SEPARATION OF WATER FROM

BIODISEL-DIESEL USING POLY

(AMPS-co-IA) HYDROGEL

A PROJECT REPORT

Submitted by
MURALIDHARAN. S AC15UCH061
RAHUL. U AC15UCH073
RISHENDHAR. M AC15UCH076
SUDALAI MUTHU RAJA. B AC15UCH092

In partial fulfillment for the award of the degree

of

BACHELOR OF TECHNOLOGY

in

CHEMICAL ENGINEERING

ADHIYAMAAN COLLEGE OF ENGINEERING (AUTONOMOUS)

(Approved by AICTE New Delhi, Accredited by NBA-AICTE, New Delhi,

Accredited by NAAC –UGC, New Delhi with ‘B + ’grade)

ANNA UNIVERSITY: CHENNAI 600 025

APRIL 2019
 ANNA UNIVERSITY: CHENNAI 600 025

BONAFIDE CERTIFICATE

Certified that this project report SEPARATION OF WATER FROM BIODISEL-

DIESEL USING POLY (AMPS-co-IA) HYDROGEL is the bonafide work of
MURALIDHARAN.S (AC15UCH061), RAHUL.U (AC15UCH073),
RISHENDHAR.M (AC15UCH076) and SUDALAI MUTHU RAJA. B
(AC15UCH092) who carried out the project work under my supervision.

SIGNATURE SIGNATURE
Dr. V. VENKATESHAM Mr. S. YUVARAJ
Head of the Department Assistant Professor And Supervisor
Department of Chemical Engineering Department of Chemical Engineering
Adhiyamaan College of Engineering Adhiyamaan College of Engineering
Hosur - 635130 Hosur – 635130

Submitted for the Final year B. Tech. Chemical engineering viva-voce

held on ____________________ at ADHIYAMAAN COLLEGE OF
ENGINEERING, HOSUR.

Internal examiner External examiner

 ACKNOWLEDGEMENT

We would like to express our sincere thanks to our beloved Principal

Dr. G. RANGANATH Adhiyamaan College of Engineering for his keen interest

and affection toward us.

Our respectful thanks to our Dr. N. S. BHADRINARAYANA Dean

(Autonomous) ACE for helping us and providing us the necessary benefits at our

department to make our project success.

We are highly indebted to Dr. V. VENKATESHAM Professor and head,

Department of Chemical Engineering, Adhiyamaan College of Engineering, for

permitting and encouraging us to do this project work.

We also thank our project co-ordinator Dr. D. MITALI DAS &

Mr. P. EZHIL KUMAR M.E., for their Guidance and providing us the necessary

facilities to make our project success.

We express our heartfelt and profound thanks to our Assistant Professor

and our guide Mr. S. YUVARAJ for his co-operation and guidance in each and

every stage of the project.

Muralidharan. S
Rahul. U
Rishendhar. M
Sudalai Muthu Raja. B

iii
 ABSTRACT

In this work, hydrogel of 2-Acrylamido2-methylpropane sulfonic acid Co-

polymer with itaconic acid (AMPS-Co-IA) was obtained by free radical

polymerization of 2-Acrylamido2-methylpropane sulfonic acid with itaconic acid

in the presence of N, N'- methylene bisacrylamide (MBAAm), in aqueous media.

The hydrogels were cut and dried before to be used in saturated fuels. Saturated

blends of biodiesel and diesel were mixed in appropriate amounts to form B0 (0%

biodiesel and 100% diesel by volume), B20, B40, B60 and B100. A large study

was done to synthesize an absorbing material to have appropriated characteristics

to be used as water absorbing of fuel samples. The most suitable material must

present high swelling ratio combined with an enough density of cross-linked

structure that enables handling the material. The dried hydrogels were added to

the saturated biodiesel, diesel and blends. The reductions of water content for

B20, B60 and B100 were 58, 57 and 64% respectively, after 180 min of treatment

with hydrogel.

KEYWORDS: Hydrogel, Biodiesel Blends and Water Reduction

iv
 TABLE OF CONTENTS
CHAPTER TITLE PAGE NO
ABSTRACT iv
LIST OF FIGURES vi
LIST OF TABLES vii
1 INTRODUCTION 1
1.1 Water Content In Biodiesel And Diesel 1
1.2 Hydrogel Absorbents 3
2 LITERATURE REVIEW 5
3 EXPERIMENTAL METHODOLOGY 11
3.1 Materials 11
3.2 Blends of Saturated Biodiesel-diesel 12
3.3 Synthesis of Hydrogel Samples 13
3.4 Swelling Measurements 13
3.5 Karl Fischer Measurement 13
4 RESULTS AND DISCUSSION 15
4.1 AMPS-co-IA Hydrogel 15
4.2 Effect of Monomer Ratio 15
4.3 Effect of Initiator Concentration 17
4.4 Effect of Cross-linker Concentration 19
4.5 Water Absorption from Biodiesel, Diesel
And Blends 25
4.6 Effect of Hydrogel on B100 Sample 26
4.7 Effect of Hydrogel on B60 Sample 26
4.8 Effect of Hydrogel on B20 Sample 27
5 CONCLUSION 29

v
 LIST OF FIGURES

FIGURE NO. TITLE PAGE NO.

1 Pictorial Representation Of Hydrogel 4
2 Chemicals Used to Prepare Hydrogel 11
3 Blends of Biodiesel-Diesel 12
4 Karl Fischer Titrator 14
5 AMPS-co-IA Hydrogel 15
6 Effect of Monomer Ratio 17
7 Effect of Initiator Concentration 19
8 Cross Linking of AMPS and IA 21
Monomers
9 Effect of Cross Linker Concentration 23
10 IR of AMPS Hydrogel 23
11 SEM Images of AMPS Hydrogel 24
12 Blends of Biodiesel-Diesel at Shaker 25
13 Effect Of Hydrogel On B100 Sample 26
14 Effect Of Hydrogel On B60 Sample 27
15 Effect Of Hydrogel On B20 Sample 28

vi
 LIST OF TABLES

TABLE NO. TITLE PAGE NO.

1 Effect of Monomer Ratio 16
2 Effect of Initiator Concentration 18
3 Effect of Cross Linking Concentration 22

vii
 CHAPTER-1
INTRODUCTION

Fuels can incorporate water during the production, transportation and

storage. Water in fuels has always been a problem, promoting severe damage on
fuel injection equipment and/or contributing to corrosion in storage tanks. Issues
related to fuel thermal oxidation stability, fuel filterability, fuel lubricity,
promotion of soluble and insoluble gum growth, development of particulate
matter, fuel filter plugging, fuel injector clogging, and fuel combustion efficiency
degradation all may be related to water contamination in fuels
It is important to find alternative methods for removing water from biodiesel,
diesel and blend fuels Instead of energy-expensive processes such heating, in case
of removing water from biodiesel, and salt columns, in case of removing water
from diesel fuels. One alternative is to use a water absorbent Material.

1.1 WATER CONTENT IN BIODIESEL AND DIESEL

The water content in Biodiesel and diesel fuels can be classified in free,
emulsionated and soluble water. The solubility of water is dependent on
temperature and composition of the fuel. Therefore, the hygroscopic nature of the
biodiesel can lead to an increase in soluble water content during the storage.
During biodiesel production, water is used to remove catalyst, soap and traces of
glycerol. Limits to the maximum value of 0.05% (w/w). Water is introduced into
biodiesel during the production process and may remain in it if the drying
procedure is not efficient. It can also be absorbed during storage, since FAMEs
are hygroscopic compounds, making the biodiesel much more hydrophilic than
the regular diesel. The amount of water in biodiesel affects its calorific value and,
above all, the shelf life of the fuel, since biodiesel with a high water content
clearly has a lower oxidation stability. The lower the oxidation stability, the larger

1
is the probability that oxidation products will be formed during long storage
periods. These can cause engine problems particularly within the injection system
(blocking due to deposits formed and also wearing of the zinc and chrome parts).
The presence of water can also cause biological growth and can cause the esters
to react, producing soaps and, consequently, modifying the biodiesel composition
and lowering its quality.2,3 The capacity to describe the water solubility in fatty
acid ester systems and biodiesels is, therefore, important to ensure the fuel quality
during production. Biodiesel has the Characteristics of absorbing more moisture
than petroleum diesel, since fatty acid methyl esters are hygroscopic compounds,
making the biodiesel much more hydrophilic than the regular diesel. Once Stored,
biodiesel can absorb more humidity than petroleum diesel since fatty acid methyl
esters (FAMEs) are hygroscopic compounds, making biodiesel much more
hydrophilic than regular diesel. Biodiesel clearly offers environmental,
commercial and performance benefits, since biodiesel does not contain sulphur,
aromatic hydrocarbons, metals or crude oil residues. The Maximum amount of
allowed water content in biodiesel as specified in ASTM standard D6751 is 500
Ppm. After the biodiesel production, the method to reduce the water content level
below 500 ppm involves heating the wet biodiesel at 50ºC for 1 hour, requiring
energy for heating.

However, even the biodiesel has the water content specification after its
production, water absorption occurs throughout the storage time, and this fact is
intensified depending on the temperature and moisture of the environment. The
presence of water in biodiesel and diesel fuels causes biological growth in storage
tanks. This fact could lead to corrosion of metals (especially iron and steel),
formation of sludge and slime, thereby causing blockage of fuel filters and fuel
lines, which could in turn damage vehicle fuel injection system. In fact, the
removal of water from fuels is difficult or indeed not possible. Gravity separation,

2
centrifugal separation, absorbent polymer separation, coalescing-based filtration,
and vacuum dehydration are well-known water decontamination techniques in
the quality maintenance of diesel fuels. For water removal during biodiesel
production energy-expensive processes such as heating or a vacuum flash are
used. Few studies aim to develop techniques of detection of water content in
biodiesel. Bampi determined experimentally the water content and average
droplet size of emulsions prepared from industrial biodiesel using infrared
spectroscopy.

Knowledge of the water content present in biodiesel and diesel is quite

important and very little information is available on this aspect in literature.
This research employs dry polymeric hydrogel for removal of the water
content of diesel and biodiesel samples. Based on the advantages of the
hydrophobicity that hydrogels possess, Water absorption capacity, we have
investigated the use of these polymeric materials for water removal from fuels.

The reason for investigating the use of hydrogels for removing water from
biodiesel, diesel and blends is based on the advantages that hydrophilic hydrogels
particles swell in presence of a water solvent and soak the solvent (water in this
case) into the cross-linked matrix of the particle.

1.2 HYDROGEL ABSORBENTS

Hydrogels are three-dimensional networks of hydrophilic polymer chains,
which can absorb and retain a large amount of water. The extent of swelling is a
unique property of micro gel particles. Their Properties make them useful in a
variety of fields including the oil recovery, molecular separation, Environment
sensitive display devices, biomedical and pharmaceutical applications. In this
study, micro gel particles have been investigated aiming to remove water from

3
saturated biodiesel, diesel and blends fuels. Many researches are being done on
hydrogels to increase and improve their applications in various fields. Cross-
linked hydrophilic polymers made hydrogels have capacity for expanding their
volumes by their high capacity for water absorption, that makes them suitable for
purification of wastewater, drug delivery, and so forth. The use of hydrogels is
known since the late 1950 since the form of the bioengineered contact-lenses.
Recently hydrogels such as poloxamers are useful in regenerative medicine. The
adsorption ability of aromatic organic molecules of the polymer hydrogels has
provided a very good option for polymer adsorbents.

Figure 1 Pictorial Representation of Hydrogel

4
 CHAPTER-2

LITERATURE REVIEW

1. Materials for adsorption purification of water from petroleum and oil

products
Chemistry for sustainable development (2005)
E.E.Sirotkina, L.YU.Novoselova
The most interesting results among those described in literature on the
development and application of the materials for adsorption purification of water
from petroleum and oil products are considered and generalized. Sorbents used
both for elimination of oil outflow and for purification of oil-containing waste
water are considered. Natural (plant- and mineral based), artificial and synthetic
sorbents are described. Fibrous (non-woven, in the form of chaotically positions
fibres, wool, pressed, etc.) materials are considered along with those used in the
dispersed or granulated form. It is stressed that combination of materials
differing both in origin and in the state of aggregation, with additional
modifications if necessary (for thepurpose of enhancing the actual properties or
imparting new characteristics) leads to a multiple increase in the efficiency of
purification process. In this we came to learn about how the water is separated
from petroleum products.

2. Water absorbing Material to removal water from biodiesel and diesel

Procedia Engineering (2012)
M.R Wolf Maciel.,
In this work, hydrogel of polyacrylamide (PAAm) was obtained by free
radical polymerization of acrylamide (AAm) in the presence of N,N'-
methylenebisacry1amide (MBAAm), in aqueous media. The hydrogels were cut

5
and dried before to be used in saturated fuels. Saturated blends of biodiesel and
diesel were mixed in appropriate amounts to form B0 (0% biodiesel and 100%
diesel by volume), B20, B40, B60 and B100. A large study was done to synthesize
an absorbing material to have appropriated characteristics to be used as water
absorbing of fuel samples. The most suitable material must present high swelling
ratio combined with an enough density of cross-linked structure that
enables handling the material. The dried hydrogels were added to the saturated
biodiesel, diesel and blends. Amount of water removal using Hydrogel adsorbent
on diesel and biodiesel by Karl Fischer Technique.

3. In Situ Disassembling Behavior of Composite Hydrogels for the Efficient

Removal of Crystal Violet Dye from Aqueous Solution
ISRN Polymer Science (2014)
Venkatesan Srinivasan et all.,

A novel method for the disassembly of synthetic hydrogels in situ and

thereby enhanced adsorption of crystal violet dye is reported. Silicon present in
the husk ashes of Panicum miliare is used as the trigger for disassembly of poly
(2acrylamido-1-propane sulfonic acid-co-itaconic acid) hydrogels.
Disassembling ability of the ash was determined by changing the temperature of
the husk ash. Surface area and particle sizes of both the disassembled and
assembled forms of the hydrogels were determined by E. Suito’s method.
Removal of crystal violet dye from aqueous solution and the respective
adsorption capacities of disassembled and assembled forms of hydrogels were
compared by varying parameters such as pH, temperature, and agitation speed.
Concentration of the dye in aqueous solution was determined by using UV-
Visible spectrophotometer. FTIR analysis was carried out for the characterization

6
of the hydrogels, ash blended hydrogels, and the free ashes. SEM imaging was
carried out to differentiate the surfaces of the assembled and disassembled
hydrogels. From this we learn how the hydrogel was prepared with efficient
manner.

4. Removal of water content from biodiesel and diesel fuel using hydrogel
adsorbents
Procedia Engineering (2012)
P. B. L. Fregolente, M. R. Wolf Maciel and L. S. Oliveira.

The removal of water content present in fuels such as biodiesel and diesel
is quite important to adequate the fuel to standards for commercialization and to
avoid corrosion of storage tanks and injection equipment in diesel engines. In this
study, hydrophilic hydrogels were employed to remove the water content in
biodiesel and diesel fuel samples. The results showed that the hydrogels were
capable of decreasing the free water content and also the soluble water content
present in the samples. This paper is more useful to learn how the biodiesel and
diesel separated from water by using absorbent.

5. A cellulose based hydrophilic, oleophobic hydrated filter for water/oil

separation
Chemcom Royal society of chemistry (2014)
Kathleen Rohrbach et all.,

A hydrated regular cellulose paper filter modified with nanofibrillated

cellulose (NFC) hydrogel was successfully fabricated for water/oil separation.
The fabricated filter’s hydrophilic and oleophobic properties resulted in increased
filter life and decreased environmental impact,while displaying water flux of 89.6
L h_1 m_2 with efficiency Z99% under gravitational force. Study was done on
the separation of water and oil using hydrated filter with NFC hydrogel.

7
6. Removal of Oil from Water by Calcium Alginate Hydrogel Modified
with Maleic Anhydride
Journal of Polymers and the Environment (2015)
Asma Eskhan, Fawzi Banat.

Calcium alginate hydrogel was prepared and used as a biosorbent for the
removal of oil from aqueous solutions. Calcium alginate hydrogel was further
chemically modified by esterification with maleic anhydride. The changes in the
physicochemical properties of maleic anhydride modified calcium alginate were
investigated via multiple techniques (FTIR, SEM, BET and DSC/TGA).
Adsorption batch experiments were carried out to compare the oil adsorption
capacities of native and modified calcium alginates. Adsorption experiments
were carried out as a function of solution pH, temperature and ionic strength to
determine the optimal conditions for the adsorption of oil. Equilibrium and
kinetic studies were conducted for the modified alginate. Results revealed that
the maleic anhydride modification of calcium alginate improved its adsorption
capacity towards oil. Effect of Calcium alginate hydrogel as a bio sorbent for the
removal of oil from aqueous solutions was studied.

7. Waste management in crude oil processing: Crude oil Dehydration and

desalting.
International Journals of Water Resources(2012)
Hussein K Abdel-Aal, Khaled Zohdy and Maha Abdelkreem

Some of the techniques that are proposed for waste management would
include: modifications in process design or in used process equipment; choosing
alternative approaches or routes for a given process; and recycling. Such methods
are recommended in order to mitigate waste formation. Our main aim in this paper
is to examine in details crude oil treatment, which involves dehydration and
desalting in order to unearth and seize opportunities for waste minimization. In

8
addition, some problems that would lead to waste formation are identified, and
their solutions are recommended. Some factors that are relevant to waste
formation are investigated. They include: desalting temperature, wash water ratio
(dilution water), and type of de-emulsifiers. Various Methods for the dehydration
of crude oil and emulsion treatment followed by desalting was studied.

8.Optimization of Biodiesel Washing by Water Extraction.

WCECS 2007
Suprihastuti Sri Rahayu and Aswati Mindaryani

Castor oil methanolysis produces biodiesel and glycerol. The reaction

catalyzed by potassium hydroxide with excess methanol. It forms a homogeneous
reaction mixture. Due to the limited solubility of the glycerol in the biodiesel,
after the
residual methanol been removed, the glycerol then be separated from the
biodiesel. To confirm the alternative diesel fuel standards, the biodiesel be
washed to remove the residual catalyst and glycerol. On washing, a certain
amount of distilled water poured to the flask while stirring. When the stirring has
stopped, the water will eventually separate and slowly sink taking with it any
soluble material, mainly the remaining glycerol, while the biodiesel will remain
on the top. Experiments have been performed in order to determine the optimum
conditions of the washing and to find a correlation of the extraction variables. As
crude biodiesel, it was quite caustic with a pH more than 9 with glycerol content
0.93 %. Washing the crude biodiesel was sufficient to washout all remaining
catalyst and glycerol, bringing the pH down to near neutral and the glycerol
content down to 0.05 % or less. As the biodiesel to water volume ratio and
temperature are increased, the glycerol mass transfer rates from diluent

9
(biodiesel) to solvent (water) increase, respectively. A correlation to show the
effect of biodiesel to water volume ratio on mass transfer coefficient was
developed in the form of a dimensionless equation. Study on correlation of
Biodiesel to water volume ratio by extraction was done.

10
 CHAPTER 3

EXPERIMENTAL METHODOLOGY

3.1 MATERIALS

All the experiments were performed employing fuel samples from commercial
biodiesel (90% of esters from edible soybean oil and 10% esters from edible beef
tallow, 98.0% of total Esters) obtained from Haritha biofuel, Bangalore and S50
diesel with 10 parts per million (ppm) as sulphur specification which is obtained
from Indian oil

The materials needed for the synthesis of hydrogels are 2-Acrylamido-2-methyl-

1-propane sulfonic acid (AMPS) (99%, Aldrich) m.p. 194–196∘C and Itaconic
acid (IA) (99%, Aldrich), m.p. 166-167∘C, were the monomers. Potassium
persulphate (99.99%, trace metals basis, Aldrich), m.p 99∘C to 100∘C, the
initiator, and N,N methylenebisacrylamide (MBAAm) (99%, Aldrich) m.p. 301–
303∘C, the cross-linker, were all used as obtained.

Figure 2 Chemicals Used To Prepare Hydrogel

11
3.2 BLENDS OF SATURATED BIODIESEL-DIESEL

Blends of biodiesel and diesel were mixed in appropriate amounts to form B0

(0% biodiesel and 100% diesel by volume), B20 (20% biodiesel and 80% diesel),
B40 (40% biodiesel and 60% diesel), B60 (60% biodiesel and 40% diesel) and
B100 (100% biodiesel and 0% diesel). These blends were saturated with water
by mixing 70 mL of fuel (blend) with 10 vol% of distilled water. The mixture
was shaken vigorously for 30 min to ensure proper contact between organic and
aqueous phases and then it was settled for 24 h. The saturated organic phases
were separated from the aqueous phase. The ambient relative humidity in all
experiments was between 35 and 40%, at 20ºC. Samples of all blends were
carried out in duplicate.

Figure 3 Blends of Biodiesel-Diesel

12
3.3 SYNTHESIS OF THE HYDROGELS SAMPLES

Poly (AMPS-co-IA) hydrogels were synthesized by free radical

copolymerization. 1.6560 g of AMPS and 0.2615 g of IA were cross-linked using
0.1540 g of MBAAm as the cross-linker and 0.0400 g of potassium persulfate as
free radical initiator and all the ingredients were made into a 10mL solution, using
double distilled water in a 10mL measuring jar. All of them were then transferred
into a 250mL beaker placed upon a heating plate. The contents were well mixed
and accompanied with a heating rate of 2∘C/min for about 15 minutes, using a
sterile glass rodfor continuous stirring. An increase in viscosity after 10 minutes
was observed. A transparent gel was formed after 15 minutes and was placed in
hot air-oven, to complete the cross-linking process. After 24 hours of heating in
the air oven at 50–55∘C, the hydrogels were removed.

3.4 SWELLING MEASUREMENTS

Each sample of hydrogel was placed in distilled water for swelling at room
temperature. The swelling process was controlled by weighing. The ability to
swell was expressed as the swelling ratio, W, via Eq. (1), in which M1 and M2
are the weights of the swollen and dry samples, respectively:

W = M1 /M2

3.4 KARL FISCHER MEASUREMENT

Karl Fischer titration is a classic titration method in analytical chemistry that

uses coulometric or volumetric titration to determine trace amounts of water in a
sample. The Karl Fischer method is used for many substances as a reference

13
method. It is a chemical analysis procedure which is based on the oxidation of
sulphur dioxide by iodine in a methanolic hydroxide solution. In principle, the
following chemical reaction takes place:

H2O + I2 + SO2 + CH3OH + 3RN -> [RNH]SO4CH3 + 2[RNH]I …eqn ()

The titration can be performed volumetrically or coulometrically.
In the volumetric method a Karl Fischer solution containing iodine is added until
the first trace of excess iodine is present. The amount of iodine converted is
determined from the burette volume of the iodine-containing Karl Fischer
solution.

In the coulometric procedure, the iodine participating in the reaction is generated

directly in the titration cell by electrochemical oxidation of iodide until again a
trace of unreacted iodine is detected. Faraday's law can be used to calculate the
amount of iodine generated from the quantity of electricity required.

Figure 4 Karl Fischer Titrator

14
 CHAPTER 4

4. RESULTS AND DISCUSSION

4.1 AMPS-co-IA HYDROGEL

For the choice of the more suitable AMPS hydrogel for removal water from the
fuel samples (biodiesel and diesel fuel), a large study was carried out, where
different hydrogels have been produced with different proportions of AMPS
monomer and MBAAm cross-linking agent. For the purpose of the research, the
absorbing material must present some appropriated characteristics such as high
swelling ratio combined with an enough density of cross-linked structure that
enables handling the material.

Figure 5 AMPS-Co-IA Hydrogel

4.2 EFFECT OF MONOMER RATIO

The milli molar ratio of IA/AMPS was varied from 0.11 to 9 as shown
in the table 4.8. Weight of the initiator was maintained constant throughout the
experiment as 0.081 g. Weight of Cross-linker was maintained as 0.399g
throughout the experiment. Experiment was carried out at room temperature. The
maximum removal was observed as 99% with 10/90 IA/AMPS monomer ratio.

15
With all other monomer ratio, the %R was found lesser than 10/90. The regular
decrease in the %R with decrease in molar ratios, shows an inverse relationship
between molar ratio and the %R. An increase in the AMPS contribution at
monomer feed composition increased the adsorption capacity of the hydrogels.
This is due to the strongly ionizable sulphonate group present in the molecular
structure of AMPS [181]. The corresponding changes are shown in figure 4.10.

Considering all these facts, IA/AMPS molar ratio was maintained optimum as
10/90 for all the rest of the adsorption experiments.

Table 1 Effect of Monomer Ratio

S.N Weight of Millimoles Weight Millimoles Weight of Molar ratio
o AMPS of AMPS of IA (g) of IA the cross of
(g) linker (g) IA/AMPS
1. 3.726 9 0.262 1 0.399 10/90=0.11
2. 3.312 8 0.523 2 0.399 20/80=0.25
3. 2.898 7 0.786 3 0.399 30/70=0.43
4. 2.484 6 1.048 4 0.399 40/60=0.67
5. 2.07 5 1.31 5 0.399 50/50=1
6. 1.656 4 1.572 6 0.399 60/40=1.5
7. 1.242 3 1.834 7 0.399 70/30=2.33
8. 0.828 2 2.096 8 0.399 80/20=4
9. 0.414 1 2.358 9 0.399 90/10=9

16
 100
98
96
94
92
%R

90
88
86
84
82
0 0.5 1 1.5 2 2.5
molar ratio of IA/AMPS

Figure 6 Effect of Monomer Ratio

4.3 EFFECT OF INITIATOR CONCENTRATION

The role of initiator in the preparation of assembled poly (AMPS-co-IA)
hydrogels is indispensible, since free radical type of addition polymerization is
followed as the mechanism of polymerization. Potassium persulfate is used as the
initiator for the polymerization of AMPS and IA in the presence of MBA as the
cross-linker. The effect of initiator concentration by varying the amount of
Potassium persulfate on the removal of Cr (VI) was studied. The mass of the
assembled hydrogels was maintained constant as 0.1g and the experiment was
carried out at room temperature itself. In order to determine the appropriate
quantity of initiator for this specific polymerization reaction, the molar mass of
the initiator content was varied within 0.25-2.50% of the total molar masses of
the monomers and the cross-linker. The experimental data obtained are tabulated
in table 4.9. The maximum removal of the metal ion was observed at 1% initiator
content and is shown in the fig 4.11. Both lesser and greater initiator
concentrations showed inappreciable efficiency in removing the Cr (VI)

17
concentration. In the case of the lower quantity of initiator, less number of
monomers was initiated for free radical addition polymerization. This should
have lead to the least number of cross-linking between the monomers. However,
in the case of very high quantity of initiator also, the %R is inappreciable. This is
due to the inability to form a polymer network efficiently with small and further
number of radicals in the free radical polymerization [182]. The %R is maximum
obtained in the region of 1% initiator. Therefore, 1% of the initiator was chosen
as the optimum condition for the adsorption of Cr (VI) on assembled hydrogels.

Table 2 Effect of Initiator Concentration

S.No. Weight of the Weight of the % %R
monomers initiator (g) contribution
(AMPS+IA) and of the initiator
crosslinker (g)
1. 4.387 0.011 0.25 88
2. 4.387 0.022 0.5 90
3. 4.387 0.033 0.75 92
4. 4.387 0.044 1 98
5. 4.387 0.054 1.25 97
6. 4.387 0.067 1.5 96
7. 4.387 0.078 1.75 93
8. 4.387 0.089 2 93
9. 4.387 0.098 2.25 90
10. 4.387 0.11 2.5 87

18
 100

98

96

94
%R

92

90

88

86
0 0.5 1Percentage
1.5of initiator2 2.5 3

Figure 7 Effect of Initiator Concentration

4.4 EFFECT OF CROSS-LINKER CONCENTRATION

Addition mechanism requires the contribution of a cross-linker in order
to form a network. As the monomers AMPS and IA have unsaturated carbon-
carbon double bonds, the presence of large quantity of pi-bonds with the MBA is
chosen as the cross-linker. The increase in cross-linker is expected to increase the
quantity of cross-linking between the monomers and thereby, will increase the
mechanical strength of the hydrogels. The cross-linker concentration was varied
in the range 1.0-10.0% of the total monomer mole, in order to find the effect of
cross-linked on removal of Cr (VI) from aqueous solution. The mechanical
strength of the hydrogels naturally increases with the increase in cross-linker
degree. Using the figure 4.13, it is well shown that with the increase of MBA
concentration, the percentage removal of Cr (VI) is slightly increased. With the
increase in the contribution of the cross-linker, the polymer network structure is
supposed to increase, which results because of an increased degree of cross-
linking. This fact is explained with the help of the molecular interactions between
the monomers and the highly unsaturated cross-linker as shown in the figure 4.12.

19
Therefore, the possibility for the formation of uncross-linked hydrogels
decreases. This leads to the availability of a greater number of sites which are
needed for adsorption process. This is the reason for the greater %R with an
increase in the percentage of cross-linker MBA. The corresponding experimental
data by variation of the cross-linker concentration are shown in the table 4.10.
The maxima is obtained with the 10% cross-linker concentration and because of
this reason, 10% cross-linker contribution was chosen as the optimum cross-
linker concentration for all the rest of the experiments.

20
Figure 8 Cross-Linking Of AMPS And IA Monomers

21
 Table 3 Effect of Cross-Linker Contribution
Sl. Total weight of the Weight of the Percentage %R
No monomers cross-linker contribution of
(AMPS+IA) (g) (g) cross-linker
1. 3.988 0.019 0.5 23
2. 3.988 0.039 1 28
3. 3.988 0.059 1.5 31
4. 3.988 0.079 2 36
5. 3.988 0.099 2.5 37
6. 3.988 0.119 3 40
7. 3.988 0.139 3.5 43
8. 3.988 0.159 4 46
9. 3.988 0.179 4.5 53
10. 3.988 0.199 5 59
11. 3.988 0.219 5.5 63
12. 3.988 0.239 6 68
13. 3.988 0.259 6.5 71
14. 3.988 0.279 7 75
15. 3.988 0.299 7.5 80
16. 3.988 0.319 8 90
17. 3.988 0.339 8.5 91
18. 3.988 0.359 9 93
19. 3.988 0.379 9.5 96
20 3.988 0.399 10 98

22
 120

100

80
%R

60

40

20

0
0 2 4 6 8 10 12
Percentage of cross-linker

Figure 9 Effect of Cross-Linker Concentration

Figure 10 IR of AMPS Hydrogel

23
Figure 11 SEM Images Of AMPS Hydrogel

24
4.5 WATER ABSORPTION FROM BIODIESEL, DIESEL AND BLENDS

Once established the suitable hydrogels to be used in the research, they

were used to absorbing water from B100, B60 and B20 saturated samples. Three

concentrations of Hydrogel (20, 30 and 50 mg/mL) were set into three

different mixers containing B100, B60 and B20 saturated samples. It was kept in
the shaker for

180mins for the proper contact between the Hydrogel and Biodiesel –
diesel samples for the absorption of water content. The volumetric Karl Fischer
technique was used to determine the water content in biodiesel and diesel and
biodiesel/diesel blends. In this study, a MA – 101C Karl Fischer from Spectral
lab was used. The reagents used (Hydranal Solvent Oil and Hydranal Titrant 2)
were purchased from Sigma-Aldrich.

Figure 12 Biodiesel-Diesel Blends at Shaker

25
4.6 EFFECT OF HYDROGEL ON B100 SAMPLE

Figure 1(A) shows that B100 sample containing 30 mg/mL of H9

presented a decreasing of water content from 3926 ppm to 3366.62 ppm of water
in 3 hours. The B100 sample containing 50 mg/mL of H9 showed a quickly
decreasing of water content from 3926 ppm to 3305.36 ppm in 3 hours and the
B100 sample containing 20 mg/mL showed a slower reduction of water content
from 3926 ppm to 3692 ppm in 3 hours and lesser efficiency than others.

Figure 13 Effect of Hydrogel On B100 Sample

4.7 EFFECT OF HYDROGEL ON B60 SAMPLE

Figure 1(A) shows that B60 sample containing 30 mg/mL of H9 presented

a decreasing of water content from 2695 ppm to 1976.63 ppm of water in 3 hours.
The B60 sample containing 50 mg/mL of H9 showed a quickly decreasing of
water content from 2695 ppm to 1343.68 ppm in 3 hours and the B60 sample
containing 20 mg/mL showed a slower reduction of water content from 2695 ppm
to 2342.32 ppm in 3 hours and lesser efficiency than others.

26
 3000

2695
2500
2342.32

2000 1976.63
ppm

1500
1343.68

1000

500

0
0 10 20 30 40 50 60
Wt of gel mg/mL

Figure 14 Effect of Hydrogel on B60 Sample

4.5 EFFECT OF HYDROGEL ON B20 SAMPLE

Figure 1(A) shows that B20 sample containing 30 mg/mL of H9 presented

a decreasing of water content from 2672.02 ppm to 1887.21 ppm of water in 3
hours. The B20 sample containing 50 mg/mL of H9 showed a quickly decreasing
of water content from 2672.02 ppm to 1685.97 ppm in 3 hours and the B20
sample containing 20 mg/mL showed a slower reduction of water content from
2672.02 ppm to 2577.32 ppm in 3 hours and lesser efficiency than others.

27
Figure 15 Effect of Hydrogel On B20 Sample

28
 CHAPTER 5

CONCLUSION

Based on the results obtained in this work, new hydrogels composed of

different hydrophilic monomers will be synthesized and tested for their ability to
remove water from fuel. The tests may also be extended to other liquid fuels such as
gasoline and jet fuel. The performance of these hydrophilic hydrogel particles could
be applicable for adsorbing water from other liquid fuel types and has the potential
for development of new technologies for removing water from fuels.

Biodiesel is a fuel comprised of mono-alkyl esters of long chain fatty acids derived
from vegetable oils or animal fats. However, the hydrophilicity of both fuel (diesel
and biodiesel) is different due to the presence of ester bonds in the biodiesel fuel
which gives it a higher absorption capacity of water. Thus, the addition of biodiesel
in diesel increases the water holding capacity of blend, as evidenced by initial water
content of the blends at 30ºC For (B100), the water content was reduced down to
3305 ppm from 3926 ppm (reduction of 60% of water content). The reductions of
water content for B20, B60 were 30%, 45 %, respectively, after 180 min of treatment
with hydrogel.

29
 REFERENCES

1. Oliveira MB, Varanda FR, Marrucho I M, Queimada AJ, Coutinho AP.

Prediction of Water Solubility in Biodiesel with the
CPA Equation of State. Ind Eng Chem Res 2008;47:4278-4285.

2. ASTM Standands. D6751-03a. Specification for biodiesel fuel (B100) blend

stock for distillate fuels. West Conshohocken,
Penn.: ASTM, 2003.

3. Nur H, Snowden MJ, Cornelius VJ, Mitchell JC, Harvey PJ, Benee LS.
Colloidal microgel in removal of water from
biodiesel. Colloids and Surfaces A: Physicochem Eng. Aspects 2009;335:133-
137.

4. Bücker F, Santestevan A N, Roesch LF, Jacques R J S, Peralba M C R,

Camargo F A O. Impact of biodiesel on
biodeterioration of stored Brazilian diesel oil. Int Biodet Biodegradation
2011;65:172-178.

5. Sørensen G, Pedersen D V, Nørgaard A K, Sørensen K B, Nygaard S D.

Microbial growth studies in biodiesel blends.
Biores Technol 2011;102:5259-5264.

6. He BH, Thompson JC, Routt DW, Van Gerpen JH. Moisture Absorption in
Biodiesel and its Petro-Diesel Blends. Appl Eng
Agric 2007;23:71-76.

7. Qunwei T, Jihuai W, Hui S, Jianming L, Shiun F, De H.

Polyaniline/polyacrylamide conducting composite hydrogel with a
porous structure. Carbohydr Polym 2008;74:215-219.

8. Bassil M, Davenas J, Tahchi ME. Electrochemical properties and actuation

mechanisms of polyacrylamide hydrogel for
artificial muscle application. Sensors and Actuators B 2008;134:496-501.

9. Deligkaris K, Shiferaw T, Olthuis W, Van der Berg A. Hydrogel-based devices

for biomedical applications. Sensors and
Actuators B 2010;147:765-774.

30
10. A. S. Hoffmann, “Hydrogels for biomedical applications,” Advanced Drug
Delivery Reviews, vol. 54, no. 1, pp. 3–12, 2002.

11. N. A. Peppas, Y. Huang, M. Torres-Lugo, J. H. Ward, and J. Zhang,

“Physicochemical foundations and structural design of hydrogels in medicine
and biology,” Annual Review of Biomedical Engineering, vol. 2, pp. 9–29,
2000.

12. X. Y. Hu and Y. B. Chen, “Adsorption properties of chemical crosslinked

polymer gel,” Advanced Materials Research, vol. 87- 88, pp. 22–26, 2009.

13. R. Coskun, “Removal of cationic dye from aqueous solution by adsorption

onto crosslinked poly(4-vinylpyridine/crotonic acid) and its N-oxide
derivative,” Polymer Bulletin, vol. 67, no. 1, pp. 125–140, 2011.

14. S. C¸avus¸ and G. G¨urdaˇg, “Noncompetitive removal of heavy metal ions

from aqueous solutions by poly[2-(acrylamido)- 2-methyl-1-propanesulfonic
acid-co-itaconic acid] hydrogel,” Industrial and Engineering Chemistry
Research, vol. 48, no. 5, pp. 2652–2658, 2009.
.
15. Kirk, R.E. , and Othmer D.F. (1980), Encyclopedia of Chemical
Technology, 9, pp.306-308, John Wiley and Sons, New York.

16. Swern D. (1982), Bailey’s Industrial Oil and Fat Product, 2, 4 ed., pp
130-133, John Wiley and Sons, New York.

17. Freedman B., Pryde E.H. and Mount T.L. (1984), Variables Affecting the
Yields of Fatty Ester from Transesterification Vegetables Oils, JAOCS,
61, 1638 – 1642.

18. Levenspiel, Octave, (1972), Chemical Reaction Engineering, 2nd ed., John
Wiley and Sons, New York.

19.Treybal, R.E. (1980), Mass Transfer Operations, McGraw Hill

Kogakusha Ltd.,Tokyo.

20. Paquot, C.(1979), Standard Methods for the Analysis of Oil Fats and
Derivatives, 6th ed, pp 52-57, A. Wheaton & Co. Ltd, Exeter.

21. Perry, R.H. and Green, D.E. (1997), Chemical Engineer’s Handbook,
McGraw-Hill Book Company Inc., New York.

31
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