REMOVAL OF PHENOL FROM WASTE

WATER
USING TAMARIND NUT ACTIVATED
CARBON

ABSTRACT:

Environmental pollution shows a profound effect on living beings.It has

become a major problem in these days .Many harmful compounds are
released continuously through water and many solid by products are
deposited on to the soil.Removal of these toxic compounds from water
is essential .Among the toxic compounds that are released into the
environment phenol is one of the harmful organic compound. Higher
concentration levels of phenol leads to several adverse effects.The
potential sources of phenol in waste water are oil refineries, gas works,
coke plants, fertilizer industry, plastics manufacturing plants, textile
industries etc., In these days solid waste disposal is also a major
problem.Among the solid wastes, agriculturer waste can be utilized as
a fertilizer and as a food for the animals.

Removal of phenol can be achieved economically by using a

cost effective technique like adsorption on to activated carbon, a
valued product obtained from solid wastes like coconut shell date
seeds and tamarind nuts. Removal can also be done using activated
alumina and other methods.These processes have the limitation of
technical and/or economic constraints. So it is better to choose an
economic and ecofriendly method to remove this harmful compound
phenol. Our present work deals with the prepararion of tamarind nut
activated carbon and removal of phenol using this activated carbon.
Comparative study on the adsorption capacities of tamarind nut
activated carbon and commercially activated carbon is done.

INTRODUCTION:

1.1 AGRICULTURAL WASTES:

Many agricultural byproducts are deposited on to the soil and most of them are utilized as
food for the animals and as a fertilizer. Some of the agricultural wastes that can be used
for the production of activated carbon are saw dust, coconut shells, tamarind nuts, rice
husk,date seeds, corncorbs,coconut coir,ground nut,soyabean shells.
1.2 PHENOL: Phenol is the organic compound with chemical formula C6H5OH.

Properties Of Phenol:

Physical Properties: Phenol is a colorless to pink solid or thick liquid with a

characteristic sweet tar like odor. Boiling point: 181.90 C; Melting point: 40.90 C;

Vapor pressure: 0.36mmHg at 200 c; Flash point:78.90 c

Solubility: Water at 25: 87g/L; Organic solvent(s): Very soluble in Alcohol, chloroform,
Ether, Benzene, Acetone, Water.

Sources Of Phenol:

• The effluents from oil refineries, gas works, coke plants, and chemical
industries contribute phenols and phenolic compounds in the water.
• The major industrial sectors include pulp, paper and wood products, the
mineral product sector ,the chemical product sector, the steel and metal product
sector, and the petroleum refining and products sector, coal conversion plants
,municipal waste treatment plant discharges or spills. Phenol is found naturally
in animal wastes and decomposing organic material.etc.

1.3 ADSORPTION: Adsorption is a surface phenomenon which involves the

accumulation of a substance at a surface or interface. The process can occur at an
interface between any two phases such as : Liquid- Liquid , Gas- Liquid or Liquid- Solid.
The material being adsorbed is known as adsorbate and the adsorbing phase is called
adsorbent. Adsorption technology is currently being used extensively for the removal of
organic and inorganic micro pollutants from the aqueous phase and since its first
introduction in the 1940’s , active carbon has become the water industries’ standard
adsorbent for the reclamation of municipal and industrial waste water to a portable water
quality. The use of carbon adsorption for the direct treatment of the liquid industrial
waste streams is a relatively recent practice but has been successfully utilized for the
reclamation of metals from electro plating waste and the removal of phenol from
Chloroalkali plant waste water prior to recycling.

Types of Adsorption: There are two types of adsorption: Physical Adsorption and
Chemisorption.

*Physical Adsorption: It is a readily reversible phenomenon, is the result of

intermolecular forces of attraction between molecules of solid and substance adsorbed. In
this type of adsorption, the adsorbent can be reused after regeneration.

*Chemisorption or Activated Adsorption: It involves the chemical interaction between the

solid and the adsorbed substance and so the adhesive forces are generally much greater
than Physical Adsorption. The heat liberated is usually large, of the order of heat of
chemical reaction. The process is frequently irreversible and on desorption, the original
substance will often be found to have undergone a chemical change. Kinds of
chemisorption are: 1. Activated 2.Non-Activated

‘Activated Chemisorption’ means that the rate varies with temperature according to finite
activation energy. In some systems, chemisorption occurs very rapidly, suggesting
activation 1energy near zero. This is termed as ‘Non-Activated Chemisorption’. It is
often found for a given gas and solid, the initial chemisorption is non activated while later
stages of the process are slow temperature dependent (Activated Adsorption.)The same
adsorbent can exhibit physical adsorption at low temperatures and chemisorption at high
temperatures and both phenomena may be occurring at the same time.

Principles of Adsorption: When heterogeneous systems are considered, the boundary

between the phases is called Interface. The system may exist in equilibrium or non-
equilibrium state. Adsorption takes place when the molecules or atoms are concentrated
only at the surface when one of the phases consists of a solid. It is accompanied by a
decrease in free energy of the systems and involves a decrease in entropy and is always
exothermic.

Adsorption of Solute from Dilute Solutions: When an adsorbent is mixed with a binary
solution, adsorption of both solute and solvent occurs. The relative adsorption of a solute
is determined. Due to adsorption of solute, its concentration in the liquid is observed to
fall from initial value Co to final equilibrium value C* mass of solvent / volume of liquid.
The extent of adsorption of a given solute always decreases at increased temperature.

Mechanism of Adsorption: 1.Diffusion of solute particles from the bulk phase to solid
surface. 2. Collection of solute on the surface of adsorbent.& 3. Diffusion of solute into
the pores.

Adsorption Forces: The forces which cause cohesion in solids and liquids and which are
responsible for the deviation of real gases from ideal gases/ the basic forces causing
adsorption are: 1.Vander Walls forces and 2.Chemical forces

Phenomena related to Adsorption

*Adsorption Equilibrium: It is defined when the number of molecules arriving on the

surface is equal to the number of molecules leaving the surface to go into the bulk phase.

*Adsorption Isotherms: Isotherms as measured under existing conditions can yield

qualitative information about the adsorption process and also give indication of the
fraction of the surface coverage of adsorbent. Adsorption isotherms are most commonly
used to select the adsorbent or even adsorption process. The adsorption isotherm is the
relation between C, the concentration of absorbable component in the gas (or the partial
pressure P) and C, the concentration on the solid surface (or ‘pi’ degree or coverage) at
equilibrium conditions and constant temperature.

1. Longmuir Adsorption Isotherm: It relates the adsorption of molecules on solid surface

to gas pressure or concentration above the surface at fixed temperature.

2. Freundlich Adsorption Isotherm: Relates the conc. of a solute on the surface of an

adsorbent to the conc. of solute in the liquid with which it is in contact.

3. BET Isotherm: It tells about the molecules forming multiple layers. It is better for
physisorption.

BET theory:

A theory for monolayer molecular adsorption to multilayer adsorption and is

expressed by 1 1 1

_______ = _______ (P/P0) + _________ -----(1)

V[(P0/P)-1] Vm C Vm

P and P0 are the equilibrium and the saturation pressure, V –adsorbed gas quantity
and Vm is the monolayer adsorbed gas quantity, C is the BET constant given as

C=Exp[(E1-EL)/RT] ---------(2)

E1 is the heat of adsorption for the first layer; El is for 2nd higher layers and equal
to heat of liquefaction.

The BET method is used for the calculation of surface areas of solids by
physisorption of gas molecules.

Stotal = (VmNs) S = Stotal

________ and _______

M a

N: Avogadro’s Number ; S: Adsorption cross section; M: Mol.Wt of adsorbate. a: Wt. of sample solid

The factors affecting are: Temperature, Heat of adsorption, Pressure and Heat of wetting.

Adsorbents: Adsorbents are the substances used in separation of fluid- solid operatrions.
These are generally used in granular form. They must have adequate strength and
hardness. Certain solids exhibit sufficient specificity and adsorptive capacity to make
them useful as Industrial Adsorbents. Large surface area per unit weight is essential to all
adsorbents. The pores on the adsorbents are very small but should be in large number.

The favorable properties of Adsorbents :

1. Surface area should be more. 2. Pore size distribution will be generally small. But in
Liquid phase applications, larger pores are preferred. 3. Nature of adsorbent surface: The
Non polar adsorbents adsorb Non polar substances in preference to Polar substances and
vice-versa.4. Attrition Resistance gives an idea about the losses incurred during
adsorption.

Type of Adsorbents: Depending on the requirements, generally used adsorbents in

industry are: Activated carbon, Activated Clay, Bauxite, Bone char, Decolorizing
carbons, Synthetic Polymeric adsorbents and Silica gel and molecular sieves.

1.4 ACTIVATED CARBON: It contains carbon materials mostly derived from charcoal,
having high surface area, large amount of micro porosity which gives sufficient
activation.

PROPERTY VALUE
Bulk density 0.59
Percentage moisture 9.16
Percentage Ash 0.87
Percentage fixed carbon 99.2
Surface area(m2/gm) 405
Decolorizing power(mg/gm) 50.9
Ion Exchange capacity 0.0149
% matter soluble in water 1.26
% matter soluble in acid 1.54

General properties of activated carbon

Applications: Metal extractions, Water purification, Waste water treatment, etc.

Preparation of Activated Carbon: Activated carbon can be prepared from various

cellulosic materials. Methods for its preparation are: Sulphate Process, Chloride Process
and Carbonate Process. Its activation may be either chemical activation or steam
activation.

THE AIM OF THE PAPER: The aim is to study Preparation of tamarind nut activated
carbon and removal of phenol from water using prepared activated carbon.

PROPOSED EXPERIMENTAL DETAILS:

Preparation of Tamarind Nut Activated Carbon:

• Procurement of tamarind nuts is done from the market and washed with
distilled water to remove any inorganic matter and soil material
• Preparing Tamarind Nut Powder: The nuts are dried at 1100 C and cut into
small pieces using roll crusher and sieved to 20-50 mesh.
• Preparing Charcoal: The crushed material is treated with conc. H2SO4 1:1
weight ratio
• Activation and further steps to prepared activated carbon: The above
material is kept in hot air oven at 150 0 C for 24 hours and is washed with
distilled water to remove the free acid and dried at 1050 C and then it is
repeatedly soaked in 1% NaHCO3 until effervescence ceased and soaked in the
same solution for two days to remove any residual acid. The material was then
washed with distilled water dried at 1050 C and sieved to 20-50 mesh size.

Flow Sheet:

Comparison Properties of TAC and CAC:

Property TAC CAC

Physical appearance Granular (20-50 mesh) Powder
2
Surface Area 247 m /gm 405 m2/gm

TAC : Tamarind nut Activated Carbon and CAC : Commercial Activated Carbon

ESTIMATION OF PHENOL: (Diazo Method): Fox devises this method and gauge
determines both mono hydric and dihydric phenols. Monohydric phenols can be
determined if they are separated by steam distillation.

Principle: Phenols coupled with diazotized sulphuric acid and produce yellow to red
color according to the concentration.

2SO3H.C6H4.N2.NH2+ 2HNO2+ H2SO4  (SO3H.C6H4N2)2SO4+4H2O

2C6H50H+(SO3H.C6H4N2)2SO4  2SO3H.N:N.C6H4OH+ H2SO4

Reagents:

Phenol stock solution: 1gm of phenol is dissolved in distilled water and made up to 1000
ml in a volumetric flask prepared freshly. Standardize the solution every time.

Standardization: 25 ml of phenol stock sol is pipetted out into an iodine flask and diluted
up to 100 ml. 20 ml bromate sol. (0.5N prepared by dissolving 6.96 gm Potassium
Bromate and 37.5gm Potassium bromide in 500ml) is pipetted into flask. 10ml 1+3
H2SO4 sol. are added and stoppered the flask immediately. The neck of the flask is sealed
with 10ml of 10% potassium iodide solution. The liberated iodine is treated with 0.25N
sodium thiosulphate using starch as indicator.

Phenol working solution: Appropriate volume of Phenol stock solution is diluted to

100ml such that 1ml of dil sol contains 10 microgms phenol. The solution is prepared
freshly before use.

Sodium Hydroxide Solution: 10gms of NaOH is dissolved in 100ml of distilled water.

Reagents for Diazotized solution:

Sulphanalic Acid Sol: 764 gm Sulphanalic acid is dissolved in water and diluted to 100ml

Sulphuric Acid(1+3): 25ml conc. H2SO4 is added into 75ml distilled water and cooled

Sodium Nitrite Sol: 340gm Sodium Nitrite is dissolved in 1000ml distilled water and
prepared freshly.

Diazotized Solution is prepared as follows: 50ml H2SO4 and 10ml 1+3 H2SO4 are mixed
in a 250ml beaker kept in an ice bath. 50ml Sodium Nitrite sol. is slowly added and
stirred well. This sol is just prepared before use.

PROCEDURE: Calibration curve is drawn with the known conc. samples.

1. Different vol of phenol working sol ranging from 0.5 ,1.0,1.5,2.0 till 6.0
are taken in 50ml volumetric flasks
2. To each sample, 5ml freshly prepared Diazotized sol and 2ml NaOH is
added.
3. w.r.t. intensities of color different optical densities are obtained
4. Then a graph is drawn between Optical densities and Vol of Phenol.

RESULTS AND DISCUSSIONS:

*Effect of amount of Adsorbent: The effect of amt of adsorbent on the removal of phenol
is studied by varying the amount of adsorbent from 0.05 to 0.5 gm. It is found that with
increase in amt of adsorbent, the % of removal increases and stay constant afterwards.
So the optimum weight of adsorbent is 0.5gm for the conditions followed.(at 31 0 C for
1hr)

Concentration of Phenol in the feed: 10mg/100ml

Weight of adsorbent in gm % removal of phenol

0.05 10.5
0.1 45.7
0.2 60.9
0.3 81.9
0.5 82.9

Graph:

*Effect of Temperature: With an increase in temperature % removal of phenol

decreases.Amount : 0.5gm

Concentration of Phenol in the feed: 10mg/100ml for 1hr

Temperature in 0C % removal of phenol

28.5 82.9
45 80.1
55 78.5
60 70.2
65 68.4

Graph:
*Effect of Equilibrium time: With increase in this, % removal of phenol increases till
60min and constant afterwards.Amount: 0.5gm @ 310C

Concentration of Phenol in the feed: 10mg/100ml for 1hr

Time in min % removal of phenol

10 73.52
30 79.84
60 82.9
120 82.8

Graph:

Comparison of adsorption characteristics of CAC with TAC : Amount: 0.5gm @ 310C

Concentration of Phenol in the feed: 10mg/100ml

Time in min % removal of phenol by CAC % removal of phenol by TAC

30 54.5 79.84
60 62.5 82.9
120 80 82.79

Graph:

REFERENCES:

1.Vogel’s book of quantitative analysis, 6th edition

2. Robert E.Treybol “Mass transfer operations” 3rd edition , Mc Graw Hill international editions

3. Manivasakam, Physico chemical methods for water analysis, 4th edition, Prentice hall

4. Indian Journal of chemistry, vol12, July 2005.

Document By
SANTOSH BHARADWAJ REDDY
Email: help@matlabcodes.com
1.Engineeringpapers.blogspot.com
2.www.matlabcodes.com
3.microcontroller-project-codes.blogspot.com
4.microcontroller-library.blogspot.com
5.arduino-projects-here.blogspot.com
6.labview-projects.blogspot.com
7.java-basics.blogspot.com
8.itsnanoworld.blogspot.com
More Papers,Projects and Presentations available on above sites.