GUJARAT TECHNOLOGICAL UNIVERSITY

Chandkheda, Ahmedabad

Affiliated

FACULTY OF ENGINEERING TECHNOLOGY & RESEARCH

A
project
report

on

To Study Synthesis and Esterification of Bio-Derived Organic Acid with Different Alcohols.

B. E. IV, Semester – VII

SR NO. NAME PAN NO.

1 DOBARIYA NIKUNJ 150840105008
2 GOLAKIYA RAVI 150840105016
3 PATEL DHRUVI 150840105033
4 RAMOLIYA AKASH 150840105049
5 SELADIYA VIVEK 150840105055
(Chemical Branch)

Dr. J.M. BARAD

(Head of Department)

Academic Year

(2018-2019)

1
 CERTIFICATE

This is to certify that the project entitled “To Study Synthesis and Esterification
of BioDerived Organic Acid with Different Alcohols.” submitted by
DOBARIYA NIKUNJ(150840105008), GOLAKIYA RAVI(150840105016),
PATEL DHRUVI(150840105033), RAMOLIYA AKASH (150840105049),
SELADIYA VIVEK(150840105055) in partial fulfilment of the requirement for
the project of BACHELOR OF CHEMICAL ENGINEERING of the Gujarat
Technological University, Ahmadabad. This work has been carried out under my
supervision,during academic year 2018-19.

Date: / /2018

Place :FETR ,BARDOLI

Faculty Guide

Prof. Kevin V. Vadanagara

 CERTIFICATE

This is to certify that the Project entitled “To Study Synthesis and
Esterification of Bio-Derived Organic Acid with Different Alcohols.” has been
carried out by DOBARIYA NIKUNJ(150840105008), GOLAKIYA
RAVI(150840105016), PATEL DHRUVI(150840105033), RAMOLIYA
AKASH (150840105049), SELADIYA VIVEK(150840105055) at Department of
CHEMICAL ENGINEERING DEPARTMENT of FACULTY OF
ENGINEERING
TECHNOLOGY AND RESEARCH in partial fulfilment of the requirement for
project of BACHELOR OF CHEMICAL ENGINEERING of the Gujarat
Technological University, Ahmadabad.

Date:

External Examiner Name and SIGN:

 ACKNOWLEDGEMENT
This project report is made possible through the help and support from
everyone, including: parents, teachers, family, friends, and in essence,
all sentient beings. Especially, please allow us to dedicate our
acknowledgment of gratitude toward the following significant advisors
and contributors:

First and foremost, we would like to thank Prof. Kevin V. Vadanagara

for his most support and encouragement. He kindly read our report and
offered invaluable detailed advices on grammar, organization, and the
theme of the report.

Finally, we sincerely thank to our parents, family, and friends, who

provide the advice and financial support. The preparation of this project
report would not be possible without all of them.
 Abstract
The chemical industry consumes non renewable resources. Non
renewable resources are limited and also they have sever environmental
effect, due to that now a days chemical industry shift towards to use
renewable resources. Economically effective and environmentally
benign large amount of product can be produced from renewable energy
source biomass. Levulinic acid is used as surfactant, detergents,
pharmaceuticals and food additives as well as ingredient in animal feeds.
Advantages of LA are Versatility allowing a wide range of downstream
transformation, feed stock flexibility ,high conversion yield, high
productivity and concentration process stream result in cost-competitive
economic. Cost- competitive economics are key for fast and successful
market introduction of LA as well as substantial market growth in the
coming years. Esters of (LA) are used in different chemical industries
like food, chemical, pharmaceutical etc. Succinic esters are produced by
the esterification reaction. It is the reaction between acid and alcohols.
Because of reaction reversible in nature and very slow reaction it require
catalyst to increase reaction rate . In this work first we have synthesized
Bio-Derived acid naturally from the plant later the esterification
reactions of LA with different alcohols and different catalysts are
studied. sample will be characterised by FTIR & Finally surface
morphology will be studied by performing SEM & TEM Analysis. The
conversion of LA carried out by both sample and at the end of our work
we will Compare our results with different acid to alcohol ratio.
 CONTENTS

Chapter 1 Introduction 7
1.1 Background 7
1.2 Motivation 8
1.3 Objective of Project 8
Chapter 2 Literature review 9
2.1 Esterification of lauric acid with n- 9
butanol
2.2 Effect of amount of PW(12- 9
Tungstophosphoric acid) supported
onto MCM- 41(Mobil Composition
of Matter No. 41)
2.3 Effect of mole ratio 10
2.4 Effect of amount of catalyst 11
2.5 Effect of reaction time 11
2.6 Effect of reaction temperature 12
2.7 Recycling of the catalyst 13
Chapter 3 Experimental Set Up 14
3.1 Apparatus 14
3.2 Procedure 14
Chapter 4 Synthesis and Analytical Method 16
4.1 Synthesis 16
4.2 Analytical Method 17
Chapter 5 Conclusion 21
Chapter 6 Reference 22
Chapter: 1 Introduction
1.1 Background:
Usually, esters are derived from a carboxylic acid and
an alcohol. Glycerides, which are fatty acid esters of glycerol, are
important esters in biology, being one of the main classes of lipids, and
making up the bulk of animal fats and vegetable oils. Esters with low
molecular weight are commonly used as fragrances and found in
essential oils.
Now a days, in manufacturing of any esters are preffered in bio-derived
manner. Because of Non- bio-derived esters are manufactured from
Non- Renewable sources. So ultimately, we need to manufacturing of
esters from Renewable sources which are also less cosly compared to
NonRenewable sources, Thus we can make the esterification process
Eco- Friendly by the uses of differents Bio-Derived acids and alcohols.
1.2 Motivation:
Succinic acid among the other bio platform chemicals of the
futurebiorefineries,has been reported as a promising candidate (Patel and
Weusthuis, 2006). This dicarboxylicacid(succinic acid) is an
intermediate of the tricarboxylic acid cycle thatcould replace the maleic
anhydride which is produced from oil as a C4 buildingblock chemical
(Okino et al., 2008). As succinic acid is an intermediate, the catalytic
reactions for the production of the derivatives directly in the
fermentation broth is profitable. The bio succinic acid market was
51,000 tons in 2013 and is expected to increase to 593,400 tons by 2020
(Zeikus et al., 1999). It would avoid the expensive purification of
succinic acid from the fermentation broth. The resulting derivatives from
the succinic acid should have different physico-chemical properties that
will ease their final
purification. This constitutes the primary motivation to select succinic
acid among the other bio-based organic acid.

1.3 Objectives

The esterification reaction of bio-platform molecule (succinic acid) with

different alcohols using solid acid catalyst is to be carried out in a round
bottom flask placed in a oil bath and it is attached with Dean-Stark
apparatus for removing water formed during the reaction and condenser
to remove heat. The reaction-mixture is to be heated and after the
reaction is to be completed the % yield of the ester is to be found. The
esterification reaction is to be carried out for the different acid/alcohol
ratio, different time interval, different amount of catalyst loading and at
different reaction temperature.

• The conversion of succinic acid for particular amount of solid acid

catalyst for different time interval is to be determined by titration with
NaOH solution.
• The determination of effect of acid/alcohol ratio on esterification
reaction for particular amount of catalyst is to be carried out.
• The effect of amount of catalyst loading , effect of reaction
temperature and reaction time on esterification reaction is to be
determined.
 Chapter-2: Literature review

2.1 Esterification of lauric acid with n-butanol:

The esterification of lauric acid is an equilibrium-limited reaction. In
order to overcome the equilibrium limitation, it is necessary either to
carry out esterification by taking one of the reactant in excess. The
yields can be increased by increasing the concentration of either alcohol
or acid. In a practical means, to obtain maximum yield for economic
reasons, the reactant that is usually less expensive is taken in excess. In
present study corresponding alcohol is taken in.

2.2 Effect of amount of PW(12-Tungstophosphoric acid) supported

onto MCM-41(Mobil Composition of Matter No. 41):
The esterification reaction was carried out with 10% PW/MCM-41,20%
PW/MCM-41, 30% PW/MCM-41 and 40% PW/MCM-41. The obtained
results are shown in Fig.(1). It is observed from the fig-that with increase
in the % loading of PW onto MCM-41, yield also increases. For 10%
and 20% loading, yields for butyl laurate are cosiderably low. For 30%
and 40% loading, the difference in yield isnot that much appreciable.
Hence the catalyst containing 30% loading of PW, i.e. 30% PW/MCM-
41 was used for the detail study.
 Fig.1. Dependence of butyl laurate yield on the PW content supported on MCM-41.

2.3 Effect of mole ratio:

The reaction was carried out by varying mole ratio of lauric acid to n-
butanol, with 0.2 g of the catalyst for 3 h at 90 C. It is observed that with
increase in concentration of alcohol the yield of the product; butyl
laurate increases. With 1:2 mol ratio of lauric acid to n-butanol
maximum yields up to 95 was achieved. With further increase in n-
butanol concentration not much difference was observed. Hence, further
reactions were carried out in1:2 mol ratio of acid to alcohol.

Fig.2. Effect of molar ratio of acid/alcohol on the butyl laurate yield (reaction 10
conditions: 0.2 g catalyst, 90 C, 3 h).
2.4 Effect of amount of catalyst:
To study the effect of the amount of the catalyst, the reaction was carried
out with different amount of the catalyst keeping the mole ratio of acid
to alcohol 1:2 for 4 h at 90 C. The yield of butyllaurate is reported in
Fig. 5. It is seen from the figure that initially the activity increases with
an increase in the amount of the catalyst. On further increase with the
amount from 0.25 to 0.25 g of the catalyst, maximum yields of ester was
obtained. The effect of the amount of the catalyst was studied keeping
all other parameters (temperature, reaction time, mole ratio of alcohol to
acid) constant. Under these conditions, no increase in the yield with
increase in amount of catalyst indicates the attainment of the maximum
equilibrium. The obtained results are as expected. Hence, 0.2 g is the
optimized amount of the catalyst.

Fig.3. Effect of catalyst amount on the butyl laurate yield (reaction conditions:acid/alcohol 1:2, 90 C, 3 h).

2.5 Effect of reaction time:

With increase in reaction time the yield of butyl laurate increases Up to
3 h maximum yield of butyl laurate was achieved. Further it does not
increase with time.
11
Fig.4. The yield of butyl laurate in the course of reaction (reaction conditions: acid/ alcohol 1:2,
0.2 g catalyst, 90 C, 3 h).

2.6 Effect of reaction temperature:

With increase in reaction temperature the yield of butyl laurate
increases. At 90 C maximum yield was obtained. The optimum
conditions for esterification of lauric acid using30% PW/MCM-41 are:
mole ratio of acid to alcohol 1:2; amount of catalyst 0.2 g; reaction
temperature 90 C and reaction time 3 h.

Fig.5. Effect of reaction temperature on the butyl laurate yield (reaction conditions: 12
acid/alcohol 1:2, 3 h).
2.7 Recycling of the catalyst:
The catalyst was recycled in order to test its activity as well as stability.
The catalyst was separated from the reaction mixture only by simple
filtration, washed with conductivity water till thefiltrate is free from the
acid dried at 100 C and the recovered catalyst was charged for the
further run. There is no appreciable change in the yield of butyl acetate
using regenerated catalyst upto four cycles.

Fig.6. PW/MCM-41 recycling in esterification of lauric acid with n-butanol(reaction conditions:

acid/alcohol 1:2, 0.2 g catalyst, 90 C, 3 h).

13
 Chapter: 3 Experimental Set Up
3.1 Apparatus:

The esterification reaction of succinic acid with different alcohols are

carried outin a round bottom flask in a constant temperature oil bath.
Round bottom flask attached to Dean-Stark apparatus to remove the
water formed during the reaction and condenser to remove heat. It is also
attached to thermometer to measure the temperature of reaction mixture.
Round bottom flask with oil bath is placed on heating mental. The
reaction mixture is agitated using magnetic stirrer which is placed into
the round bottom flask. Stop watch to note the time for the reaction.
Titration set to determine acid content into the reaction mixture.
Measuring cylinder require to measure the chemicals.

3.2 Procedure:

Connect the all apparatus. Add succinic acid and alcohol in round
bottom flask (Different acid to alcohol ratio for different experiment).
Heat the reaction mixture at desired temperature. After the desired
temperature is achieved add the acid catalyst (Different amount of
catalyst for different experiment). Allow the reaction mixture to react for
different time interval. For different time interval determine the acid
content remain into the reaction mixture by collecting 2ml of reaction
mixture and titrating it with NaOH solution use phenolphthalein as
indicator. After the reaction is completed product is to be analyzed by
Gas Chromatography.
Fig. Schematic diagram of Esterification.
 Chapter: 4 Synthesis and Analytical Method
4.1 Synthesis

Levulinic acid
The original synthesis of levulinic acid is done by heating hexoses
(glucose, fructose) or starch in dilute hydrochloric acid or sulfuric
acid. The yield depends on the nature of the acid, acid concentration,
temperature and pressure. In addition to formic acid further, partly
insoluble, by-products are produced. These are deeply colored and their
complete removal is a challenge for most technologies.

Many concepts for the commercial production of levulinic acid are based
on a strong acid technology. The processes are conducted in a
continuous manner using lignocellulose as inexpensive starting material
which is impregnated by dilute mineral acid and transferred to a high
pressure reactor where it is heated with steam to allow the reaction to
form levulinic acid to take place. After cooling the reaction mixture and
filtering off the solid by-products, the levulinic acid that is formed is
separated from the mineral acid catalyst by extraction without
neutralization of the acid catalyst. This allows the acid catalyst to be
recycled, while the levulinic acid can be purified from the acid-free
organic solvent. Pure levulinic acid is isolated by evaporation of the
extraction solvent and distillation of the levulinic acid.
Properties:

4.2 Analytical Method

FTIR
Fourier-transform spectroscopy is a less intuitive way to obtain the same
information. Rather than shining a monochromatic beam of light (a
beam composed of only a single wavelength) at the sample, this
technique shines a beam containing many frequencies of light at once
and measures how much of that beam is absorbed by the sample. Next,
the beam is modified to contain a different combination of frequencies,
giving a second data point. This process is repeated many times.
Afterwards, a computer takes all this data and works backward to infer
what the absorption is at each wavelength.

The beam described above is generated by starting with a broadband

light source one containing the full spectrum of wavelengths to be
measured. The light shines into a Michelson interferometera certain
configuration of mirrors, one of which is moved by a motor. As this
mirror moves, each wavelength of light in the beam is periodically
blocked, transmitted,
blocked, transmitted, by the interferometer, due to wave interference.
Different wavelengths are modulated at different rates, so that at each
moment the beam coming out of the interferometer has a different
spectrum.

FTIR Scanning
Microscope

SEM (Scanning Electron Microscope)

A scanning electron microscope (SEM) is a type of electron microscope
that produces images of a sample by scanning the surface with a focused
beam of electrons. The electrons interact with atoms in the sample,
producing various signals that contain information about the
surface topography and composition of the sample. The electron beam is
scanned in a raster scan pattern, and the position of the beam is
combined with the detected signal to produce an image. SEM can
achieve resolution better than 1 nanometer. Specimens are observed in
high vacuum in conventional SEM, or in low vacuum or wet conditions
in variable pressure or environmental SEM, and at a wide range of
cryogenic or elevated temperatures with specialized instruments.
Scanning Process
In a typical SEM, an electron beam is thermionically emitted from
an electron gun fitted with a tungsten filament cathode. Tungsten is
normally used in thermionic electron guns because it has the highest
melting point and lowest vapor pressure of all metals, thereby allowing it
to be electrically heated for electron emission, and because of its low
cost. Other types of electron emitters include lanthanum hexaboride
(LaB6) cathodes, which can be used in a standard tungsten filament SEM
if the vacuum system is upgraded or field emission guns (FEG), which
may be of the cold-cathode type using tungsten single crystal emitters or
the thermally assisted Schottky type, that use emitters of zirconium
oxide.

Scanning electron
microscope
image (500x
magnification) of
pollen grains from
a variety of
common plants:
sunflower,castor
bean etc.

TEM (Transmission electron microscopy)

Transmission electron microscopy is a microscopy technique in which a
beam of electrons is transmitted through a specimen to form an image.
The specimen is most often an ultrathin section less than 100 nm thick or
a suspension on a grid. An image is formed from the interaction of the
electrons with the sample as the beam is transmitted through the
specimen. The image is then magnified and focused onto an imaging
device, such as
a fluorescent screen, a layer of photographic film, or a sensor such as
a charge-coupled device.
Transmission electron microscopes are capable of imaging at a
significantly higher resolution than light microscopes, owing to the
smaller de Broglie wavelength of electrons. This enables the instrument
to capture fine detail—even as small as a single column of atoms, which
is thousands of times smaller than a resolvable object seen in a light
microscope.
At lower magnifications TEM image contrast is due to differential
absorption of electrons by the material due to differences in composition
or thickness of the material. At higher magnifications complex wave
interactions modulate the intensity of the image, requiring expert
analysis of observed images. Alternate modes of use allow for the TEM
to observe modulations in chemical identity, crystal orientation,
electronic structure and sample induced electron phase shift as well as
the regular absorption based imaging.

Staphylococcus
aureus platinum
replica image shot on
a TEM at 50,000x
magnification
 Chapter: 5 Conclusions

• We can concluded that when we used 0.2 gm solid acid catalyst for
3h then we got 95% yield of butyle laurate.
• When molar ratio of acid/alcohol is taken 1:2 .then we got
maximum yield of butyle laurate.
• Thus, Finally we can concluded that when we used 0.2gm solid
acid catalyst at 90c for 3h then yield of Butyle laurate is maximum.
 Chapter: 6 References

1. Peter R. Griffiths; James A. De Haseth (Fourier Transform

Infrared Spectrometry )(2nd ed.) (2007).
2. Stokes, Debbie J (Principles and Practice of Variable Pressure
Environmental Scanning Electron Microscopy )(2008)
3. Ernst Ruska; translation by T Mulvey. (The Early Development of
Electron Lenses and Electron Microscopy)
4. Sharma P, Patel A (Tungstophosphoric acid supported onto
hydrous zirconia physicochemical characterization and
esterification of 1 and 2 alcohol (2006).