EXPERIMENTAL STUDIES ON EXTRACTION OF VALUABLE

EXPERIMENTAL STUDIES ON EXTRACTION OF VALUABLE
EXPERIMENTAL STUDIES ON EXTRACTION OF VALUABLE
FUELS FROM KARANJA AND NEEM SEED BY PYROLYSIS
A THESIS SUBMITTED IN THE PARTIAL FULFILLMENT OF THE
REQUIRMENT FOR THE DEGREE OF
Bachelor of technology
In
Chemical Engineering
Submitted by
NIRAJ KUMAR NAYAN
Under the guidance of
Prof. R.K.SINGH
Department of chemical engineering
National Institute of Technology, Rourkela
2011
CERTIFICATE
This is to certify that the thesis entitled, “EXPERIMENTAL STUDIES ON
EXTRACTION OF VALUABLE FUELS FROM KARANJA AND NEEM
SEED BY PYROLYSIS” submitted by Mr. Niraj Kumar Nayan (107CH008) in
partial fulfillments for the requirements for the award of Bachelor of Technology
Degree in Chemical Engineering at National Institute of Technology, Rourkela
(Deemed University) is an authentic work carried out by him under my supervision
and guidance.
To the best of my knowledge, the matter embodied in the thesis has not been
submitted to any other University / Institute for the award of any Degree or
Diploma.
Date
(PROF. R.K.SINGH)
Department of Chemical Engineering
National Institute of Technology
Rourkela – 769008
ACKNOWLEDGEMENT
I express my sincere gratitude to Prof. R. K. Singh (Faculty Guide) and Prof. H. M.
Jena (Project coordinator) of Department of Chemical Engineering, National
Institute of technology, Rourkela, for their valuable and timely suggestion during
the entire duration of my project work, without which this would not have been
possible.
I owe a depth of gratitude to Prof. K. C. Biswal (Head of Department), Department
of Chemical Engineering, for all the facilities provided during the tenure of entire
project work. I want to acknowledge the support of all the faculty and friends Of
Chemical Engineering Department, NIT Rourkela.
I would also like to thank Mr. Sachin Kumar (PhD Scholar), Ms. Debalaxmi
Pradhan and Mr. Ankit Agarwalla who have helped without any hesitation during
my project
Thanking you.
(NIRAJ KUMAR NAYAN)
107CH008
CHEMICAL ENIGEERING
Contents
Chapter 1: Introduction
Page No.
1.1 Introduction……………………………………………………....2
1.2 Literature Review…………………………………………….….7
Chapter 2: Materials and method
2.1 Materials…………………………………………………………17
2.2 Thermo gravimetric analysis ………………………………...…18
2.3 Experimental set up……………………………………………..18
2.4 Sample pyrolysis run……………………………………………20
2.5 Characterization of char, run…………………………….……...20
2.6 Physical Characterization of bio-oil…………………………….21
2.7 Chemical Characterization of bio-oil……………..…………….21
Chapter 3: Result and discussion
3.1 Thermo gravimetric analysis…………………………………….23
3.2 Observations……………………………………………………...24
3.3 Characterization of seed & char…………………………………27
3.4 Physical properties of pyrolyctic oil……………………………..28
3.5 Fouriers Transform infrared spectroscopy……………………..31
3.6 GC-MS…………………………………………………………….34
3.7 SEM……………………………………………………………….39
Chapter 4 : Conclusion……………………………………………………….44
References………………………………………………………………………45
LIST OF FIGURES
S. No.
Title
Page No.
Figure 1
India’s oil production and consumption
4
Figure 2
CO2emission from fuel combustion in India
5
Figure 3
Pyrolysis of rapeseed
11
Figure 4
Product distribution from pyrolysis of CWS
13
Figure 5
Product distribution from pyrolysis of CSS
14
Figure 6
Neem seed
17
Figure 7
Karanja seed
17
Figure 8
Experimental setup
19
Figure 9
TGA plot for neem seed
23
Figure 10
TGA plot for karanja seed
24
Figure 11
Observational graph for neem pyrolysis
25
Figure 12
Observational graph for karanja pyrolysis
26
Figure 13
FT-IR of neem oil
32
Figure 14
FT-IR of karanja oil
33
Figure 15
Chromatogram of neem oil
34
Figure 16
Chromatogram of karanja oil
37
Figure 17
SEM image of karanja char at 80 magnification
39
Figure 18
SEM image of karanja char at 200 magnification
40
Figure 19
SEM image of neem char at 200 magnification
41
Figure 20
SEM image of neem char at 80 magnification
41
LIST OF TABLES
S. No.
Title
Page No.
Table 1
Fossil fuel reserve of India (2008)
3
Table 2
Cost effectiveness of some RE in India
6
Table 3
Observation for soybeen seed by Niehaus and Schwab
10
Table 4
Standard method for physical property analysis
21
Table 5
Observation for neem seed
25
Table 6
Observation for karanja seed
26
Table 7
Seed and char characterization
27
Table 8
Physical properties of neem oil
28
Table 9
Physical properties of karanja oil
29
Table 10
Comparison of physical properties with other fuels
30
Table 11
Functional group in neem oil
32
Table 12
Functional group in karanja oil
33
Table 13
Compounds in neem oil
35
Table 14
Compounds in karanja oil
38
ABSTRACT
Today we see everywhere that oil has become inherent part of our daily life. Every activity is
dependent on the requirement of fuels be it directly or indirectly. The demand of fuels is
increasing day by day. Import dependence for oil in India which is about 70 per cent, is likely to
increase further. As we all know that the petroleum resources are limited and are non-renewable
in nature, we must start to think about the alternatives as we are likely to run out of the petroleum
resources in few decades or so. Stress must be given to production of energy from renewable
sources as they are biodegradable and non-toxic.
Here an attempt has made to study the feasibility of production of valuable fuels from natural but
non edible seeds such as karanja and neem seeds by the method of pyrolysis. Here the production
of the fuel can serve purpose of alternative fuels as biomass pyrolysis oil has potential to be used
as fuel oil or its substitute.
Keywords: Biomass, Thermal pyrolysis, TGA, GC-MS, Biofuels
1
INTRODUCTION
AND LITRETURE
SURVEY
2
1.1) INTRODUCTION
The reforms initiated in India since the beginning of the nineties have led to rapid economic
progress and better growth rates. In the first decade of this century the growth rates seem to be
still better. Studies by several academics and consultants forecast continued high growth rate for
the next several decades. Growth in economy is made possible by several inputs, the two most
important being energy and human resource. Growth of an economy, with its global
competitiveness, hinges on the availability of cost-effective and environmentally benign energy
sources, and on the other hand, the level of economic development has been observed to be
reliant on the energy demand
For a large country like India with its over one billion population and rapid economic growth
rate, no single energy resource or technology constitutes a panacea to address all issues related to
availability of fuel supplies, environmental impact, particularly, climate change, and health
externalities. Therefore, it is necessary that all non-carbon emitting resources become an integral
part of an energy mix – as diversified as possible – to ensure energy security to a country like
India during the present century. Available sources are low carbon fossil fuels, renewable and
nuclear energy and all these should be subject of increased level of research, development,
demonstration and deployment [1].
Below is the table that shows India’s fossil fuel reserve and its rate of production and
consumption.
3
Table 1 Fossil fuel reserve of India (2008) [3]
Resources
Oil
Proved reserve
5.8 billion barrels
Natural gas
1009 billion cubic
meters
58.6 billion ton
Coal
Production
0.76 million barrels
per day
30.6 billion cubic
meters
512.3 million tons
Consumption
2.88 million barrels
per day
41.4 billion cubic
meters
608.3 million tons
At the end of 2005, India had 0.5 % of the Oil and Gas resources of the world and 15 % of the
world’s population whereas the reserve to production ratio is 20:7. At the end of 1995 India had
the 5.5 thousand million barrels of reserves, grown only 1% till the end of 2005 whereas crude
oil consumption has grown more than 10% over the last 5 years. Domestic production of crude
oil has been a reason of worry for the Indian economy for some time now. For more than 16
years the total production of crude has stagnated around 32-33 MMT. This has been particularly
disturbing given the crude oil consumption in the country implying an increasing dependence on
imported crude. At present India’s crude dependence is around 78%. According to TERI
estimates, by 2030 India’s import dependency may shoot up to a disturbing 93%. [20]
4
Figure 1 India’s oil production and consumption [3]
Seeing the above graph and also observing the rising prices of crude oil and petroleum oil it has
become quite necessary that we must start investing in alternative sources of energy. At present,
contribution from non-conventional energy sources, such as solar, wind, biomass, small hydro
(upto 25 MW capacity ), etc. is around 3% of the total installed power generating capacity. The
strategy to enhance the grid supply of power from renewable sources of energy or from cogeneration has to aim at improving despatchability and cost competitiveness. A suitable policy
framework would need to be introduced for providing remunerative returns and encouraging
private investments.
Development and promotion of this sector, which is environmentally
benign, should not be constrained by intrusive regulation. [3]
Also global warming is another aspect in which we have to look into. The emission of the green
house gases (GHGs) needs to be controlled. India is the sixth largest greenhouse gas (GHG)
emitter in the world, and the fastest-growing one after China. We all know the adverse effect
hence the Renewable Energy Plan 2012 calls for achieving a 10 percent share for renewable
5
energy in incremental power capacity by adding about 10,000 MW of new
ew renewable energy
(RE) based generation. [2]
Figure 2 CO2emission from fuel combustion in India [2]
So as to control the emission of GHG the
he Electricity Act of 2003 has provided a major thrust to
RE technologies
hnologies via its mandate: “To promote cogeneration and generation of electricity through
renewable sources of energy by providing suitable measures for connectivity with the grid and
sale of electricity to anyy persons, and also specifying, for purchase of electricity from such
sources, a percentage of the total consumption of electricity in the area of a distribution licensee.”
Detailed cost-benefit
benefit assessments were undertaken for India’s energy sector mitigation options in
the India country study conducte
conducted under the Asia Least Cost Greenhouse
enhouse Gas Abatement
Strategy (ALGAS, ADB, 1998) project
project. [2]
6
Table 2 Cost effectiveness of some RE option in India [2]
Technologies
Investment cost
(US$/KW)
Cost effectiveness
(US$/ton CO2)
Small hydro
GHGs emission
reduction
(Kg/KWH)
1.3
1950
88
Wind farms
1.3
1405
257
Biomass
1.6
710
102
Solar thermal
1.3
3730
592
Solar PV
1.6
5952
541
Observing from the table above we can see that the biomass has the maximum potential for
GHGs emissions and also the investment cost is lowest than the other RE sources.
Here an attempt is made to study the feasibility of production of valuable fuels from natural but
non edible seeds such as karanja and neem seeds by the method of pyrolysis. As the production
of the fuel can serve purpose of alternative fuels as biomass pyrolysis oil has potential to be used
as fuel oil or its substitute. It can also be used as blend with normal diesel.
Although in European countries and USA the biodiesel are produced from edible oil as their
production of edible oil is quite high and surplus but in India we prefer non edible oil seeds as
the production of edible oil seeds in India is insufficient and we import it from other countries to
fulfill the requirements.
7
1.2) LITERATURE REVIEW
Krawcyzk (1996) - Biodiesel, an alternative diesel fuel, is made from renewable biological
sources such as vegetable oils and animal fats. It is biodegradable and non-toxic. It also has low
emission profiles and so is environmentally beneficial. [11]
Importance of biodiesel increases due to [4]:1) Rising petroleum prices
2) Limited fossil fuel reserve
3) Environmental benefits of biodiesel
Advantages of biodiesel:a) Availability and renewability of biodiesel - Biodiesel is the only alternative fuel with the
property that low concentration biofuel–petroleum fuel blends will run well in unmodified
conventional engines. It can be stored anywhere petroleum diesel fuel is stored. Biodiesel can be
made from domestically produced, renewable oilseed crops such as soybean, rapeseed and
sunflower. The risks of handling, transporting and storing biodiesel are much lower than those
associated with petroleum diesel. Biodiesel is safe to handle and transport because it is as
biodegradable as sugar and has a high flash point compared to petroleum diesel fuel. Biodiesel
can be used alone or mixed in any ratio with petroleum diesel fuel.
b) Lower emission from biodiesel - Biodiesel mainly emits carbon monoxide, carbon dioxide,
oxides of nitrogen, sulfur oxides and smoke. Combustion of biodiesel alone provides over a 90%
reduction in total unburned hydrocarbons (HC) and a 75–90% reduction in polycyclic aromatic
8
hydrocarbons (PAHs). Biodiesel further provides significant reductions in particulates and
carbon monoxide over petroleum diesel fuel. Biodiesel provides a slight increase or decrease in
nitrogen oxides depending on engine family and testing procedures. Because biodiesel is made
from renewable sources, it presents a convenient way to provide fuel while protecting the
environment from unwanted emissions
c) Biodegradability of biodiesel - Biodegradable fuels such as biodiesels have an expanding
range of potential applications and are environmentally friendly. Therefore, there is growing
interest in degradable diesel fuels that degrade more rapidly than conventional petroleum fuels.
Biodiesel is non-toxic and degrades about four times faster than petroleum diesel. Its oxygen
content improves the biodegradation process, leading to an increased level of quick
biodegradation
Different methods use for production of biodiesel [4]:1) Direct use/blending - Vegetable oil can be used directly as diesel fuel without any changes in
the engine. The very first engine (by Rudolf Diesel) was tested using vegetable oil as fuel. The
primary concern with vegetable oil as fuel is its high viscosity (atomization of vegetable oil is
difficult) which leads to problem in long run as there is carbon deposits, coking and trumpet
formation on injectors, thickening, gelling and oil ring sticking.
2) Micro emulsions – It is defined as colloidal dispersion of fluid microstructures (1-150 nm) in
solvents forming two immiscible phases. The common solvent used is methanol and ethanol.
Micro emulsion is a probable solution to high viscosity of vegetable oil. Their atomization is
relatively easy due to lower viscosity.
9
3) Pyrolysis – It is the means of conversion of one substance to another by the application of
heat. It is a thermochemical decomposition of organic material at elevated temperatures in the
absence of oxygen. Pyrolysis of organic substances produces gas and liquid products and leaves
a solid residue richer in carbon content. Catalysts are used to speed up the process. Here the oil
yield is due to the fact that cracking of larger hydrocarbons cause them to break into simpler and
smaller hydrocarbons by radicalic mechanism which are easily condensable to oil in this case
4) Trans esterification (alcoholysis) – It is a kind of organic reaction in which alcohol group in
ester is substituted. A catalyst is usually used to improve the reaction rate and yield. Because the
reaction is reversible, excess alcohol is used to shift the equilibrium to the products side.
Pyrolysis –
Pyrolysis, strictly defined, is the conversion of one substance into another by means of heat or by
heat with the aid of a catalyst (Sonntag, 1979b). It involves heating in the absence of air or
oxygen (Sonntag, 1979b) and cleavage of chemical bonds to yield small molecules (Weisz et al.,
1979). Chemistry involved in pyrolysis is difficult to characterize because of the variety of
reaction paths and the variety of reaction products that may be obtained from the reactions that
occur. The pyrolyzed material can be vegetable oil, animal fat, natural fatty acids or methyl
esters of fatty acids. The pyrolysis of fats has been investigated for more than 100 years,
especially in those areas of the world that lack deposits of petroleum. Many investigators have
studied the pyrolysis of triglycerides to obtain products suitable for diesel engines. Thermal
decomposition of triglycerides produces alkanes, alkenes, alkadienes, aromatics and carboxylic
acids. It is one of the energy recovery processes which have the potential to generate oil, char
10
and gas products. The process conditions of pyrolysis can be optimized to maximize the
production of pyrolytic oil, char or gas, all of which have a potential use as fuels. The process
parameters which have the major influence on the products are the pyrolysis temperature, heating
rate, particle size and retort atmosphere. The oil produced has a high energy density and may be
combusted directly or refined for the recovery of specialty chemicals. The production of liquid
product has advantages in that it is easier to handle, store and transport [12]
Pyrolysis can be of two types:-1) Catalytic pyrolysis - Here suitable catalyst is used in addition to
the heat which speeds up the reaction by increasing the thermal degradation rate of the substance.
2) Non-catalytic pyrolysis - Here only heat is applied for the thermal degradation of the
substance.
Chang and wan (1947) setup a large scale of thermal cracking of tung oil calcium soaps where
the oil was first converted to soap with lime and then thermally cracked to yield a crude oil,
which was refined to produce diesel fuel and small amounts of gasoline and kerosene. 68 kg of
the soap from the saponification of tung oil produced 50 L of crude oil.
Niehaus et al. (1986) (a) and Schwab et al. (1988) (b) studied fuel properties of thermally
cracked soybean oil and observed the following data:Table 3 Observation for soybeen seed by Niehaus and Schwab [12]
Properties
Cetane no.
Higher
heating value
(Mj/kg)
Pour point
(°C)
Viscosity cst ,
(37.8°C)
Soybean
oil (a)
38
39.3
Soybean
oil (b)
37.9
39.6
Cracked
soyb oil (a)
43
40.6
Cracked
soyb oil (b)
43
40.3
Diesel fuel
(a)
51
45.6
Diesel fuel
(b)
40
45.5
-12.2
-12.2
4.4
7.2
-6.7 max
-6.7 max
32.6
32.6
7.74
10.2
2.82
1.9-4.1
11
Ozlem Onay and O. Mete Kockar (2000) investigated fixed bed slow and fast
fas pyrolysis of
rapeseed. The influence of final pyrolysis temperature, heating rate, particle size range and
sweep gas velocity on the product yields were studied. In addition, the pyrolysis oil at the
maximum liquid product yield was investigated, using chromatographic and spectroscopic
techniques to determine its possibility of being a potential source of renewable fuel and chemical
feedstock. They observed the following pattern.
Figure 3 Pyrolysis of rapeseed [7]
They concluded that the oil yield was obtained as 49% from pyrolysis of rapeseed at a final
pyrolysis temperature of 550◦C,
C, particle size range of +0:6–1:8
1:8 mm with a heating rate of 30◦C
30
min−1. The oil yield only reached 51.7% with the experiments under sweeping gas atmosphere
(nitrogen flow rate of 100–200
200 cm3 min−1). Employing the higher heating rate of 300◦C
300 min−1
breaks heatt and mass transfer limitations and the oil yield reach a maximum of 68.0% at the final
12
pyrolysis temperature of 550◦C, particle size range of +0:6–1:25 mm and sweeping gas flow rate
of 100 cm3 min−1 [7].
Ozlem Onay and Ö. Mete Kockar (2003) also studied slow, fast and flash pyrolysis of rapeseed
(Brassica napus) in particular, the influence of final pyrolysis temperature, heating rate, particle
size range and sweep gas velocity. He found out that Employing the higher heating rate of 300
°C min-1 breaks mass transfer limitations and the oil yield reach a maximum of 68%, increasing
by 32%, at the final pyrolysis temperature of 550 °C. Furthermore, in flash pyrolysis conditions,
the maximum liquid product yield of 73% was obtained at final pyrolysis temperature of 550–
600 °C. [5]
S.H. Beis, O. Onay and Ö. M. Kockar (2002) also studied fixed bed pyrolysis of safflower seed
and the influence of pyrolytic parameter on product yields. They observed that at a lower heating
rate of 5°C min-1, the char yield decreased from 23 to 19% as the final pyrolysis temperature was
raised from 400°C to 700°C. For the heating rates of 40 and 80°C min-1 there are no significant
changes in yields of the conversion with increasing pyrolysis temperature from 400 to 700°C.
However, at the higher heating rates of 40 and 80°C min-1, the overall conversion yields of
pyrolysis were approximately 4% higher than that of the lower heating rate of 5°C min-1. In
contrast, the oil yields were approximately 3% lower than that of 5°C min-1. Varying the particle
size from dp>1.8 to 0.85<dp<1.25 mm at a pyrolysis temperature of 500°C with a heating rate of
5°C min-1 without any sweeping gas atmosphere had a significant effect on the pyrolysis
conversion with it increasing from 75 to 80%. Whereas a decreasing particle size from
0.85<dp<1.25 to 0.425<dp<0.85 mm had no effect on pyrolysis conversion, it remaining
constant at the level of approximately 80%. [8][9]
13
G. Duman, C. Okutucu, S. Ucar, R. Stahl and J. Yanik (2011) studied the slow and fast pyrolysis
of cherry seed in fixed bed and fluidized bed reactor at different temperatures. The effects of
reactor type and temperature on the yields and composition of products were investigated. In the
case of fast pyrolysis,
sis, the maximum bio
bio-oil
oil yield was found to be about 44 wt% at pyrolysis
temperature of 500°C for both cherry seeds ((CWS) and cherry shell seed (CSS)), whereas the bio
yields were off 21% and 15% by weight, obtained at 500
500°C
C from slow pyrolysis of CWS and
CSS,
S, respectively. Both temperature and reactor type affected the composition of bio-oils.
bio
The
results showed that bio-oils
oils obtained from slow pyrolysis of CWS and CSS can be used as a fuel
for combustion systems in industry and the bio
bio-oil produced from fastt pyrolysis can be evaluated
as a chemical feedstock. [11]
Figure 4 P
Product distribution from pyrolysis of CWS
[11]
14
Figure 5 Pyrolysis of CSS
[11]
Ozlem Onay (2007)) investigated the Influence of pyrolysis temperature and heating rate on the
production of bio-oil
oil and char from safflower seed by pyrolysis, using a well-swept
well
fixed-bed
reactor. He concluded that high volatile matter content of biomass with low ash and sulfur
content is the main criterion for pyrolysis conversion and the high volatile content of safflower
seed favors the pyrolysis conversion. He also observed significant decrease in oxygen content of
the oil (8.5%) compared to the original feedstock (27.
(27.4%)
4%) is important, because the high oxygen
content is not attractive for the production of transport fuels. As the final pyrolysis temperature
was raised from 400 to 700 °C for each heating rate, the char yield significantly decreased. In
other words, the pyrolysis
yrolysis conversion increased. The decrease in the char yield with increasing
temperature could be due either to greater primary decomposition of the safflower seed at higher
temperatures or to secondary decomposition of the char residue. Pyrolysis temperature
tempera
and
heating rate influenced the size and shape of particle through a general increase in size and
15
proportion of voids and a decrease in cell wall thickness. The fast volatile release during
pyrolysis produces substantial internal overpressure and the coalescence a more open structure.
Therefore, SEM porosity increased with a pyrolysis temperature and increasing heating rate. The
surface area was maximized at pyrolysis temperature of 600 °C and heating rate of 800 °C
min−1. Both the hydrogen and oxygen content of char decreased with increase in temperature,
indicating an increase in the carbonaceous nature of the char. [9]
R.K.Singh and K.P.Shadangi (2011) investigated Liquid fuel from castor seeds by pyrolysis and
concluded that The maximum yield of oil, 64.4% by weight a basis was obtained at a
temperature of 550°C. Though the production of oil in volume basis is same from 525°C to
600°C, due to the less completion time and low density oil obtained at 550°C, the optimum
temperature for production of oil from castor seed in slow pyrolysis process is 550°C. The
functional group present in castor seed pyrolytic oil is similar as compare to other bio oil given
in several literatures. The major compounds present in castor seed pyrolytic oil were 10undecenoic acid, oleic acid, octadecanonic acid, octadec-9-enoic acid, N-hexadecanoic acid, 3phenyl-5-(pyridin-4-ylmethylidene)-2-thioxoimidazolidin- 4-one, Z-11-pentadecenal, oleanitrile,
9-octadecenamide, (z)-, methy; 12-hydroxy-9-octadecenenoate, 2-pentylnon-2-enal, methy; 12hydroxy-9-octadecenenoate, 13-hexyl-oxa-cyclotridec- 10-en-2-one with a fewer amounts of
ester and alkali compounds. The properties of pyrolytic oil reveal that it can be used as a
substitute for fuel. Due to the absence of arsenic compound in the char materials and high
calorific value, it can be used as adsorbent as well as solid fuel. [10]
16
MATERIALS AND
METHODS
17
2.1) Materials
Here two non-edible seeds have been used namely karanja seed (also known as Pongamia glabra)
and neem seed (also known as Mellia azadirachta)which was bought from a local fodder shop in
Rourkela, Orissa, India. Both the seed were crushed using a household grinder, so that we could
feed maximum seed, almost up to the capacity so that there would be minimum void and hence
less oxygen for oxidation since pyrolysis is a process of heating substance in absence of oxygen.
Below are the figures of karanja and neem seed.
Karanja and neem seed:-
Figure 6 Neem seed
Figure 7 Karanja seed
18
2.2) Thermo gravimetric analysis
Pyrolysis is heating of a substance in absence of air at a particular temperature. Therefore, the
temperature for effective pyrolysis of the karanja and neem seed has to be determined. For this
purpose, thermo-gravimetric analysis (TGA) of the sample cake was done using a DTG60
instrument. Around 20-30 milligrams of sample cake was taken and heated up to a final
temperature of 800°C and a residence time of 1 minute at 800°C was allowed. TGA was
performed in air atmospheres at a heating rate of 10°C/Min. Thermo-gravimetric weight loss
curve was plotted against temperature. It provides a range of temperature in which maximum
thermal degradation takes place.
2.3) Experimental setup and procedure
The setup consist of a semi-batch reactor in which the seeds are placed and that is then closed
very tightly so as to avoid any leakage of gas as the result of pyrolysis. The outlet of the reactor
is connected to a condenser (circulating water is the cooling medium) which condenses the
gases/vapor coming of the outlet. Just at the other end of the condenser a measuring cylinder is
placed where the gases being condensed is collected. The reactor is heated using an electric
furnace. The temperature is controlled via PID controller.
The seeds are fed into the reactor and it is closed very tightly using screw and bolt. Once the
heating is started and after reaching a suitable temperature the reaction begins and the vapors that
are released comes out of the reactor outlet which is connected to the condenser where the vapors
are condensed and the collected in the test tube. Most of the non-condensable vapors are simply
19
released. The product mainly consists of pyrolytic oil and water which then is separated based on
density difference.
Figure 8 Experimental setup
PROCEDURE
•
Firstly approximately 25 gm of sample is taken and fed in the reactor.
•
Then the desired temperature is set and the pyrolysis is started.
•
Once the reaction begins the reaction time and the yield is noted down.
•
This is done for the entire range of temperature with 50°C interval.
•
Then the temperature is identified at which there is maximum yield.
•
Rest of the extraction is carried out at this temperature.
20
2.4) Sample pyrolysis run
To determine the temperature at which there is maximum yield in the temperature range obtained
by TGA, sample pyrolysis run were done. In the sample pyrolysis run, we took approx. 25 gm of
the seed and pyrolysis was done at different temperature in that range at the interval of 50°C, to
determine the temperature at which maximum yield of liquid product is obtained. During sample
runs various data like reaction time, yield of char, and yield of liquid product were noted down.
Variation in yield of char, liquid product and gas (volatiles) with respect to temperature is
plotted. Variation in reaction time with temperature was also plotted.
2.5) Characterization of raw material and char
The karanja and neem seed and char of these seeds were analyzed in order to observe the change
in the properties of the solid material as a result of pyrolysis.
2.5.1) Proximate analysis
It provides information on moisture content, ash content, volatile matter content and fixed carbon
content of the material. It was carried out using ASTM D3172 - 07a method.
2.5.2) Calorific value
Calorific value of a material is the amount of heat liberated when 1Kg of that material is burnt. It
was determined for both seed and char using a bomb calorimeter (Model: AC-350, LECO
Corporation, USA).
2.5.3) Scanning electron microscopy
The surface of the char obtained was viewed under a Scanning Electron Microscope (Model:
JEOL-JSM-6480LV SEM) at different magnification values to have a clear view on pore density
and size.
21
2.6) Physical characterization of bio-oil
Physical properties such as density, specific gravity, viscosity, conradson carbon, flash point, fire
point, pour point, cloud point, calorific value, sulphur content, distillation boiling range and
cetane index of the bio-oil was determined using the following standard methods:
Table 4 Standard method for physical property analysis
Physical properties
Density
Kinetic viscosity
Conradson carbon
Flash point
Fire point
Pour point
Calorific value
Distillation boiling range
Cetane index
Method
ASTM D1298 - 99
ASTM D445 - 11
ASTM D189 - 06(2010)e1
ASTM D6450 - 05(2010)
ASTM D1310 - 01(2007)
ASTM D5853 - 09
ASTM D5468 - 02(2007)
ASTM D2887 - 08
ASTM D4737 - 10
2.7) Chemical characterization of bio-oil
2.7.1) FT-IR
In order to determine the functional groups present in the pyrolytic oil, Fourier Transform
Infrared spectroscopy of the oil was analyzed in a Perkin-Elmer infrared spectrometer.
2.7.2) GC-MS :- Gas Chromatography – Mass Spectrometry of the pyrolytic oil was performed
using a GC-MS-OP 2010[SHIMADZU] analyzer in Sargam Laboratory, Chennai to determine
the chemical compounds present in the oil.
22
RESULT AND
DISCUSSION
23
3.1) THERMOGRAVIMETRIC ANALYSIS
Thermo gravimetric analysis (TGA) measures the amount and rate of change in the weight of a
material as a function of temperature. TGA is helpful in determining the range of temperature
under which the moisture and the volatile content of the substance is driven out which is then
condensed and the pyrolysed oil is recovered. Here the TGA is carried in normal atmosphere
with the rate of heating being 10°C/minute and the range being room temperature to 800°C.
1) NEEM seed
120
% weight ramaining
100
80
60
40
20
0
0
200
400
600
800
1000
Temperature oC
Figure 9 TGA plot for neem seed
The plot shows that maximum thermal degradation took place between ranges of 200°C to
600°C. The initial degradation can be explained by the fact that initially the moisture is driven
away as the temperature is increased. Then the removal of volatile matter consisting of relatively
24
less complex molecules accounts for the further degradation in weight which can be said for the
range of 400°C to 550°C. The further degradation can be explained by the fact that much more
complex molecules are driven away as the heating progresses.
2) KARANJA seed
120
% weight remaining
100
80
60
40
20
0
0
200
400
600
800
1000
Temperture oC
Figure 10 TGA plot for karanja seed
Here the range in which maximum degradation is taking place is 250°C to 600°C. Here also the
moisture is removed by initial heating and then the relatively less complex molecule and then the
removal of highly complex molecule.
3.2) OBSERVATION
3.2.1) NEEM OIL
25
Table 5 Observation for neem seed
Serial
no.
Temperature
(°C)
1
2
3
4
5
400
425
450
475
500
Weight
of
sample
(gm)
25
25.04
25.2
25
25.02
Reaction
time
(min)
Weight Density Weight
% of the of the oil % of
oil
(kg/L)
char
36
31
25
22
16
16.12
17.65
37.77
38
34.65
0.895
0.884
0.906
0.863
0.867
46.4
39.14
37.34
29.4
23.26
a) Graph for above observation
50
60
Reaction time
Char yield
gas yield
liquid yied
45
50
40
35
30
30
25
20
20
10
15
10
0
375
400
425
450
475
500
0
Temperature ( c)
Figure 11 Observational graph for neem pyrolysis
525
% yield
Reaction time (min)
40
Weight
% of
volatiles
37.48
43.21
24.88
32.6
42.08
26
3.2.2) KARANJA SEED
Table 6 Observation for karanja seed
Serial
no.
Temperature
(°C)
Weight
of
sample
(gm)
Reaction
time
(min)
Weight Density Weight
% of the of the oil % of
oil
(kg/L)
char
1
2
3
4
5
450
475
500
525
550
25
25.03
25.05
25.04
25.02
40
33
24
20
16
49.2
50.41
57.12
37.02
24.82
0.911
0.902
0.954
0.927
0.887
36.8
34.36
30.01
27.07
21.58
Weight %
of
Volatiles
14
15.23
12.86
35.90
53.59
a) Graph for above observation.
50
60
45
50
Reaction time
Char yield
gas yield
liquid yied
35
40
30
30
% yield
Reaction time (min)
40
25
20
20
10
15
10
0
425
450
475
500
525
550
575
600
0
Temperature ( c)
Figure 12 Observational graph for karanja pyrolysis
The plot between yield of liquid, solid and gaseous products vs. temperature clearly shows that
in case of neem seed, the yield of liquid product increases with increases in temperature in the
range of 400-475°C up to 500°C and then it starts decreasing. Thus maximum yield of liquid
product is obtained at 475°C which indicates it as effective pyrolysis temperature for the neem
27
seed. But in case of karanja seed, the yield of liquid product increases with increase in
temperature in the range of 450-5000C up to 5000C and starts decreasing with further increase of
temperature. So the maximum yield of liquid product is obtained at 500°C which indicates it as
effective pyrolysis temperature for the karanja seed. The reaction time decreases with increase in
temperature in both neem seed and karanja seed.
3.3) CHARACTERISATION OF SEED AND CHAR
Proximate analysis is the fastest way of analyzing the quality of the fuel oil. It gives us the
information about carbon content, ash content, volatile matter and moisture. Now for instance
high moisture content will increase transportation cost, reduce calorific value and most of the
energy will be used in removing the moisture. It also affects the conversion efficiency of the
biomass and also there is potential to loose energy as a result of decomposition. Whereas high
volatile matter means that there would more liquid product due to thermal decomposition as
volatile matter is a complex mixture of organic and non-organic compound.
Table 7 Seed and char characterization
Proximate
analysis
Moisture %
Karanja seed
Karanja char
Neem seed
Neem char
5
3.9
6
5
Ash content
3.9
8.9
4.95
17.8
Volatile matter
84
32
81
37
Fixed carbon
7.1
55.2
8.05
40.2
Calorific value
(kcal/kg)
5350
6050
5500
7100
28
As can be seen above that the calorific value of the char is quite good and hence it can serve the
purpose of alternate source of energy for heating and burning process.
3.4) PHYSICAL PROPERTIES OF THE
PYROLYTIC OIL
In the table below are shown some of the physical properties of both the Neem oil and Karanja
oil such viscosity index, pour point, fire point, cloud point, gross calorific value, kinematic
viscosity, initial and final boiling point, density, appearance, carbon residue, flash point, sulfur
content and cetane index.
3.3.1) NEEM oil
Table 8 Physical properties of neem oil
Properties
Neem pyrolytic oil
Appearance
Dark brownish oil
Density at 15°C (kg/m3)
0.9610
Specific gravity at 15°C/15°C
0.9619
Kinetic viscosity at 40°C in centistoke
22.6
Kinetic viscosity at 100°C in centistoke
3.8
Viscosity index
Plus 11
Conradson carbon residue
5.03%
Pour point
Plus 11°C
29
Cloud point
22°C
Flash point by Abel method
42°C
Fire point
62°C
Gross calorific value in Kcal/kg
7736
Sulfur content
0.48%
Calculated Cetane index
21
Initial boiling point
98°C
Final boiling point
352°C
3.3.2) KARANJA oil
Table 9 Physical properties of karanja oil
Properties
Neem pyrolytic oil
Appearance
Dark brownish oil
Density at 15°C (kg/m3)
0.9384
Specific gravity at 15°C/15°C
0.9393
Kinetic viscosity at 40°C in centistoke
27.9
Kinetic viscosity at 100°C in centistoke
4.4
Viscosity index
Plus 34
Conradson carbon residue
4.30%
Pour point
Plus 16°C
Cloud point
28°C
Flash point by Abel method
40°C
30
Fire point
58°C
Gross calorific value in Kcal/kg
8113
Sulfur content
0.05%
Calculated Cetane index
29
Initial boiling point
96°C
Final boiling point
376°C
Comparison of properties with other commonly used fuels
Table 10 comparison of physical properties with other fuels
Properties
Fuel
Neem oil
Karanja
oil
Gasoline
Diesel
Specific
Kinematic
gravity
[email protected]
15°C/15°C 40°C (Cst)
0.9619
22.6
0.9393
27.9
Flash
point
(°C)
42
40
Pour
point
(°C)
11
16
GCV
MJ/kg
IBF
(°C)
FBF
(°C)
32.38
33.9
98
96
352
376
42-46
42-45
27
172
225
350
C4-C12
C8-C25
37-40
315
350
C12-C22
40
-
-
-
Chemical
formula
0.72-0.78
0.82-0.85
2-5.5
-43
53-80
Biodiesel
0.88
4-6
Heavy fuel
oil
Rapeseed
pyrolytic
oil
Sunflower
pyrolytic
oil
0.94-0.98
>200
100170
90-180
-40
-40 to
-1
-3 to
19
-
0.993
>40
62
6
36-37
-
-
CH1.78N0.04
O0.15
1.02-1.079
50-250
58-76
-16
38-41
92
315
CH1.88
O0.15 N0.02
31
As can be seen from the above comparison, the kinematic viscosity and density of the neem as
well as the karanja oil is greater than the gasoline, biodiesel and diesel oil but is comparatively
less than the other three so one can say that the transportation and flow of these oil can be
difficult. Hence the pumping and injection of the fuel in the engine will be difficult. Also the
pour point is relatively higher than the other fuels so in the area of low temperature the flow and
piping of the will be even more difficult. We can see from the above comparison that the gross
calorific value is comparable to the other fuel which is almost 75% of gasoline and diesel oil for
both neem and karanja oil. Also the flash point is quite high which means it is safe for storage as
it will not ignite easily.
As far as the density and viscosity are concerned, we can these fuels as blend with other major
fuels as the resulting density and viscosity will be less.
3.5) FOURIER TRANSFORM INFRARED
SPECTROSCOPY (FT-IR)
FT-IR is used to determine the different functional group such as alcohol, alkane, alkynes,
alkenes and other such groups present in the substance which here is neem oil and karanja
pyrolytic oil. Although it has to be confirmed by gas chromatography-mass spectroscopy.
3.5.1) NEEM OIL
32
248.1
240
230
220
210
200
190
180
170
%T
3792.71
160
3717.33
150
140
130
120
110
1269.18
1453.22
100
1722.86
3081.23
2920.15
90
80
71.2
4000.0
3600
3200
2800
2400
2000
1800
1600
1400
1200
1000
800
cm-1
Figure 13 FT-IR analysis of neem oil
Table 11 Functional group in neem oil
Frequency
Compound
3717.33
Amide N-H stretch
3081.29
CHStretchof C=C
2920.15
CHStretch
1722.86
C=O
1453.22
C=H
1269
C=H
600
400.0
33
3.5.2) KARANJA OIL
97.9
95
90
85
80
75
70
65
60
55
50
%T
45
40
35
734.74
30
25
20
1452.39
15
1271.63
3058.82
10
1705.24
5
2923.35
-0.4
4000.0
3600
3200
2800
2400
2000
1800
1600
1400
1200
1000
800
cm-1
Figure 14 FT-IR analysis of karanja oil
Table 12 Functional group in karanja oil
Frequency
Compound
2923.34
CH Stretch
1705.24
C=O
3070.02
CHStretch of C=C
1452.39
Aromatic CH
1271.63
Aromatic CH
600
400.0
34
3.6) GAS CHROMATOGRAPHY
CHROMATOGRAPHY-MASS
SPECTROSCOPY
The chemical composition of the neem oil and the karanja oil was determined using the gas
chromatography mass spectroscopy and was found that neem oil consisted of 41 compounds and
karanja oil consisted of 21 compounds.
3.6.1) Chemical composition of neem pyrolytic oil
Figure 15 chromatogram of neem oil
35
Table 13 Compounds present in neem oil
Compound
Area %
Formula
o-Methoxyphenol
1.26
C6H4(OH)(OCH3)
1,4-Dimethoxybenzene
1.17
C6H4(OCH3)2
Tridecane
.84
C13H28
Pyrogallol 1,3-dimethyl ether
2.23
C8H10O3
1-Tetradecene
0.75
CH2=CH(CH2)11CH3
n-Tetradecane
1.46
C14H30
1,2,4-Trimethoxybenzene
1.1
C9H12O3
(E)-Isoeugenol
0.63
1-Hexadecene
0.85
Pentadecane
3.44
Toluene, 3,4,5-trimethoxy-
1.44
1-Heptadecene
1.19
C17H34
Nonadecane
2.23
C19H40
3-Heptadecene
2.31
C17H34
9-Eicosene
2.55
C20H40
1-octadecene
0.93
CH2=CH(CH2)15CH3
Heptadecane
5.42
C17H36
Phenol,2,6dimethoxy-4-(2-
1.71
C11H14O3
1-octadecene
0.58
CH2=CH(CH2)15CH3
Heneicosane
1.16
C21H44
1-Nonadecene
0.48
C19H38
Nonadecane
1.17
C19H40
Hexadecanenitrile
6.44
C16H31N
Hexadecanoic acid, methyl
6.08
C17H34O2
C10H12O2
CH2=CH(CH2)13CH3
C15H32
C10H14O3
propenyl)
36
easter
1-Nonadecanol
0.50
CH3(CH2)18OH
eicosane
0.75
C20H42
Oleanitrile
7.32
C18H33N
E-11-Hexadecenal
4.03
C16H30O
9-octadecenoic acid, methyl
6.93
C19H36O2
Octadecanenitrile
11.55
C18H35N
Stearic acid, methyl ester
6.15
CH3(CH2)16COOCH3
Hexadecanamide
2.73
C16H33NO
N-methyl hexadecanamide
0.53
C17H35NO
4-Fluorophenyl
0.86
C6H5F
2-propenyl decanoate
0.60
C13H24O2
Heptadecanenitrile
0.70
C17H33N
9-octadecenamide
4.30
C18H35NO
13-Docosenamide, (Z)-
1.98
C22H43NO
Stearic amide
2.04
C18H37NO
N-methyloctadecanamide
0.95
C19 H39 NO
Stigmast-5-en-3-ol, oleate
0.67
C47H82O2
ester
Here we can see that the major component of the neem oil are Octadecanenitrile, Oleanitrile , 9octadecenoic acid methyl ester, Stearic acid methyl ester, heptadecane, 9-octadecenamide, E-11Hexadecenal and pentadecane which are 11.55%, 7.32&, 6.93%, 6.15%, 5.42%.4.30%, 4.03%
and 3.44% respectively. They almost comprise of 43% of the total mass.
37
3.6.2) Chemical composition of Karanja seed pyrolytic oil
Figure 16 Chromatogram for karanja oil
Table 14 Compounds present in karanja oil
Compound
Area %
Formula
1-Tetradecene
0.14
CH2=CH(CH2)11CH3
n-Tetradecane
0.32
C14H30
Pentadecane
0.91
C15H32
Nonadecane
0.43
C19H40
3-Heptadecene, (Z)-
1.44
C17H34
9-Eicosene, (E)-
1.34
C31H32N2O4
n-Heptadecane
1.01
C17H36
Nonadecane
0.27
C19H40
Hexadecanenitrile
1.17
C16H31N
Methyl hexadecanoate
0.41
C17H34O2
38
Palmitic acid
2.97
CH3(CH2)14COOH
Oleanitrile
3.02
C18H33N
E-11-Hexadecenal
1.26
C16H30O
n-Heneicosane
0.48
C21H44
Methyl elaidate
1.17
C19H36O2
Octadecanenitrile
1.57
C18H35N
Oleic acid
44.30
C18H34O2
Stearic acid
33.66
C18H36O2
9-octadecenamide
2.50
C18H35NO
9-octadecenal, (Z)-
0.46
C18H34O
Nonadecanenitrile
0.43
C19H37N
2-phenyl-furo[B]benzopyran-
0.72
4(4H)-one
Here we can see that the main composition of karanja oil is oleic acid, stearic acid oleanitrile and
palmitic acid which are 44.30%, 33.66%, 3.02% and 2.97% respectively. These compounds
constitute almost 84% of the total mass.
3.7) SCANNING ELECTRON MICROSCOPY
Below are the scanning electron microscopic images of the neem char and that of karanja char.
The images are taken at magnification level of 80 and 200 which clearly shows that reasonable
amount of pores are present on the surfaces.
3.7.1) KARANJA char
39
Figure 17 SEM image of karanja char at 80 magnification
Figure 18 SEM image of karanja char 200 magnification
40
3.7.2) NEEM char
Figure 19 SEM of neem char at 200 magnification
Figure 20 SEM image of neem char at 80 magnification.
41
Pyrolysis temperature and heating rate influenced the size and shape of particle through a general
increase in size and proportion of voids and a decrease in cell wall thickness. The fast volatile
release during pyrolysis produces substantial internal overpressure and the coalescence a more
open structure. Therefore, SEM porosity increased with a pyrolysis temperature and increasing
heating rate.
42
CONCLUSION
43
CONCLUSION
The seeds used here are non-edible and hence they are perfect for biomass. It can also be
explained by the fact India do not produce enough edible oils which can be used for this
purpose.
Maximum yield of the karanja oil and neem oil are at 500°C and 475°C.
As the heating progresses the oil production increases at first and then after certain extent
it start to decrease.
Reaction time decreases as the pyrolysis temperature is increased but char decreases with
increase in pyrolysis temperature.
The fixed carbon increases in the char as most of volatile matter is driven away due to
pyrolysis. Also the volatile matter in seeds is good which accounts for the production of
fuel on pyrolysis.
The oil obtained has comparable calorific value to most of the fuel used in day to daylife
but it has comparable higher pour point , density and kinematic viscosity, so one can say
that transportation and piping of these fuels can be a tough task especially in cold areas.
Seeing the physical properties one can say that it is moderate grade fuel and can be used
as blends with other major fuels.
Neem oil consist of over forty compounds and Karanja oil over twenty compounds
functional groups such as alkanes, alkenes, alkynes, alcohols, ketones, aldehydes,
aromatics rings, amides, nitriles and nitro compounds.
44
The char of the respective seeds have good calorific value so they can be used as alternate
source of energy for heating and other purposes and they also have reasonable amount of
pores present on their surface.
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