Preparation of Zeolite-Based Catalyst from Fly Ash for the

Synthesis of Biodiesel from Waste cooking oil

Project report submitted to

Visvesvaraya National Institute of Technology,Nagpur

in partial fulfillment of the requirements for the award of the degree

Bachelor of Technology
In
Chemical Engineering
by
SHUBHANGI SOLANKE
(BT15CME078)
Under the guidance of

DR. DIWAKAR Z. SHENDE

Department of Chemical Engineering

Visvesvaraya National Institute of Technology
Nagpur 440010 (India)
April 2019
© Visvesvaraya National Institute of Technology (VNIT) 2019
 Department of Chemical Engineering

Visvesvaraya National Institute of Technology, Nagpur

Declaration

I, Shubhangi Solanke, hereby declare that this project work titled “Preparation of
Zeolite-Based Catalyst from Fly Ash for the Synthesis of Biodiesel from Waste
cooking oil” is carried out by me in the department of Chemical Engineering of
Visvesvaraya National Institute of Technology, Nagpur. The work is original and has
not been submitted earlier whole or in part for the award of any degree at this or any
other Institution.

SHUBHANGI SOLANKE

(BT15CME78)

DATE
 Certificate
This is to certify that the project titled “Preparation of Zeolite-Based
Catalyst from Fly Ash for the Synthesis of Biodiesel from Waste
cooking oil” submitted by SHUBHANGI SOLANKE in partial
fulfillment of the requirements for the award of the degree of Bachelor of
Technology in Chemical Engineering , VNIT Nagpur. The work is
comprehensive, complete and fit for final evaluation.

Dr. Diwakar Z.Shende

Assistant Professor,
Department of Chemical Engineering,
VNIT, Nagpur.
Dr. M.N. Verma,

Head, Department of Chemical Engineering,

VNIT, Nagpur

Date:
 ACKNOWLEDGEMENT

We would like to place on record our innate sense of gratitude to our guide Prof. Dr.
Diwakar Z.Shende for his indispensable guidance and constant support. We thank
him for his immense help and valuable suggestions during discussions towards the
completion of our project work.

In addition, we would like to thank Mr. Anshuman Singh ,Mtech student, VNIT, Ms.
Shraddha Wadatkar, PhD Scholar, VNIT, of Chemical engineering department for
their help and cooperation during the course of this project.

We are extremely grateful to all the faculty and staff of the Chemical engineering
Department of for providing us with immense guidance and support for the entire four
years of Bachelor’s degree course. Last, but not the least I express thanks to my
parents and friends for their constant help, support and encouragement.

Shubhangi Solanke
(BT15CME078)
Abstract
Zeolite X was prepared from the raw fly ash. It was used as a catalyst in further
process. The study involves alkali fusion followed by hydrothermal treatment. The
sample was calcinated in muffle furnace and was HCl treated to increase their activity
in zeolite formation. The acid treatment helped to dealuminate the fly ash and
removed iron to a certain extent, thereby increasing the activity, thermal stability and
acidity of the zeolite, all aiming for better catalytic applications. The characterization
of zeolite from fly ash was carried out using scanning electron microscope (SEM),
energy dispersive x-ray spectroscopy (EDS) and Fourier transform infrared
spectroscopy (FTIR) to evaluate the desired characteristics of the catalyst. Also
particle size analyzer (PSA) was done to find the particle size of the zeolite formed.

Thereafter the prepared zeolite was used as a catalyst in converting the free fatty acids
present in waste cooking oil to biodiesel by the esterification method. Finally we tried
to analyse the conversion of Free fatty acids (FFA) by titration and calculating the
acid value.
LIST OF FIGURES

Fig 1.1 Separation of Cenosphere from ash dyke…………………………

Fig1.2: fly ash contamination pathways…………………………….

Fig 1.3 Various applications of coal fly ash…………………………

Fig 1.4 SEM images of fly ash…………………………………………….

Fig.1.5 Reaction of triglyceride with methanol…………………………………….

Fig.3.1 Process flow diagram for synthesis of zeolite from fly ash………

Fig.3.2 Calcinated Fly Ash………………………………………………..

Fig.3.3 Solution kept in ultra sonic bath………………………………. …

Fig.3.4 Sample Filtration………………………………………………….

Fig.3.5 Mixture of NaOH and Fly Ash milled and fused…………………

Fig.3.6 Agitated Slurry……………………………………………………

Fig.3.7 Experimental Setup…………………………………………………………

Fig.3.8 Determining Acid Number by Titration……………………………

Fig 3.9 JEOL 6380A Scanning Electron Microscopy……………………

Fig 3.10 machine JEOL JFC-1600 Auto fine coaster………………………

Fig 3.11 Microtrac Flex particle size analayzer…………………..

Fig 3.12 Computer showing the data………………………………..

Fig 3.13 FTIR Image………………………………………….

Fig 4.1 PSA result for Run 1……………………………

Fig 4.2 PSA result for Run 2…………………

ii
Fig 4.3 Obtained FTIR Graph…………………………….

Fig 4.4 actual FTIR Graph………………………………….

Fig 4.5 SEM images of obtained zeolite at different magnifications……

Fig 4.6 Graph showing elemental composition of Zeolite………..

iii
 LIST OF TABLES

Table 1.1 Chemical Property of FLY ASH…………………………….

Table 1.2 Physical Property of fly ash………………….

Table 4.1 Result of PSA……………………….

Table 4.2 Elemental Composition of the sample by Weight………..

Table.4.3 %Conversion of FFA…………………

iv
 LIST OF ABBREVATIONS

FA Fly Ash

FAC Fly Ash Cenosphere

PSA Particle Size Analyzer

SEM Scanning Electron Microscopy

FTIR Fourier transform infrared spectroscopy

ED Energy Dispersive Spectroscopy

FFA Free Fatty Acids

FT Fusion Temperature

v
 INDEX

ABSTRACT…………………………………………………………………………..i

LIST OF FIGURES………………………………………………………………….ii

LIST OF TABLES…………………………………………………………………..iii

LIST OF ABBREVATIONS………………………………………………………..iv

INDEX………………………………………………………………………………..v

CHAPTER 1 : INTRODUCTION…………………………………………………..1

1.1 Fly ash : Overview…………………………………………………

1.1.1 Thermal power plant-largest producer of fly ash in India
1.1.2 Environmental consequences of fly ash
1.1.3 Applications of fly ash
1.1.4 Chemical and physical properties of fly ash
1.2 Zeolite from coal fly ash
1.3 Application of zeolite as a catalyst in biodiesel production
1.4 Objective of this study

CHAPTER 2: LITERATURE REVIEW

2.1 Application of fly ash

2.2 Zeolite from fly ash

2.3 Removal of free fatty acid in waste frying oil by esterification with methanol
On Zeolite catalysts

CHAPTER 3 : MATERIALS AND METHODS

3.1 Materials

3.2 Zeolite Synthesis

3.3 Application of Zeolite as a Catalyst in Bio-Diesel Production

3.3.1 Determination of Acid Number

3.4 Scanning Electron Microscopy & Energy Dispersive Spectroscopy

vi
 3.5 Particle size analyzer

3.6 Fourier transform infrared spectroscopy (FTIR)

CHAPTER 4 : RESULTS AND DISCUSSIONS

4.1 Catalyst (Zeolite) Analysis

4.11 Particle Size Analysis (PSA)

4.12 Fourier transform infrared spectroscopy (FTIR)

4.13 Powder Morphology, Characteristics and Chemical Analysis

4.2 Application of Zeolite as a catalyst in Biodiesel Production.

CHAPTER 5 : CONCLUSION

5.1 Conclusion

REFERENCES

vii
 CHAPTER 1
INTRODUCTION
1.1 Fly ash : Overview

In recent years the exhaustion of the petroleum resources has been warned. Coal has been reassessed as an
energy source from the viewpoints of low cost, large deposits and provision stability. Fly ash is one of the
products obtained after combustion of the coal, composed of fine particles that are driven out of the boiler
with the flue gases constituting about 60-80% of total combustion residues from coal fired power plants.
Globally, the annual production of fly ash is estimated to be between 0.75-1 billion tones. As demand for
cheap power rises in the developing countries this quantity is expected to increase in the coming years. As
fossil-based power is expected to remain a major source of global electricity supply in the coming years, the
absence of effective management strategies will increase the problem of fly ash waste in the environment.
There is a necessity for the development of new pathways for its utilization as a means of diverting it from
landfills where it poses a significant threat to the environment [1].

The ceramic particles of fly ash have three types of structures: cenosphere, plerosphere, and precipitator. A
few particles are strong and are empty from inside which are known as cenospheres. Precipitators are small
solid particles. Plerosphere are thin walled hollow spheres which are hollow particles of large diameters filled
with smaller size plerospheres and cenospheres.A cenosphere is a lightweight, empty sphere made to a great
extent of silica and alumina and loaded with air or inactive gas (CO2 and N2), commonly processed as a by-
result of coal burning at power plants . Cenospheres fluctuate from light black colour to practically white
shade and their specific gravity is in the range of 0.4–0.8, which offers them extraordinary lightness [2].

The Thermal Power Plant discharge fly ash generated from combustion of coal, in slurry stage and pump to
lagoons specially made for storage of fly ash. Here cenosphere gets separated and float on water which is
collected at edge of lagoons and harvested by labours with the help of shovel and collected in bags for
transport to processing plants. Below figure shows procedure of separation of cenosphere from ash dyke. The
process is shown in Fig 1.1 [1].

Fig 1.1 Separation of Cenosphere from ash dyke [12]

1
1.1.1 Thermal power plant-largest producer of fly ash in India

In meeting the demands of power generation fossil fuel plays an important part. Around the world India is the
fourth largest producer of coal. One of the world’s richest and widely distributed fossil fuel is coal. About 70-
70% of total power generated in India is produced by coal based thermal power plants. About 300 million
tons of coal are being used by thermal power plant [3].

Hence, needful efforts are being made continuously by making stringent regulations by the government to
fully utilise the ash. Currently only 50-60% of fly ash is being profitably utilized in India.

And thus further research is in progress to effectively use this by-product to produce new usable and
profitable materials as they pose major disposal and environmental problems.

1.1.2 Environmental consequences of fly ash

Although some portion of the generated fly ash is used for dam construction,as fillers in road and brick
manufacturing, a significant amount is still have been disposed in land-fills or ash ponds with several
environmental consequences. It can cause water and soil pollution, can disrupt ecological cycle. Irregular
accumulation and inappropriate disposal of fly ash will lead to its disposal over vast areas of land, with
resultant degradation of the soil and danger to both human health and the environment. Fly ash particles,
small enough to escape emission control devices, are easily suspended in air and have become a major source
of gas pollution. Repeated exposure to fly ash can cause irritation of the eyes, skin, nose, throat and
respiratory tract, and can even result in arsenic poisoning (Craig Heidrich et al., 2013).
Due to the entrainment of the particles in the air and leaching of toxic components into the soil or water
bodies, the environmental threats from the disposal of fly ash arise. This threats are documented in fig 2 [4].

Fig1.2: fly ash contamination pathways [4]

2
For instance the power companies are eliminating the cost of disposal by earning revenue from the
sale of fly ash to off takers who use it as raw materials for different products. The natural resources
would be conserved by the utilisaton of fly ash and it will also result in the reduction of landfill area
required for the disposal of fly ash.

1.1.3 Applications of fly ash

A good alternative to disposal is the recycling of coal fly ash and significant environmental and economic
benefits can be achieved as well. Some current application fly ash is illustrated in fig1.3 [4].

Fig 1.3 Various applications of coal fly ash [5]

1.1.4 Chemical and physical properties of fly ash

The chemical composition and the physical properties of fly ash in general are shown in Table 1.1 &
Table 1.2. These are generic in nature and may vary depending on various conditions of manufacturing
and grade of fly ash [5].

Table 1.1 Chemical Property of fly ash [13]

Compound Content, %wt

SiO2 59.00
Al2O3 21.00
Fe2O3 3.70
CaO 6.90
MgO 1.40
SO3 1.00
K2O 0.9

3
 Table 1.2 Physical Property of fly ash [13]

Color Whitish grey

Bulk density (g/cm3) 0.994

Specific gravity 2.288

Moisture (%) 3.14

Average particle size 6.92 µm

Surface area (m2/g) 2.9

pH 1.2-12.5

The SEM images of raw fly ash are shown in fig 1.4

Fig 1.4 SEM images of fly ash

1.2 Zeolite from coal fly ash

As per my research and study alkali fusion followed by hydrothermal treatment is the most reliable method of
obtaining zeolite selectively from fly ash of different compositions.
Hydrothermal treatment technology employes the combination of heat and water as a media to convert the
unutilized resources. There exist three steps in alkali hydrothermal reaction of zeolite synthesis: the
dissolution step of Si4+and Al3+ in coal fly ash, the condensation step of silicate and aluminate ions in alkali
solution to make aluminosilicate gel, and the crystallization step of aluminosilicate gel to make zeolite crystal.
The OH- in alkali solution remarkably contributes to the dissolution step of Si4+ and Al3+ in coal fly ash, while
Na+ in alkali solution makes a contribution to the crystallization step of zeolite.

In alkaline solutions, aluminum gives negatively charged tetrahedral [Al(OH)4]– species.

The general reaction scheme describing the zeolite synthesis process is as follows:
4
NaOH + xAl2O3.ySiO2 Na2SiO3 + Na2AlO2

It is considered that when a large quantity of silicate ion exists in the liquid phase, aluminate ions and silicate
ions are condensed to form an aluminosilicate gel with an increase in reaction temperature, and then the
aluminosilicate gel, which is a prematerial of zeolite crystal, is created [6].

1.3 Application of zeolite as a catalyst in biodiesel production

Biodiesel is biodegradable and nontoxic, has low emission profiles and so is environmentally beneficial.
Biodiesel comprises of long chain, fatty acid alkyl esters produced from vegetable oils or animal fats by
transesterification of the triglycerides [7].
Transesterification, also called alcoholysis, is the displacement of alcohol from an ester by another alcohol in
a process similar to hydrolysis. This process has been widely used to reduce the viscosity of triglycerides.
The transesterification reaction is represented by the general equation:

RCOOR′+R″→RCOOR″+RCOH

If methanol is used in the above reaction, it is termed methanolysis. The reaction of triglyceride with
methanol is represented by the general equation:

Fig.1.5 Reaction of triglyceride with methanol [14]

Mechanism:

In the transesterification mechanism, the carbonyl carbon of the starting ester react to give a tetrahedral
intermediate, which either reverts to the starting material, or proceeds to the transesterified product
(RCOOR2). The various species exist in equilibrium, and the product distribution depends on the relative
energies of the reactant and product.

5
Zeolites have been employed in biodiesel production as a heterogeneous catalyst. In my study, the direct
esterification reaction of the FFA in waste frying oil with methanol was conducted using the obtained zeolite
catalyst. The catalytic activity of the zeolite catalyst was studied on the FFA removal reaction by determining
the acid value [8].

1.4 Objective of this study

The objective of this study is to prepare a zeolite catalyst from raw fly ash by acid (HCl) treatment
followed by hydrothermal treatment process and then we shall study the catalyst. Thereafter we shall use the
catalyst in converting the free fatty acids present in waste cooking oil to biodiesel by the esterification
method. Finally we will try to analyse the conversion of FFA by titration and calculating the acid value.

6
 CHAPTER TWO
LITERATURE REVIEW

7
In this chapter literature review related to zeolite synthesis and the various uses of this zeolite in industry as
well as the application of zeolite as catalyst in transesterification process for the production of biodiesel and
their results shall be discussed.

2.1 Application of fly ash

Coal ash is discharged in large amounts from electric power plants and many other factories. Utilization is
one of the prominent strategies for the management of hazardous industrial wastes like fly ash. Although fly
ash has applications in numerous industries, the most prominent is in the construction where it is used as a
supplementary cementitious material. Other applications are in the areas of soil amendment environmental
remediation as adsorbents for gas and waste water treatment, consumer goods as detergent builders, and in
industrial processes as catalysts. Few industrial applications are explained below:

Soil amelioration:

The physicochemical properties of coal fly ash including silt and clay-sized particles, low bulk density, higher
water-holding capacity, favorable pH, and source of essential plant nutrients, etc., make it a potential
amendment for soils. In addition, use of fly ash instead of lime can reduce CO2 emission and thus reduce
global warming. Coal fly ash, being mostly alkaline, can be used for buffering the soil pH . Fly ash also
contains some useful nutrients, such as P, S, K, Ca, Mg, Cu, and Zn, which are beneficial for the plant
growth. Researchers have found other beneficial effects: improving the soil texture, aeration, percolation, and
water retention in the treated zone; reducing soil bulk density and the consumption of other soil amelioration
agents; serving as an insecticide owing to the presence of abrasive silica in fly ash; and decreasing the
mobility and availability of metals in the soil due to alkaline nature of fly ash. Fly ash application improves
the physical, chemical and biological qualities of soils to which it is applied. The use of fly ash as an
agricultural amendment can be enhanced by blending it with potentially acid-forming organic by-products
such as sewage sludge, poultry and animal manure. Co-application of fly ash with these materials has more
advantages: enhancing nutrient availability, decreasing bioavailability of toxic metals, buffering soil pH,
enhancing soil organic matter content, indirectly stimulating microbial activity, overall improving soil health
and increasing crop yield [5].

8
Construction industry:
Fly ash has predominantly been used as a substitute for material in the construction industry, especially either
as a raw material or as an additive in the cement industry. The silica in fly ash reacts with calcium hydroxide
released by the hydration of calcium oxide to produce calcium Silicate hydrate. The pozzolanic properties
make it useful for cement replacement in concrete and other building applications. Inclusion of fly ash in the
binder improves the workability and reduces the bleeding of freshly mixed concrete. Hardened fly ash
concrete, when properly designed, shows increased strength together with a lower permeability. In addition,
partial replacement of cement with fly ash could reduce production costs. fly-ash based geo polymer has
emerged as a promising new cement alternative in the field of building and construction materials. fly-ash
based geo polymer concrete has similar strength and durability properties to those of traditional cement
concrete. A benefit has been observed in recycling both the bottom ash and the FBC ash in pavement and
roadway construction applications [5].

Zeolite synthesis:
Synthesis of zeolites is gaining notice as one of the effective uses for coal fly ash, possibly due to the similar
compositions of fly ash. Zeolite synthesis is conventionally developed by hydrothermal crystallization under
alkaline conditions. However, mullite and quartz in ash are considered to be inert and difficult to dissolve. the
total reaction rate of zeolite synthesis was influenced by the Na+ concentration in the alkali solution of
NaOH. The synthesized zeolites can be used in various engineering and agricultural applications for water
purification, gas cleaning and soil amendment [5].

Catalysis:
Metal and metal oxides are widely used as catalysts in various industrial applications. Fly ash mainly consists
of various metal oxides with higher content of iron oxides and possesses higher thermal stability. Thus,
utilization of fly ash in heterogeneous catalysis could provide a cost effective and environmentally friendly
method for recycling this waste. Besides, due to the higher stability of its principal component alumino
silicates, fly ash could also be employed as catalyst supports for various reactions. Fly-ash-supported CaO has
been employed as a catalyst for the transesterification of soybean oil. It exhibited high catalytic performance
in converting soybean oil into fuel-grade biodiesel with a higher fatty acid methyl ester content. fly ash, after
pre-treatment and loading with transition metal elements, can be reasonably used as an catalyst support to
remove NO from flue gas. fly ash can be used as an effective catalyst for reactions in gas, liquid- and solid
phases, such as gas phase oxidation of volatile organic compounds, aqueous phase oxidation of organics, solid
plastic pyrolysis, and solvent free organic synthesis [5].

9
Ceramic industry:
Coal fly ash contains appreciable amounts of SiO2, Al2O3, CaO and Fe2O3, among other oxides. These oxides
have often been considered a low cost material for the ceramic industry. In addition, the fine powder form
makes it suitable to be directly incorporated into ceramic pastes with almost no pretreatment. Recent research
has investigated the production of glass, glass–ceramic and sintered materials prepared from coal fly ash. The
basis of manufacture is the temperature activation of the raw fly ash with variations in temperatures and co-
reagents directing the final form of the glass or ceramic [5].

2.2 Zeolite from fly ash

There is a necessity for the development of new pathways for the utilization of fly ash as a means of diverting
it from landfills where it poses a significant threat to the environment. Several approaches have been made for
proper utilization of fly ash, either to reduce the cost of disposal or to minimize the environmental impact.
One of the approaches is the conversion of fly ash to zeolites, which have wide applications in ion exchange,
as molecular sieves, catalysts, and adsorbents. In general, zeolite synthesis processes involve the addition of a
caustic agent to the fly ash slurry at higher temperatures. The coal fly ash contains mainly SiO2, Al2O3 and
some amount of Fe2O3 and the oxides of Mg, Ca, P, Ti etc. Alkali fusion is a conventional method for
chemical analysis to decompose materials containing silicon and/or aluminum. The sodium hydroxide present
in the reaction mixture acts as an activator during fusion to form soluble silicate and aluminate salts, which
further takes part in zeolite formation during hydrothermal process. Na+ cation also plays an important role in
zeolitization. Sodium ions are known to stabilize the sub-building units. The sodium to aluminum ratio of the
treated ash was also found to increase with the increase in NaOH content of the mixture during fusion. The
higher the sodium contents in the reactant mixture during fusion, the higher is the production of water-soluble
sodium silicates. Increased formation of sodium silicates again enhances the yield of zeolitic materials
produced in subsequent stages. Crystallization of the zeolitic materials occurs through nucleation reaction and
crystal growth. Nucleation again depends upon the alkalinity. Thus, crystallinity of the resultant products is a
function of the alkalinity of the reaction mixture. alkali present in the fusion mixture reacts with the silica and
alumina present in the fly ash and form silicate and aluminate salts. Silicate anions react readily with Al (III)
precursors to form aluminosilicate compounds [6].
The properties of synthesized zeolitic materials are affected by fusion temperature (FT). The ratio increases
with fusion temperature. During fusion, the silica and alumina present in the fly ash react with the alkali and
form Na-salts soluble in water. The crystallinity was also found to change with fusion temperature. The
zeolite synthesis reaction takes place at the interface between particle and alkali solution.Therefore, as the

10
condensation reaction of aluminosilicate and the formation of a zeolite crystal proceed, aluminate ions and
silicate ions are not supplied from coal fly ash because the particle surface is covered with the deposit
material, such as an aluminosilicate gel and a zeolite crystal. When aluminate ions remaining in an alkali
solution are completely consumed, Si and Al ingredients in the alkali solution are not supplied and consumed.
As a result, it is considered that Si4q and Al3q concentrations reach an equilibrium state. Alongwith SiO2 and
Al2O3, fly ash contains several other components that are undesirable in synthesized zeolites. Some of these
components act as poison during catalytic applications of zeolites. Some of these unwanted materials could be
removed by acid treatment. In the present study, HCl was used to reduce the concentration of iron and alkali
oxides present in fly ash, which were located mainly in the outer part of the ash particles and also to leach
some amount of Al2O3.Thus, it helped in increasing the SiO2 content of the reaction mixture. On acid
treatment, iron oxide present in the original fly ash was removed to some extent. After the zeolite is made it is
is used as a catalyst in biodiesel production [9].

2.3 Removal of free fatty acid in waste frying oil by esterification with methanol on
zeolite catalysts

Conventionally, biodiesel is produced using a homogeneous mineral acid or alkali catalysts. In addition to the
corrosion problems, these homogeneous catalyst-based
processes involve elaborate process steps for removal of FFAs and water from the feedstock and catalyst from
the products. Zeolites are microporous crystalline solids with well defined structures. Generally they contain
silicon, aluminum and oxygen in their framework and cations. Zeolites are finding applications in many areas
of catalysis, generating intense interest in these materials in industrial and academic laboratories. As catalysts,
zeolites exhibit appreciable acid activity with shape selective features not available in the compositionally
equivalent amorphous catalysts. More recent research on alcoholysis has focused on the use of heterogeneous
catalysts. Zeolites have been employed in biodiesel production as a heterogeneous catalyst. In present study,
the direct esterification reaction of the FFA in waste frying oil with methanol was conducted using various
zeolite catalysts.
The conversion of FFA was slightly improved to 80% with increasing of reaction temperature, but it exhibited
no more increase at above 60oC. The conversion of FFA also became higher with increasing of loading
amount of zeolite. However, it did not show a significant increase above 1.0 g of catalyst loading. The
conversion of FFA increased with proceeding of reaction and it reached to equilibrium after 90 min. To
compare the catalytic activities of the zeolite catalysts in the FFA removal reaction, the reaction conditions
were adjusted as 1.0 g of catalyst loading, 60oC of reaction temperature, and 3 h of reaction time [10].

11
 CHAPTER THREE
MATERIALS AND METHODS

12
3.1 Materials

Materials used are Sodium Hydroxide Pellets, Hydrochloric Acid, Distilled water (pure), Methyl Alcohol,
Waste frying oil, Isopropanol, Potassium Hydroxide, Fly Ash.

3.2 Zeolite Synthesis

Fig.3.1 Process flow diagram for synthesis of zeolite from fly ash [6]

The steps followed are listed below

1. The required amount of Raw Fly Ash first screened through a BSS Tyler sieve of 80-mesh size to
eliminate the larger particles.
2. The unburnt carbon (4–6%) along with other volatile materials present in fly ash were removed by
calcination at 800 ± 10°C for 2 hours.

13
 Fig.3.2 Calcinated Fly Ash

1. 1 Molar HCl solution was prepared, (1:2) Weight/Volume Ratio of Fly Ash to HCl solution was taken
and kept in an ultrasonic bath for 1 hour. After the treatment sample was filtrated, washed and dried at
100oC overnight. The acid treatment helped to dealuminate the fly ash and removed iron to a certain
extent, thereby increasing the activity, thermal stability and acidity of the zeolite, all aiming for better
catalytic applications.

Fig.3.3 Solution kept in ultra sonic bath Fig.3.4 Sample Filtration

2. Mixture of sodium hydroxide and fly ash (calcined and HCl treated) in a pre-determined ratio, was
milled and fused in a stainless steel tray at different temperatures ranging from 500 to 650°C for 1
hour. The sodium hydroxide to fly ash ratio (by weight) was varied from 1 to 1.5.

14
 Fig.3.5 Mixture of NaOH and Fly Ash milled and fused

3. The resultant fused mixture was then cooled to room temperature, ground further and added to water
(10 g fly ash/100 ml water).
4. The slurry thus obtained was agitated mechanically in a glass beaker for 1 hour.

Fig.3.6 Agitated Slurry

5. It was then kept at around 90°C for 6 hours without any disturbance.
6. The resultant precipitate was then repeatedly washed with distilled water to remove excess sodium
hydroxide, filtered and dried. The sodium hydroxide added to the fly ash not only works as an
activator, but also adjusts the sodium content in the starting material. Mullite and α-quartz present in
the fly ash are the sources of aluminium and silicon, respectively, for zeolite formation.

3.3 Application of Zeolite as a Catalyst in Bio-Diesel Production

Steps followed are listed below:

The reaction of Free Fatty Acid removal over zeolite catalysts was carried out by batch-type reactor equipped
mechanical stirrer and a water-cooled condenser.

15
 1. The reactants consisted of methyl alcohol and a waste frying oil.
2. The Molar ratio of waste frying oil and methyl alcohol was adjusted to 1.5 (v/v) according to
literature.
3. The reactants were charged, and then were stirred in a round bottom flask. The speed of stirring
maintained with 600 rpm.
4. The mixture was separated in a separating funnel.

Fig.3.7 Experimental Setup

3.3.1 Determination of Acid Number:

These are the steps followed for Determination of Acid Number

1. Acid number was determined by Titration.

2. The sample was mixed with Isopropanol. 3-4 drops of phenolphthalein indicator was added to the
mixture.
3. It was titrated with alcoholic Potassium Hydroxide. The reading was noted at which the color of the
solution turns pink.
Acid number was the quantity of base, expressed as mg KOH/g of sample, required to titrate the sample to a
specified end point.

16
 Fig.3.8 Determining Acid Number by Titration

3.4 Scanning Electron Microscopy & Energy Dispersive Spectroscopy

The micrographs of the powder samples were examined using JEOL 6380A Scanning Electron Microscope at
different magnifications. The SEM is equipped with secondary electron (SE) detector and back-scattered
electron (BSE) detector. The samples, prior to SEM were coated with Gold using sputtering machine JEOL
JFC-1600 Auto fine coater.
EDS analysis of the powders was carried out in order to quantify the powder composition and confirm the
presence of the required elements in the powder samples.

Fig.3.9 JEOL 6380A Scanning Electron Fig.3.10 machine JEOL JFC-1600

Microscopy Auto fine coater.

3.5 Particle size analyzer

17
The average particle size of the powder sample on volume basis was determine using a particle size analyzer
named Microtrac Flex. The system has an injection port in which the powder sample dissolved in distilled
water has to be filled. The continuous supply of distilled water is given. Specifications of the powder sample
has to be entered into the computer. As soon as the sample is entered into the port data is generated in the
computer.The particle size can be determined by analyzing the data obtained.

Fig 3.11 Microtrac Flex particle size analayzer

Fig 3.12 Computer showing the data

18
3.6 Fourier transform infrared spectroscopy (FTIR)
Infrared spectroscopic analysis of different materials was carried out to study their structural features and
acidity.

Fig 3.13 FTIR Image

19
 CHAPTER 4
RESULTS AND DISCUSSION

20
4.1 Catalyst (Zeolite) Analysis
4.11 Particle Size Analysis (PSA)

Fig 4.1 PSA result for Run 1

Fig 4.2 PSA result for Run 2

Table 4.1 Result of PSA

RUN NUMBER PARTICLE SIZE (µm) AVERAGE PARTICLE

SIZE (µm)

1 88.83

2 85.39 87.11

21
Particle size analysis, particle size measurement, or simply particle sizing is the collective name of the
technical procedures which determines the size range, or average or mean size of the particles in a
powder sample.

From the particle size values obtained, it can be concluded that the average mean diameter of the

synthesized powder on volume basis is found to be 87.11 µm. The size range of the powder obtained

is found to be 4-400 µm.

4.12 Fourier transform infrared spectroscopy (FTIR)

Fig 4.3 Obtained FTIR Graph

Fig 4.4 actual FTIR Graph

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 4.13 Powder Morphology, Characteristics and Chemical Analysis

Field Emission Scanning Electron Microscope (SEM)

It is a non-destructive imaging technique to study the morphology of the
material with very high resolution. The SEM images of the sample are shown in Fig.
4.5.

Fig 4.5 SEM images of obtained zeolite at different resolutions

The absence of the spherical particles in treated fly ash (as evident from the SEM) indicates high
conversion of fly ash to crystalline zeolite on hydrothermal treatment. The crystal structure of
the synthesized zeolite was determined to be distorted octahedral.

Energy Dispersive X-ray spectroscopy (EDS)

• It is an analytical technique used for elemental or chemical characterization of
the sample.

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 • It relies on an interaction of some source of X-ray excitation and the sample.
• The fundamental principle is that each element has a unique atomic structure
allowing unique set of peaks on its electromagnetic spectrum.

cps/eV

50

40

30

20

10 Au
O Al Au
Na Si
Au
0
2 4 6 8 10 12 14
keV

Fig 4.6 Graph showing elemental composition of Zeolite

Table 4.2 Elemental Composition of the sample by Weight

Element Weight %

O 45.30

Si 20

Al 10.24

Au 12.08

Na 12.28

The data obtained from EDS confirms the presence of Si and Al which are the main constituents of Zeolite.
So from these it can be said that the sample is a zeolite. The presence of Na is due to the alkali fusion method.
The sodium hydroxide present in the reaction mixture acts as an activator during fusion to form soluble
silicate and aluminate salts, which further takes part in zeolite formation during hydrothermal process. Na+
cation also plays an important role in zeolitization.

4.2 Application of Zeolite as a catalyst in Biodiesel Production.

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 Acid number was calculated according to the below equation:

N acid = 56.1*M*(A-B)/W

where N acid = acid number

M = concentration of KOH (mol/l)

A = volume of KOH used to reach end point corresponding to basic buffer (ml)

B = volume corresponding to A for blank titration (ml)

W = mass of sample (g).

The conversion of the FFA was defined as the fraction of the FFA removed.

The conversion of FFA (x FFA) was determined from acid number ratio using below equation:

x FFA=as-at/as

where as is the initial acid number of the reactant

at is the acid number of product at a ‘t’ time.

The acid number of product was measured after separating from methanol.

Sr no. as at % Conversion
1 1.96 1.17 38.77 %
2 2.35 0.98 58.20 %
Table.4.3 %Conversion of FFA

As it can be seen that the acid value of the oil is more at time t=0 than the acid value of the oil at time t=t, so
it can confirmed from these that the there is a conversion of triglyceroids to biodiesel which proves the
catalytic activity of the zeoite.

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CHAPTER 5
CONCLUSION

26
5.1 Conclusion
Zeolite of X-type was synthesized from fly ash by alkali fusion followed by hydrothermal treatment.
The main crystalline phase of fly ash, quartz, could be converted to pure X-type at suitable treatment
conditions. The properties of zeolitic material formed strongly depended upon the treatment conditions and
concentrations of the raw materials. During the fusion process of Fly ash and NaOH, different types of fusion
techniques was done which includes directly mixing of the NaOH pellets with Fly ash or crushing the NaOH
pellets and mixing that powder with Fly ash. It was observed that the fusion was more proper in the second
case when crushed NaOH pellets was mixed with Fly ash. Characterisation of the obtained zeolite was done
by SEM and FTIR. From SEM the crystal structure was obtained as distorted octahedral. The FTIR graph
obtained from experimental procedure was found to be similar to the FTIR graph in the literature at the same
wave number range of 0-1200 cm-1. EDS confirmed the presence of silicon and aluminium and their oxides.
From all these results the formation of Zeolite was confirmed. Further the zeolite was used as a catalyst for
the removal of free fatty acid in waste frying oil by esterification method. Acid value was calculated to find
out the conversion of FFA. The %conversion was found to be 58% which confirmed the catalytic activity of
the Zeolite.
In conclusion, the study and the process of making the zeolite from fly ash and its application as a catalyst in
the production of biodiesel is open to further research and development. And surely there might be much
higher conversions observed with some developments in the catalyst and optimization.

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