A Project Report

On
“Synthesis and Characterization of PEG-
SO3H Catalyst”

Subject: Project II (2180504)

Academic Year: 2018-19 (8th Semester)
Team ID: 53816

Submitted by
Yagnesh Gopani 150110105006
Dhruvil Patel 150110105024
Vastal Patel 150110105032
Urvesh Rana 150110105038

Guided By
Prof. Dipen Chauhan
Assistant Professor

DEPARTMENT OF CHEMICAL ENGINEERING

G H PATEL COLLEGE OF ENGINEERING & TECHNOLOGY
VALLABH VIDYANAGR – 388120, GUJARAT, INDIA
GUJARAT TECHNOLOGICAL UNIVERSITY, AHMEDABAD
 Acknowledgment

We appreciate the GTU for giving us a platform which can transform our idea into a design or
any product which can help people in their day to day life.
We are specially thankful to the Government of Gujarat and Er. Bhikhubhai Patel
(Chairman CVM) for support under SSIP.
We are also thankful to Dr. Himanshu Soni (Principal, GCET) Dr. Kaushik Nath (HOD
Chemical Department) for granting us permission to work in college laboratories and use
college properties. And we are also thankful to Dr. Anand Metre (Associate Professor) and Dr.
Tejal Patel (Associate Professor) for evaluating our project progress eventually.

We are thankful to Prof. Vinay Patel (Finance Member, SSIP) and Prof. Dipen Chauhan
(SSIP member, SSIP) for full support in providing us SSIP grant.

We are specially grateful to our project guide Prof. Dipen Chauhan(Assistant Prof.) for
standing with us throughout whole year and guiding us on each and every step of our project
frequently, for their valuable guidance & the efforts that they have put in each of us. We would
not have been able to complete our project without their cooperation, encouragement and
immense help.

Yagnesh Gopani Enrollment No. 150110105006

Dhruvil Patel Enrollment No. 150110105024
Vastal Patel Enrollment No. 150110105032
Urvesh Rana Enrollment No. 150110105038

i
 CERTIFICATE

This is to certify that the project entitled “Synthesis and characterization of PEG-SO3H
catalyst” has been carried out by Yagnesh Gopani (150110105006), Dhruvil Patel
(150110105024), Vastal Patel (150110105032) and Urvesh Rana (150110105038) under my
guidance in fulfillment for the degree of Bachelor of Engineering in Chemical engineering
(8th Semester) of Gujarat Technological University, Ahmedabad during the academic year
2018-19.

Date:

Dr. Kaushik Nath Prof. Dipen Chauhan

Head of Department (CH) Assistant Professor (CH)

ii
Table of Content
1. Introduction .................................................................................................................... 1
1.1 Problem summary and introduction ......................................................................... 1
1.2 Aim and objective .................................................................................................... 1
1.3 Problem specification............................................................................................... 1
1.4 Literature survey ...................................................................................................... 2
1.4.1 Sulfonation process ........................................................................................ 2
1.5 Preparation of PEG-SO3H catalyst........................................................................... 3
1.6 Benefits of PTC ........................................................................................................ 4
1.7 Benefits of acid catalyst over base catalyst .............................................................. 5
1.8 Advantages of PEG-SO3H catalyst over conventional methods .............................. 5
1.9 Materials/Equipment required ................................................................................. 6
1.10 Safety measures of materials .................................................................................. 8
1.10.1 Safety measures of PEG-6000 ....................................................................... 8
1.10.2 Safety measures of Chlorosulfonic acid ......................................................... 8
1.10.3 Safety measures of Dichloromethane ............................................................. 9
1.10.4 Safety Measures of Diethyl ether ................................................................... 9

2. Synthesis of PEG-SO3H catalyst ................................................................................ 10

2.1 Addition of primary raw materials ........................................................................... 10
2.2 Stirring of mixture.................................................................................................... 10
2.3 Vacuum drying......................................................................................................... 10
2.4 Addition of Diethyl ether ......................................................................................... 11
3. Results ........................................................................................................................... 12
4. Characterization .......................................................................................................... 14
5. Application.................................................................................................................... 17
5.1 Benefits of biodiesel ................................................................................................ 17
5.2 Biodiesel production ................................................................................................ 18
5.3 Experiment process .................................................................................................. 18
5.3.1 Chemicals required in experimental set up .................................................... 18
5.3.2 Process description ......................................................................................... 19
5.3.3 Procedure........................................................................................................ 19
5.4 Result and characterization ...................................................................................... 20
5.4.1 Analysis report of Fatty Acid Composition ................................................... 21
5.4.2 Oil to Methanol ratio 1:12 sample GC ........................................................... 23
5.4.3 Oil to Methanol ratio 1:12 sample GC ........................................................... 25

6. Conclusion .................................................................................................................... 28
7. References ..................................................................................................................... 29
iii
# List of figures:
Number Name Page Number
Figure 1.1 Process Reaction 3
Figure 1.2 Process flow diagram 5
Figure 1.3 Magnetic stirrer 7
Figure 1.4 Ice bath 7
Figure 1.5 Vacuum dryer set-up 8
Figure 2.1 Stirring mixture overnight 10
Figure 2.2 Mixture after vacuum drying 11
Figure 2.3 Adding Diethyl ether and filtration 11
Figure 3.1 10 mmol chlorosulfonic acid 12
Figure 3.2 5 mmol chlorosulfonic acid 12
Figure 3.3 15 mmol chlorosulfonic acid 13
Figure 4.1 FT-IR of 10 mmol chlorosulfonic acid 14
Figure 4.2 FT-IR of 5 mmol chlorosulfonic acid 15
Figure 5.1 Experimental Set-up for biodiesel 19
Figure 5.2 Fatty acid composition 21
Figure 5.3 Peaks fatty acid composition sample 1 22
Figure 5.4 Chromatogram sample 1 23
Figure 5.5 Peaks of fatty acid composition sample 2 25
Figure 5.6 Chromatogram sample 2 26
Figure 5.7.1 Sample of bio-diesel (1:12) 27
Figure 5.7.2 Sample of bio-diesel (1:10) 27
Figure 5.7.3 Sample of bio-diesel (1:8) 28

iv
# Abbriviation:
PEG Polyethylene glycol
PEG--SO3H Polyethylene glycol bound SO3H
PTC phase transfer catalyst
– SO3Cl sulfonyl Chloride group
CH2Cl2 DiChloro Methane
FFAs Free Fatty Acids
FT-IR Fourier-transform infrared spectroscopy
GC Gas Chromatography

v
 ABSTRACT

Present report is on preparation of PEG-SO3H catalyst which inertially used as catalyst for
bio-diesel production. In this study the supported acidic PEG catalyst was prepared via
anchoring chlorosulfonic acid onto polyethylene glycol. This polymeric catalyst was used as
homogeneous for production of bio-diesel. Here, an attempt is made to synthesis of PEG-
SO3H catalyst in the laboratory. The objective is preparation and characterization of PEG-
SO3H solid acid catalyst using precipitation method. For preparation of catalyst at 0°C known
amount of chlorosulfonic acid is added to a solution of PEG-6000 in dichloromethane. After
this mixture was stirred for overnight. The mixture was filtered and washed with known
amount of diethyl ether and dried at room temperature to afford of PEG-SO3H as a white
gummy solid. The Produced PEG-SO3H was used for the preparation of Bio-diesel by acid
catalyst transesterification process. Three runs with varying oil to methanol molar ratio were
taken 1:12, 1:10, 1:8 respectively. The Resulted Products were characterized by GC analysis.

Key Words: PEG-SO3H, Precipitation Process, Green catalyst, Bio-Diesel, Acid Catalyst

Synthesis and Characterization of PEG-SO3H Catalyst vi

1. INTRODUCTION

1. INTRODUCTION
1.1 Problem Summary and Introduction [11]

Polyethylene glycol is a polyether compound with many applications, from industrial

manufacturing to medicine. PEG is also known as polyethylene oxide or polyoxyethylene,
depending on its molecular weight. The structure of PEG is commonly expressed as in below
figure. Polymerization of ethylene glycol in water yields a variety of products containing
varying no. of ethylene glycol units called PEGs. Polyethylene glycol is the main ingredient
in anti-freeze and used in Industries like food and pharmaceutical. In preparation of PEG-
SO3H catalyst using Precipitation process, there are some challenges like handling of
hazardous chemicals, concentration of solution mixture under vacuum, maintaining 0℃ temp.
in process etc. PEG-SO3H catalyst is acid catalyst. So, It has some benefits over base catalyst.

Chemical Formula of PEG [11]

1.2 Aim and objective

Main objective is to prepare PEG-SO3H catalyst by Precipitation process. It is phase transfer

catalyst (PTC). PTC is especially used in Green Chemistry. PEG-SO3H is a solid acid
catalyst. Using PTC in process, we can faster the reaction, reduce byproducts & get higher
conversion. [11]

1.3 Problem Specifications

In preparation of PEG-SO3H catalyst, we use precipitation process. In this process, we

require PEG-6000, Chlorosulfonic acid, Dichloromethane and Diethyl ether chemicals which
are hazardous chemicals. So, handling of these chemicals is required in proper way. In the
process, the Chlorosulfonic acid is added to mixture of PEG-6000 & CH2Cl2 at 00C. So, we
require cooling bath which maintain the 00C temperature. In the process, the solution mixture
is concentrated under vacuum. So, we require vacuum dryer set up. We have to maintain the
pressure in such way that concentration takes place in proper manner. Characterization of
PEG-SO3H catalyst is carried out by some analysis like FT-IR etc.

Synthesis and Characterization of PEG-SO3H Catalyst 1

1. INTRODUCTION

1.4 Literature Survey [10]

We referred NPTEL – Catalyst Science & Technology and get information about preparation
of solid catalyst. The catalyst preparation methods can broadly categorized as follows:

(1) Bulk preparation process

Bulk catalysts and supports are prepared by this method. Bulk preparation is mainly done by
the following methods:

(a) Precipitation Process

(b) Sol gel Process

(2) Impregnation Process

Supports are first prepared by bulk preparation methods and then impregnated with the
catalytically active material. The active materials can be deposited on the supports by various
methods. Most of the methods involve aqueous solutions and liquid solid interface. In some
cases, deposition is done from the gas phase and involves gas – solid interface.

(3) Physical Mixing

Mixed agglomerated catalysts are prepared by this method. These catalysts are prepared by
physically mixing the active precursors of support in ball mill. The final mixture is then
agglomerated and activated. We use precipitation process in preparation of PEG-SO3H
catalyst.

1.4.1 Sulfonation Process [9]

It may be defined as any chemical process by which the sulfonic acid group – SO3H or the
corresponding salt or sulfonyl halide group (e.g. – SO3Cl) is introduced into an organic
compound.

There are three types of sulfonation:

(1) Sulfochlorination: Introduction of an – SO2Cl group into an alkane using SO2 and Cl2.

(2) Halosulfonation: Reaction of a halo– sulfonic acid (- Cl SO3H or - F SO3H) with an

aromatic or heterocyclic compound to introduce an – SO2Cl or an – SO2F group.

Synthesis and Characterization of PEG-SO3H Catalyst 2

1. INTRODUCTION

(3) Sulfoxidation: Use of SO2 & O2 to sulfonate an alkane.

The reaction of alcohol with chlorosulfonic acid is as follow:

[1]
ROH(l) + ClSO3H(l)  ROSO2OH(l) + HCl(g)

The above reaction indicates that HCl gas is formed and we get alcohol sulfate liquid form.
Polyethylene glycol contains the alcohol group. The reaction between PEG-6000 and
chlorosulfonic acid is similarly happened as above reaction in preparation of PEG-SO3H
catalyst.

Figure 1.1 Process Reaction [6]

Above figure shows that the process is maintained at 0 c temperature. – Cl from

Chlorosulfonic acid and – H from PEG-6000 make HCl gas in presence of CH2Cl2. We get
PEG-SO3H catalyst in precipitates which are washed with appropriate amount of ether and
then dry at room temperature.

We refer some research papers which mentioned in references which give the process detail
of preparation of PEG –SO3H catalyst which is as follow:

1.5 Preparation of PEG-SO3H catalyst [1]

The Precipitation Process is used in preparation of PEG- SO3H Catalyst. At 0℃,

Chlorosulfonic acid (10 mmol) is added to a solution of PEG-6000 (1 mmol) in
Dichloromethane (10 ml), and the resulting solution is stirred at room temperature overnight.
Then, the solution is concentrated under the vacuum. Appropriate ether is added, and the
precipitate filtered and washed with ether three times to afford the PEG-SO3H.

From this information, we calculate required amount of chemicals.

Synthesis and Characterization of PEG-SO3H Catalyst 3

1. INTRODUCTION

1. Chlorosulfonic acid

Molecular weight: 116.52 gm/mol

Density: 1.753 gm/mol

10 mmol = 1.1652 gm

Volume = = 0.6646 ml

2. PEG-6000

Molecular weight: 6000 gm/mol

Density: 1.2 gm/mol

1 mmol = 6 gm

Then, we scale up 10 times. So, we get

PEG-6000 chemical amount = 6 × 10 = 60 gm

Chlorosulfonic acid volume = 0.6646 × 10 = 6.646 ml

Dichloromethane volume = 10 × 10 = 100 ml

We take 110 ml Diethayl ether as adding quantity and 45 ml (four times) as washing quantity.

We also get information regarding benefits of PTC, benefits of acid catalyst over base
catalyst and advantages of PEG-SO3H catalyst over conventional methods.

1.6 Benefits of PTC [4]

PEG-SO3H catalyst is phase transfer catalyst. PTC is a special form of heterogeneous catalyst
which facilitates the migration of a reactant from one phase to another. Generally ionic
reactants are soluble in aqueous solution but insoluble in organic phase in absence of PTC.
Using PTC in process, we can faster the reaction, reduce byproducts & get higher conversion.

Synthesis and Characterization of PEG-SO3H Catalyst 4

1. INTRODUCTION

1.7 Benefits of acid catalyst over base catalyst [4]

Base catalyst needs anhydrous condition and feed stocks with low levels and free fatty acids.
Water promotes the formation of FFAs in process deactivates the base catalyst and produces
soap while acid catalysts are less sensitive to FFAs.

1.8 Advantages of PEG-SO3H catalyst over conventional methods

In preparation of Benzoxazoles other catalysts are eco-friendly but not economical while
PEG-SO3H is economical.[6] In production of quinolone derivatives PEG-SO3H provides
relatively inexpensive catalysts and single product formation over existing procedures.[2]
With this catalyst process offers flexibility in tuning the molecular complexity and diversity,
without using any chromatographic techniques. The advantages of using PEG-SO3H for
synthesis of acylals from aldehydes and acetic anhydride are high yield, short reaction time,
low cost, cleaner reaction profile.[3]

PEG-SO3H catalyzed method for synthesis of pyrroles offers advantages like short reaction
time, recyclability of catalyst.[5] PEG-SO3H is soluble in polar solvents like water and makes
an aqueous solution.

PEG – 6000 (60 gm)

At 00 C ChloroSulfonic acid
in CH2Cl2 (100ml)
(6.65 ml)
Sol.

Sol. is Resulting Solution

Diethyl Concentrated Stirred
ether under vacuum mechanically at
(110 ml) (650 mm Hg& Room Temp.
50 -60 c ) Overnight

Resulted Washed with Diethyl ether

Precipitate PEG – SO3H as a
(45 ml) 4 times Gummy Solid
is Filtered

Figure 1.2 Process flow diagram

Synthesis and Characterization of PEG-SO3H Catalyst 5

1. INTRODUCTION

It represents following steps:

Step 1: Prepare the solution of solid PEG- 6000 (60 gm) in liquid Dichloromethane (100 ml)
in a magnetic stirrer.

Step 2: Prepare the ice-bath with the help of Ice, salt and Methanol (98 % v/v).

Step 3: Place the stirred solution in ice – bath and maintain 0 c. After the condition achieved,
the Chlorosulfonic acid (6.65 ml) is added drop-wise.

Step 4: Stirr the resulted solution on magnetic stirrer for approximate 12 hrs at room
temperature.

Step 5: The Resulting stirred mixture is concentrated by vacuum dryer. (By maintaining 650
mm Hg & 50 -60 c)

Step 6: The 110 ml Diethyl ether is added to resulted concentrated solution.

Step 7: The Resulted mixture is filtered by using the whatman filter paper.

Step 8: Resulted Precipitates are washed four times by using 45 ml Diethyl ether each time.

Step 9: Solid Precipitates are dried at room temperature.

Step 10: Weight the Solid PEG-SO3H powder.

1.9 Materials /Equipment required

Chemicals:

1) PEG-6000 (60 gm)

2) Chlorosulfonic acid (6.65 ml)

3) Dichloromethane (100 ml)

4) Diethyl Ether (290 ml)

Equipment:

1) 500 ml Beaker

2) Measuring cylinder

Synthesis and Characterization of PEG-SO3H Catalyst 6

1. INTRODUCTION

3) 500 ml conical flask

4) Magnetic Stirrer

Figure 1.3 Magnetic stirrer

5) Ice + Methanol cooling bath

Figure 1.4 Ice bath

6) Weight Balance

Synthesis and Characterization of PEG-SO3H Catalyst 7

1. INTRODUCTION

7) Vacuum Dryer

Figure 1.5 Vacuum Dryer setup

1.10 Safety measures of Materials

1.10.1 Safety measures of PEG-6000[25]
If inhaled: If breathed in, move person into fresh air. If not breathing, give artificial
respiration.
In case of skin contact: Wash off with soap and plenty of water.
In case of eye contact: Flush eyes with water as a precaution.
If swallowed: Never give anything by mouth to an unconscious person. Rinse mouth with
water.

1.10.2 Safety measures of Dichloromethane[23]

Eyes: In case of contact, immediately flush eyes with plenty of water for at least 15 minutes.
Get medical aid.
Skin: In case of contact, flush skin with plenty of water. Remove contaminated clothing and
shoes. Get medical aid if irritation develops and persists. Wash clothing before reuse.
Ingestion: If swallowed, do not induce vomiting unless directed to do so by medical
personnel. Never give anything by mouth to an unconscious person. Get medical aid.
Inhalation: If inhaled, remove to fresh air. If not breathing, give artificial respiration. If
breathing is difficult, give oxygen. Get medical aid.

Synthesis and Characterization of PEG-SO3H Catalyst 8

1. INTRODUCTION

1.10.3 Safety Measures of Chlorosulfonic acid[22]

If inhaled: If breathed in, move person into fresh air. If not breathing, give artificial
respiration. Consult a physician.
In case of skin contact: Take off contaminated clothing and shoes immediately. Wash off
with soap and plenty of water. Consult a physician.
In case of eye contact: Rinse thoroughly with plenty of water for at least 15 minutes and
consult a physician.
If swallowed: Do NOT induce vomiting. Never give anything by mouth to an unconscious
person. Rinse mouth with water. Consult a physician.

1.10.4 Safety Measures of Diethyl ether[24]

If inhaled: If breathed in, move person into fresh air. If not breathing, give artificial
respiration. Consult a physician.
In case of skin contact: Wash off with soap and plenty of water. Consult a physician.
In case of eye contact: Flush eyes with water as a precaution.
If swallowed: Do NOT induce vomiting. Never give anything by mouth to an unconscious
person. Rinse mouth with water. Consult a physician

Synthesis and Characterization of PEG-SO3H Catalyst 9

2. Synthesis of PEG-SO3H Catalyst

2. Synthesis of PEG-SO3H Catalyst

2.1 Addition of primary raw materials:

First of all we diluted PEG-6000 (60gm) into Dichloromethane (100 ml) at room temperature
on magnetic stirrer. We prepare ice cooling bath with additional methanol and salt, which
helped us to decrease the temperature of our process. After all the PEG added to the
Dichloromethane is completely dissolved, the beaker is inserted into ice bath where at 0ºC
temperature Chlorosulfonic acid is added dropwise with the help of burette. HCl is liberated
during this process in the form of vapours.

2.2 Stirring of mixture:

After the addition of Chlorosulfonic acid in the solution of PEG and Dichloromethane, the
resulting mixture is stirred mechanically using magnetic stirrer for approximately 16 hours at
room temperature and atmospheric pressure.

Figure 2.1 Stirring mixture overnight

2.3 Vacuum Drying

The solution obtained after the overnight stirring is a semi viscous whiteish liquid. Now the
solution is placed in the vacuum dryer at 0.85 atm and 50 – 60 ℃ temperature for 1 hour. The
unreacted Dichloromethane is vaporized and more viscous solution is obtained at the end of
the process.

Synthesis and Characterization of PEG-SO3H Catalyst 10

2. Synthesis of PEG-SO3H Catalyst

Figure 2.2 Mixture after vacuum drying

2.4 Addition of Diethyl ether

110 ml of Diethyl ether is added to the obtained solution and is stirred with glass rod. Thus,
resulting in semisolid white substance. Now some more amount of Diethyl ether is added (45
ml) 4 times and the excess ether was filtered using whatman filter paper. Thus, the obtained
gummy white solid is the required product which is then weighed.

Similarly, this process was repeated 2 times by taking different amount of Chlorosulphonic
acid keeping all the other component amount same and the reacting conditions.

Figure 2.3 Adding Diethyl ether and filtration

Synthesis and Characterization of PEG-SO3H Catalyst 11

3. Results

3. Results
Experiment 1 (Chlorosulfonic acid: 10 mmol)

PEG-6000 = 10*6 = 60 gm

Chlorosulfonic Acid = 10*0.664 = 6.64 ml

Dichloromethane = 10*10 = 100 ml

Diethyl ether = 110 ml + (45 ml <4 times> = 180 ml) = 290 ml

In this a gummy solid form of white coloured PEG-SO3H weighing 59.2 gm.

Figure 3.1 10 mmol chlorosulfonic acid

Experiment 2 (Chlorosulfonic acid: 5 mmol)

Chlorosulfonic Acid = 10*0.3323 = 3.323 ml

In this, we obtained solid powder form of the catalyst weighing 79 gm.

Figure 3.2 5 mmol chlorosulfonic acid

Synthesis and Characterization of PEG-SO3H Catalyst 12

3. Results

Experiment 3 (Chlorosulfonic acid: 15 mmol)

Chlorosulfonic Acid = 10*0.997 = 9.97 ml

In this, we obtained a light yellow viscous liquid as the final product and solid form of
catalyst was not obtained.

Figure 3.3 15 mmol chlorosulfonic acid

Synthesis and Characterization of PEG-SO3H Catalyst 13

4. Characterization

4. Characterization
Catalyst characterization and analysis plays a key role in catalyst development, ongoing
quality control during manufacturing and also during fouling or performance related
investigations. Laboratory testing expertise and services. Understanding the composition, the
physical micro/nano-structure, porosity and surface properties can all assist in achieving a
better performance or resolve a failure issue.[12]

We have conducted FT-IR analysis of our obtained two catalysts. The result after
characterization is as shown below.

Figure 4.1 FT-IR of 10 mmol chlorosulfonic acid

From the IR frequency table the following result was obtained:

Synthesis and Characterization of PEG-SO3H Catalyst 14

4. Characterization

Sr NO Peak Value Name of Group

1 3420.71 OH Stretching
2 2910.71 CH Stretching
3 2879.62 CH Stretching
4 1638.48 C=C Stretching
5 1468.92 CH Bending
6 1457.30 CH Bending
7 1400.27 CH Bending
8 1352.13 S=O Stretching
9 1295.71 CO Stretching
10 1245.75 CO Stretching
11 1106.97 CO Stretching
12 952.65 C=C Bending
13 847.14 CH Bending

Table 4.1 Peak values of 10 mmol chlorosulfonic acid[21]

Figure 4.2 FT-IR of 5 mmol chlorosulfonic acid

Synthesis and Characterization of PEG-SO3H Catalyst 15

4. Characterization

From the IR frequency table the following result was obtained:

Sr NO Peak value Name of Group

1 3426.20 OH Stretching
2 2881.16 CH Stretching
3 1720.93 C=O Stretching
4 1635.59 C=C Stretching
5 1467.44 CH Bending
6 1456.34 CH Bending
7 1400.69 CH Bending
8 1351.59 S=O Stretching
9 1279.63 CO Stretching
10 1248.40 CO Stretching
11 1227.72 CO Stretching
12 1193.22 CO Stretching
13 1112.68 CO Stretching
14 952.37 C=C Bending
15 886.54 C=C Bending
16 843.23 CH Bending
17 835.54 CH Bending
Table 4.2 Peak values of 5 mmol chlorosulfonic acid[21]

From the above result, it was concluded that SO3H group has been attached to PEG 6000
compound. As the product obtained was gummy solid and not in pure crystalline form XRD
cannot be performed.

The Melting point and Boiling point was obtained by heating the capillary tube filled with
catalyst in the Paraffin oil bath. When the catalyst in the capillary turns into transparent
liquid, it is the melting point of the catalyst. When on further heating the transparent liquid
starts to boil, it is known as the boiling of catalyst.

Sample 1 (10 mmol) Sample 2 (5mmol)

Boiling point 118℃ 132℃
Melting point 44℃ 48℃
Table 4.3 Melting point and boiling point of catalyst

Synthesis and Characterization of PEG-SO3H Catalyst 16

5. Application

5. Application
We intended to use the catalyst in preparing Biodiesel. Biodiesel is similar alternative fuel of
conventional or ‘fossil’ diesel. Biodiesel is produced from straight vegetable oil, animal
oil/fats, tallow and waste cooking oil. The process used to convert oils to Biodiesel is called
transesterification. The largest possible source of suitable oil is obtained from oil crops such
as rapeseed, palm or soybean. In the UK rapeseed shows the greatest potential for biodiesel
production. Most biodiesel produced at present is done from waste vegetable oil sourced from
restaurants, chip shops, industrial food producers etc. Though oil straight from the
agricultural industry represents the greatest potential source it is not being produced
commercially simply because the raw oil is too expensive. After the cost of converting it to
biodiesel has been added on it is simply too expensive to compete with fossil diesel. Waste
vegetable oil can often be sourced for free or sourced already treated for a small price. (The
waste oil must be treated before conversion to biodiesel to remove impurities). The result is
Biodiesel produced from waste vegetable oil can compete with fossil diesel.

5.1 Benefits of Biodiesel [10]

Biodiesel has many environmentally beneficial properties. The main benefit of biodiesel is
that it can be described as ‘carbon neutral’. This means that the fuel produces no net output of
carbon in the form of carbon dioxide. This effect occurs because when the oil crop grows it
absorbs the same amount of Carbon dioxide as is released when the fuel is combusted. In fact
this is not completely accurate as Carbon dioxide is released during the production of the
fertilizer required to fertilize the fields in which the oil crops are grown. Fertilizer production
is not the only source of pollution associated with the production of biodiesel, other sources
include the esterification process, the solvent extraction of the oil, refining, drying and
transporting. All these processes require an energy input either in the form of electricity or
from a fuel, both of which will generally result in the release of greenhouse gas. To properly
assess the impact of all these sources requires use of a technique called life cycle analysis.
Biodiesel is rapidly biodegradable and completely non-toxic, meaning spillages represent far
less of a risk than fossil diesel spillages. Biodiesel has a higher flash point than fossil diesel
and so is safer in the event of a crash.

Synthesis and Characterization of PEG-SO3H Catalyst 17

5. Application

5.2 Biodiesel Production [11]

Almost all biodiesel is produced using base catalyzed transesterification as it is the most
economical process requiring only low temperatures and pressures and producing a 98%
conversion yield. But we will use Acid catalyst for the same. Hence, we will use Acid
catalyzed transesterification process. The Transesterification process is the reaction of a
triglyceride (fat/oil) with an alcohol to form esters and glycerol. A triglyceride has a glycerin
molecule as its base with three long chain fatty acids attached. The characteristics of the fat
are determined by the nature of the fatty acids attached to the glycerin. The nature of the fatty
acids can in turn affect the characteristics of the biodiesel. During the esterification process,
the triglyceride is reacted with alcohol in the presence of a catalyst. The alcohol reacts with
the fatty acids to form the mono-alkyl ester, or biodiesel and crude glycerol. In most
production methanol or ethanol is the alcohol used (methanol produces methyl esters; ethanol
produces ethyl esters). The reaction of oil and alcohol is a reversible reaction and so the
alcohol must be added in excess to drive the reaction towards the right and ensure complete
conversion.

[11]

5.3 Experiment Process

5.3.1 Chemicals required and Experimental setup

The following list if chemicals are required for the experiment:

 Crude corn oil

 Methanol
 PEG-SO3H Catalyst

The apparatus required are:

 DNS apparatus
 Three neck flask

Synthesis and Characterization of PEG-SO3H Catalyst 18

5. Application

 Condenser
 Temperature controller
 Mechanical stirrer
 Heater

Figure 5.1 Experimental Set-up for biodiesel[20]

5.3.2 Process Description [11]

Firstly, the acid value of the corn oil sample is to be calculated. Acid value also known as
acid number or neutralization number is the mass of potassium hydroxide KOH required to
neutralize one gram of oil sample. Thus, by titrating the mixture of 25 ml Toluene + 25 ml
iso-propyl alcohol + 5 gm sample oil against 0.1 N KOH, the acid value was found to be
2.6928.

Acid Value =

Where V is KOH consumed ml, N is Normality of KOH, W is weight of oil sample.

Synthesis and Characterization of PEG-SO3H Catalyst 19

5. Application

Now percentage of FFA in oil is calculated by using the Acid value to be 1.3846 %

% FFA =

Where Molecular weight of oil = 288.46 gm/mole.

5.3.3 Procedure

Firstly, the mixture of oil and methanol is taken in 1:12 molar ratio in the three neck flask.
The resulting mixture contains 89 ml methanol and 61 ml corn oil. To this mixture 3.2 gm of
PEG-SO3H catalyst is added. The flask is heated using heater and the temperature is kept
65℃ using temperature controller. Mechanism is made for the total reflux condition of the
methanol during the heating process. The solution is also stirred using mechanical agitator at
the same time. This process is continued for 6 hours. The resulting mixture is poured into the
separating funnel. Thus two layers get separated, the upper layer is the mixture of biodiesel
with some amount of methanol and the lower layer is glycerol with some amount of
methanol.

Similarly, this procedure is repeated two times by varying the oil to methanol ratio 1:10 and
1:8 respectively and keeping all of the operating conditions same as above.

5.4 Result and Characterization

Sample (Oil to Methanol ratio) Quantity obtained (ml)

1:12 67
1:10 53
1:8 49
Table 5.1 Amount of biodiesel obtained

Gas chromatography: Gas chromatography (GC) is a common type of chromatography used

in analytical chemistry for separating and analyzing compounds that can be vaporized
without decomposition. In gas chromatography, the carrier gas is the mobile phase. The rate
of flow of the carrier is carefully controlled to give the clearest separation of the components
in the sample. The sample being measured is injected into the carrier gas using a syringe and
instantly vaporizes. The results of the gas chromatography are shown as below. [12]

Synthesis and Characterization of PEG-SO3H Catalyst 20

5. Application

5.4.1 Analysis report of Fatty Acid Composition:

Figure 5.2 Fatty acid compositions

Synthesis and Characterization of PEG-SO3H Catalyst 21

5. Application

5.4.2 Oil to Methanol ratio 1:12 sample GC:

Figure 5.3 Peaks fatty acid composition sample 1

Synthesis and Characterization of PEG-SO3H Catalyst 22

5. Application

Oil to Methanol ratio 1:12 sample GC:

Figure 5.4 Chromatogram sample 1

Synthesis and Characterization of PEG-SO3H Catalyst 23

5. Application

Peak No. Name RT (min)

1 Methyl Palmitate 17.19
2 Methyl Palmitoleate 18.71
3 Methyl Eicosonate 23.13
4 Methyl Eicosadienaote 23.59
5 Methyl Eicosatrienoate 24.79
6 Methyl Erucate 26.37

Table 5.2 Peak values of sample 1 (GC) [12]

Synthesis and Characterization of PEG-SO3H Catalyst 24

5. Application

5.4.3 Oil to Methanol ratio 1:10 sample GC:

Figure 5.5 Peaks of fatty acid composition sample 2

Synthesis and Characterization of PEG-SO3H Catalyst 25

5. Application

Oil to Methanol ratio 1:10 sample GC:

Figure 5.6 Chromatogram sample 2

Synthesis and Characterization of PEG-SO3H Catalyst 26

5. Application

Peak No. Name RT (min)

1 Methyl Palmitoleate 18.82
2 Methyl Eicosonate 23.24
3 Methyl Eicosadienoate 23.73
4 Methyl Eicosetrienoate 24.85
5 Methyl Erucate 26.53
[12]
Table 5.3 Peak values of sample 2 (GC)

The product obtained is as shown below:

Figure 5.7.1 Sample of bio-diesel (1:12)

Figure 5.7.2 Sample of bio-diesel (1:10) Figure 5.7.3 Sample of bio-diesel (1:8)

Synthesis and Characterization of PEG-SO3H Catalyst 27

6. Conclusion

6. Conclusion
From the experiments to obtain PEG-SO3H catalyst, it was concluded that the quantity of the
catalyst obtained was more in case of 5 mmol Chlorosulfonic acid i.e 79 grams whereas, for
10 mmol Cholosulfonic acid it was only 59.2 grams. But the catalyst 5 mol Cholosulfonic
acid was degraded giving dark yellow color and foul smell after 4 to 5 months of preparation.
Whereas, the catalyst with 10 mmol Chlorosulfonic acid showed no such change. From the
FT-IR of both the catalyst sample it was concluded that the sulfonic group is being attached
to PEG compound.

Now, for the application of the prepared catalyst, three runs were taken of 6 hours each with
varying molar ratio of oil to methanol i.e 1:12, 1:10 and 1:8 respectively. The product
obtained with 1:8 molar ratio was not up to our expectation. The quantity of the product
obtained with 1:12 molar ratio was more that was 67 ml whereas; with 1:10 ratio it was 53
ml. The products were taken out and were given for the gas chromatography. The results of
the GC report showed that there was conversion of fatty acid to alkyl ester. But yield was not
to the expectation. Thus, proper conversion was not obtained. Some amount of unreacted
reactants was obtained with the bio-diesel. But the peaks of the chromatography report
showed the Methyl ester formation. Thus, there was some amount of Bio-diesel formed in
this process.

There is future scope for getting the required conversion by trial and error method with use of
PEG-SO3H catalyst.

Synthesis and Characterization of PEG-SO3H Catalyst 28

7. References

7. References
Research Papers
1) Ali Reza Kiasat, Mehdi Fallah Mehrjardi, PEG-SO3H as eco-friendly polymeric
catalyst for regio selective ring opening of epoxides using thiocyanate anion in water:
An efficient route to synthesis of b-hydroxy thiocyanate, Catalysis Communications
(2007), 1497–1500.
2) M.A. Nasseri, S.A.Alavi, B Zakerinasab, PEG-SO3H as catalyst in aqueous media: A
simple, proficient and green approach for the synthesis of quinoline derivatives, J.
Chem. Sci. 125(2013), 109–116.
3) A. Zare, A. Hasaninejad, E. Rostami , A.R. Moosavi - Zare and M. Merajoddin, PEG-
SO3H as a New, Highly Ecient and Homogeneous Polymeric Catalyst for the
Synthesis of Acylals from Aldehydes and Acetic Anhydridel ,17(2010), 24-30.
4) Xue-li Song, Xio-bo Fu, Cheng-wu Zhang, Preparation of novel carbon based solid
acid catalyst for bio-diesel production via a sustainable route, 142(2012), 869-874.
5) A Hasaninejad, M. Schekouhy, A. Zare, PEG- SO3H as a new highly efficient and
homogeneous polymeric catalyst for the synthesis of Bis(indolyl)methanes, 8(2011),
411-423.
6) Rupesh V. Chikhale, Amit M. Pant, Sunil S. Menghani, Pankaj G. Wadibhasme and
Pramod B. Khedekar; Poly (Ethylene Glycol)-Bound Sulphonic Acid as a Novel
Catalyst for Synthesis of Benzoxazoles, S. Afr. J. Chem., .66(2013), 254-262.
7) G.M. Nazeruddin, M.S.Pandharpatte, K.B.Mulani, PEG- SO3H: A mild and efficient
recyclable catalyst for the synthesis of coumarin derivatives,Comptes Rendus Chimie,
15(2011), 91-95.
8) Sanjay Paul and Asish R. Das, A new application of polymer supported,
homogeneous and reusable catalyst PEG– SO3H in the synthesis of coumarin and
uracil fused pyrrole derivatives, Catalyst Science & Technology, 2(2012), 1130-1135.
9) P.H. Groggins, “Unit processes in organic synthesis”, McGraw Hill Education, 5 th
edition, May 2001, Page no. 303-310.
10) M. Thirumarimurugan, V.M. Sivakumar, A. Merly Xavier, D. Prabhakaran, T.
Kannadasan, Preparation of biodiesel from sunflower oil by transesterification,
International Journal of Bioscience, 2(2012), 441-444.
11) N.A. Khan, H.Dessouky,Biodiesel production from corn oil by transesterification
process, The Nucleus, 46(2009), 241-252.
12) James D. McCurry, “G.C. analysis for fatty acid ethyl ester and methyl linolenate in
bio-diesel using revised EN 14103:2011 method”, Agilent Technologies.
13) Sayyed Siraj R., B. M. Gitte, S. D. Joshi, H. M. Dharmadhikari, Characterization of
bio-diesel, IJERT, 2(2013), 2077-2082.
14) M. Canakci, J. Van Gerpen, Biodiesel production via acid catalyst, ASAE, 42(1999),
1203-1210

Synthesis and Characterization of PEG-SO3H Catalyst 29

7. References

15) Crizel MG, Lenz V, Ritter M, Pacheco B and Pereira CMP, Viscosity Analysis: A
Potential Protocol to Detect Adulteration in Biodiesel, Austin Environ Sci., 1(2016),
1-5.
16) Jana Orsavova , Ladislava Misurcova , Jarmila Vavra Ambrozova , Robert Vicha and
Jiri Mlcek, Fatty Acids Composition of Vegetable Oils and Its Contribution to Dietary
Energy Intake and Dependence of Cardiovascular Mortality on Dietary Intake of Fatty
Acids, Int. J. Mol. Sci., 16(2015), 12871-12890.
17) Nur Syakirah Talha and Sarina Sulaiman, Overview of Catalysts in Bio diesel
production, ARPN , 11(2016), 439-448.
18) N Nedambale, N Ndlovu, T Ntombela, M Low and KG Harding, Alternative testing
methods to determine the quality of biodiesel, Chemical technology Article, (2014),
16-20.
19) Shubham Gupta, Sumit Kumar , Experimental investigation of Bio diesel with corn
oil, International journal of Mechanical and Production engineering, 3(2015), 73-78.
20) Konda raja kumar, Dr. P. Sreenivasulu, R.Sam Sukumar, Exprimental Investigation
on Diesel Engine Fueled with corn Biodiesel Using CeO2 nano particles, International
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21) IR spectroscopy table
URLS:
22) https://www.fishersci.com/store/msds?partNumber=AC304491000&productDescripti
on=CHLOROSULFONIC+ACID+97%25+100ML&vendorId=VN00032119&countr
yCode=US&language=en
23) https://www.fishersci.com/msdsproxy%3FproductName%3DD3720%26productDescr
iption%3DMETHYLENE%2BCHLOR%2BCERT%2BACS%2B20L%26catNo%3D
D37-20%2B%26vendorId%3DVN00033897%26storeId%3D10652
24) https://www.fishersci.com/store/msds?partNumber=E138500&productDescription=E
THY+ETHER+ANHYDROUS+ACS+500ML&vendorId=VN00033897&countryCo
de=US&language=en
25) https://www.cdhfinechemical.com/images/product/msds/37_117579208_Polyethylene
Glycol6000-CASNO-25322-68-3-MSDS.pdf

Synthesis and Characterization of PEG-SO3H Catalyst 30