilotica and hybrid Eucalyptus can successfully be used for the removal of
various heavy metals such as Cadmium, Chromium and Lead in aqueous systems.

Effect of pH

The study of pH on the sorption of metal ions by Derris indica, Acacia

nilotica and hybrid Eucalyptus is important in establishing the optimum sorption of
metals ions at the solid liquid interface. The studies showed that probably the most
important parameter affecting the adsorption process is pH since this affects the
solubility of the metal ions . Cadmium removal was optimal at pH 7.37. Chromium
and Lead showed maximum adsorption at pH 3.37 and 3.43 respectively.

Effect of Initial metal concentration

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The study shows a decline in adsorption capacity of Derris indica, Acacia

nilotica and hybrid Eucalyptus with the increase in the concentration of metal ions
which may be attributed to the availability of smaller number of surface sites on the
adsorbent(Derris indica, Acacia nilotica and hybrid Eucalyptus) for a relatively larger
number of adsorbing species of higher concentration.

Effect of adsorbent dosage

The percentage of removal of metal ions increased with the increase in

adsorbent dosage and reached a particular constant value after particular adsorbent
dosage. This is mainly due to the fact that a larger mass of adsorbent could adsorb
larger amount of metal ions due to the availability of more surface area of the
adsorbent. Results showed no further increase in adsorption after a certain amount of
adsorbent was added. These results also suggest that after a certain dose of adsorption
, the maximum adsorption sets in and hence the amount of ions bound to the adsorbent
and the amount of free ions in the solution remain constant even with a further addition
of the adsorbent dosage(8). This may be due to the overlapping of adsorption sites as
a result of overcrowding of adsorption particles.

Adsorption Isotherm

The capacity of adsorption isotherm provides a panorama of the course

taken by the system under study in a concise form , indicating how effectively an
adsorbent will adsorb and allows an estimate of the economic viability of the
adsorbents commercial applications for the specified solute. Sorption isotherms
usually describe the equilibrium relation between sorbent and sorbate, i.e. the
equilibrium relationship between the quantity of metal sorbed and the remaining in the
aqueous solution at the fixed temperature. By plotting solid phase concentration
against liquid phase concentration, it is
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possible to predict the equilibrium isotherm. The isotherm thus yield certain constants
whose values express the surface properties and affinity of the sorbent. Adsorbent data
obtained from the present study are fitted into Langmuir and Freundlich isotherms.
Langmuir isotherm parameters are KL, qm and RL were determined . The values of
dimensionless separation factor RL calculated for different metals were in the range
of 0< RL< 1, which indicates that the adsorption of metals onto Derris indica , Acacia
nilotica and hybrid Eucalyptus is favourable. Freundlich isotherm parameters KF and
1/n were also calculated. The Langmuir and Freundlich isotherms (9,10) are found to
be applicable in the present metals adsorption, which may be attributed to the
formation of monolayer on the surface of the adsorbent.

In column studies the volume of wastewater that can be treated using 2.1
cm diameter column having a bed depth of 5 cm and 2.5 cm diameter column having
a bed depth of 7 cm using wood of Derris indica , Acacia nilotica and hybrid
Eucalyptus based carbon were tried with a flow rate of 2 mL/ min .

Desorption studies

Desorption studies help to elucidate the nature of adsorption and recycling

of the spent adsorbent and the metal ions. The metal ions were all desorbed by
hydrochloric acid and sodium hydroxide which indicates that the metal ions were
adsorbed onto the activated carbon through by physisorption mechanisms.

Chapter 6 draws the conclusion of the thesis. Activated carbon was

prepared from the wood of Derris indica , Acacia nilotica and hybrid Eucalyptus. The
results show that the wood of Derris indica , Acacia nilotica and hybrid Eucalyptus
can easily be envisaged as a new sorbent for the metal clean up operations in aqueous
systems. Wood of Derris indica , Acacia
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nilotica and hybrid Eucalyptus was successfully used for the removal of various toxic
metal ions. Batch mode studies were conducted using the above adsorbent for the
metal ions: Cd(II), Cr(III) and Pb(II). Effect of pH was studied The amount of metals
retained on unit weight of adsorbent (q, mg/g) increased with increasing of initial
metal ion concentration from aqueous solution. At the same time , the percentage of
metal removal sharply decreased with the increasing of initial concentration. The
results show that the adsorption of metals increased rapidly with increase in amount
of adsorbent and reached equilibrium after a point. Langmuir isotherm parameters are
KL , qm and RL were evaluated. . Freundlich isotherm parameters KF and 1/n were
found.
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on activated rice husk carbon and activated alumina", Bioresour. Technol.,
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LIST OF PUBLICATIONS

Journal

1. Venkatesan, G. and Senthil Nathan, U. "Adsorption Batch Studies on the

Removal of Cadmium using Wood of Derris Indica based Activated Carbon"
,Research Journal of Chemistry and Environment, Vol. 17, No. 5, pp. 19-
24,May 2013.

2. Venkatesan, G., Senthil Nathan, U. and Shameela Rajam, "Cadmium

Removal from aqueous solutions using hybrid eucalyptus wood based
activated carbon: adsorption batch studies, (Published Online) DOI. 10.1007/S
10098-013-0628-0.

3. Senthil Nathan, U. and Venkatesan, G. "Removal of Chromium from

aqueous solutions using Wood of Derris Indica based Activated Carbon",
Environmental Protection Engineering, (Accepted for publication).

4. Senthil Nathan, U. and Venkatesan, G. Removal of Chromium with

economical adsorbents-A review" Research Journal of Chemistry and
Environment, (Accepted for publication).

Conference

Senthil Nathan, U. and Venkatesan, G. Absorption kinetics on removal of

Chromium from waste water using Acacia nilotica wood based activated
carbon, urban environmental pollution 2013 Asian Edition, Beijing, China
(Submitted).