Thesis on

CO-PYROLYSIS OF SPENT ENGINE OIL AND JUTE WITH

LIFE CYCLE ANALYSIS AND PARAMETRIC SENSITIVITY
ANALYSIS
Submitted by

NAMRATA T BISWAS
[Examination Roll No: M4CHE1512]
[Class Roll No: 001310302019]
[Registration No: 124712 of 2013-14]
Session: 2013-2015
Under the Guidance of

Prof. (Dr.) Ranjana Chowdhury

In the partial fulfilment for the award of the degree

Of
MASTER OF CHEMICAL ENGINEERING
DEPARTMENT OF CHEMICAL ENGINEERING
JADAVPUR UNIVERSITY, KOLKATA 700032

Declaration of Originality and Compliance of Academic Ethics

I hereby declare that this thesis contains literature survey and original
research work by the undersigned candidate, as part of her Master of
Chemical Engineering studies. All information in this document have
been obtained and presented in accordance with academic rules and
ethical conduct. I also declare that, as required by these rules and
conduct, I have fully cited and referenced all material and results that
are not original to this work.
Name: Namrata T Biswas

Exam Roll No.- M4CHE 15-12

Class Roll Number: 00131302019

Thesis Title: Co-pyrolysis of spent engine oil and jute with life cycle
analysis and parametric sensitivity analysis.

Signature with date:

CERTIFICATE
This is to certify that Ms. Namrata T Biswas, a final year student of
Master of Chemical Engineering (M.Che) Examination of Chemical
Engineering Department, Jadavpur University (Exam Roll- M4CHE 1512 ; Class Roll-; 00131302019;Registration No.- 124712 of 2013-14),
has completed theProject work, titled : Co-pyrolysis of spent engine
oil and jute with life cycle analysis and parametric sensitivity
analysis. under the guidanceof Prof. (Dr.) RanjanaChowdhury during
her Masters Curriculum. This workhas not been reported earlier
anywhere and can be approved for submission inpartial fulfillment of
the course work.

___________________________
Prof. (Dr.) RanjanaChowdhury
Project Supervisor, Professor,
Chemical Engineering Department,
Jadavpur University.

Forwarded by:

______________________________
Prof. (Dr.) Chandan Ghua
Department Head of and Professor
Technology
Chemical Engineering Department,
Jadavpur University.

_______________________________
Dean, Faculty of Engineering &
Jadavpur University

ACKNOWLEDGEMENT
I would like to express my immense gratitude to the Chemical Engineering Department of
Jadavpur University for assigning me the project entitled Co-pyrolysis of spent engine oil
and jute with life cycle analysis and parametric sensitivity analysis
I would like to express my heartiest gratitude to my supervisor Prof. (Dr.) Ranjana
Chowdhury of Chemical Engineering Department of Jadavpur University, Kolkata for
allowing me to complete this work under her elegant supervision and guidance.
I am grateful to Prof. (Dr.) Chandan Guha, Head of Department of Chemical Engineering
for providing me with all necessary facilities to carry out the work. I am also very much
grateful to research scholar Mrs.Aparna Sarkar, Mr Shiladitya Ghosh, Mr. Subhasis Das
and Mr. Biswajit Debnath of Chemical Engineering Department, for their constant help,
kind and heartily cooperation and incredible suggestions in completing my project.
My thanks to all technical lab assistants, library, the office staff members and
classmates of department of Chemical engineering for their hearty cooperation
during my project work of this thesis.
Finally, I would thank my parents Mr. K.C Biswas and Mrs Suvra Biswas and my brother
without their blessing and support I could not have completed this Master of Chemical
Engineering course.

Date

Namrata T Biswas

CONTENTS
Chapter 1

11-18

1 Introduction
1.1 Waste-to-energy or energy-from-waste
1.2

Co-Pyrolysis

Chapter 2

19-23

2. Literature survey
Chapter 3

24-25

3. Aims and objectives

Chapter 4

26-29

4.1 Material and methods:

4.2 Mechanism of the Co-Pyrolysis Process
Chapter 5

30-40

5.1 Theoretical Analysis

5.2. Kinetics of Secondary Cracking:
5.3. Mathematical Modelling of Pyrolyser:
5.4 Pyrolyser Model
Chapter 6

41-69

6. Results and discussions

6.1. SEM analysis:6..2 pH of tar :-

6..3 Primary Kinetics:

6.4 A, E calculation:
6.5 FTIR analysis of pyro oil
6.6 Life cycle analysis:
Chapter 7

71-72

7. Conclusions:
7.1

Future Prospectus

References

73

APPENDIX 1: Nomenclature

75

APPENDIX 2 : Calculation sheet

77

List of Figures
FIGURENO.

DESCRIPTION

PAGE NO

Fig. 1

U.S. Energy Consumption by Energy

Source 2014

Fig. 2

Renewable electricity generation by fuel

type in the Reference case, 2000-2040
(billion kilowatt hours)

Fig 3

Schematic of Co-Pyrolysis of Biomass

Fig 4

Spent engine oil and jute (raw materials)

17

Fig 5

Experimental Set up

19

Fig 6.

Product yield at 50% oil + jute

33

Fig 7

Product yield at 50%oil + jute

33

Fig 8

Product yield at 35%oil + jute

34

Fig 9

Product yield at 30% oil + jute

34

Fig 10

Product yield at 25 %oil + jute

35

Fig 11

Product yield at 1% oil + jute

35

Fig 12

Product yield at 2% oil + jute

36

Fig 13

Product yield at 3%oil + jute

36

Fig 14

Product yield at 4%oil + jute

37

Fig 15

Product yield at 5% oil + jute

37

Fig 16

Product yield at6% oil + jute

38

Fig 17

SEM images 900 C

40

Fig 18

SEM images 700 C

40

Fig 19

SEM images 500 C

40

Fig 20

Represents the %Wt loss of residue v/s Time 41

( 1%)

Fig 21

Represents the %Wt loss of residue v/s Time

( 2%)

Fig 23

: Represents the
Time ( 5%)

Fig 24

Represents the %Wt loss of residue v/s Time 43

( 6%)

Fig 25

Represents the %Wt loss of residue v/s Time 43

( 7%)

Fig 26

Represents the %Wt loss of residue v/s Time 44

( 9%)

42

%Wt loss of residue v/s 42

Fig 27

Represents the %Wt loss of residue v/s Time 44

( 20%)

Fig 28

Represents the %Wt loss of residue v/s Time 45

( 25%)

Fig 29

Represents the %Wt loss of residue v/s Time 45

( 35%)

FIG 30

Represents the %Wt loss of residue v/s Time 46

( 50%)

FIG 31& 32

FTIR graph

50,51

Fig 33

LCA Boundraies

54

Fig 34

Incineration

55

Fig 35

SENSITIVITY ANALYSIS

56

List of Tables

TABLE

DESCRIPTION

PG NO

Table 6.1

A, E calculation:

48,49

Table 6.2

FTIR ANALYSIS

52

Tab 6.a, 6.b, LCA calculations

6.c,6.d,6.e,6.f

10

57, 58,59

CHAPTER 1

11

1. INTRODUCTION
The sole concern in todays world is sustainable development and to preserve fossil
fuel and reduce its load by finding out alternative energy sources which have as high
efficiency as the fossil fuels and at the same time are environment friendly. The
decrease of fossil fuel resources such as coal, petroleum, and natural gas has
encouraged researchers to develop new approaches to find or invent renewable fuel.
According to an article the coal reserves will be available until at least 2112, and it
will be the sole fossil fuel in the world after 2042. In this regard, most of the effort
has been contributed by research into biomass energy. During the last three decades,
more than half of the global research has been focused on biomass as renewable
energy (56%), followed by solar energy (26%), followed by wind energy (11%),
geothermal energy (5%) and hydroelectric power (2%).[2] The high percentage of
research into biomass energy can be supported by the availability of biomass
resources which are the worlds largest sustainable energy source and represent
approximately 220 billion dry tons of annual primary production.[3]To minimize
environmental concerns, it is necessary to consider controlling the pollutant
emissions. The use of renewable energy resources can be an optional solution since
it significantly contributes to decreasing the negative environmental impacts,
reducing the dependence on the use of fossil fuels, and is followed by an increase of
net employment and the creation of export markets. There are numerous alternative
energy sources available worldwide which can be used to substitute fossil fuels.
In 2014, total renewable energy production and consumption reached record highs
of nearly 10 quadrillion Btu each. Hydroelectric power production in 2014 was
about 6% below the 50-year average, but increases in production from all other
renewable sources increased the overall total contribution of renewable energy.
Production of energy from wind and solar were at record highs in 2014 [Fig 1],

12

Fig. 1 U.S. Energy Consumption by Energy Source 2014

It is particularly important to consider selection of the proper alternative energy

through several factors such as the availability of the source, economic benefit, and
environmental benefit. In this respect, biomass is one of the potential sources that
fulfil the criteria of all these factors. Biomass is very abundant and can be easily
found in diverse forms such as agriculture residues, wood residues and municipal
solid waste. Furthermore, the use of biomass as an energy source has been proven to
have environmental benefits since it has been determined as a carbon-neutral energy
source. [4] Biomass is widely accepted as a potential source of energy and is the
only renewable energy source that can be converted into several types of fuels,
including liquid, char, and gas, which also promise flexibility in production and
marketing.
There is a growing need to develop the processes to produce renewable fuels and
chemicals due to the economic, political, and environmental concerns associated

with fossil fuels. The only economically sustainable source of renewable carbon is
the carbon fixed in biomass by photosynthesis. Lignocellulosic biomass is an
excellent renewable feedstock because it is both abundant and inexpensive. Several
routes are being studied to convert lignocellulosic biomass to fuels and chemicals
including fast pyrolysis, gasification \, catalytic fast pyrolysis\ , and aqueous phase
processing. The non-renewable resources are depleting as the demand of energy has
been exponentially increasing. An effort in development in technology for usage of
Renewable sources of energy .The energy comes from:

Solar energy: Solar energy is a resource that is not only sustainable

for energy consumption; it is indefinitely renewable (at least until the sun runs out in
billions of years). Solar power can be used to generate electricity; it is also used in
relatively simple technology to heat water (solar water heaters).

Wind energy: Advantages of Wind Power. It's a clean fuel source. Wind
energy doesn't pollute the air like power plants that rely on combustion of fossil
fuels, such as coal or natural gas. Wind turbines don't produce atmospheric
emissions that cause acid rain or greenhouse gasses.

Geo thermal energy:-Geothermal energy is heat energy that is stored within the
earth. It is the heat from the Earth. It's clean and sustainable. Resources of
geothermal energy range from the shallow ground to hot water and hot rock found a
few miles beneath the Earth's surface, and down even deeper to the extremely high
temperatures of molten rock called magma

Tidal

energy:

It

is

an

inexhaustible

source

of

energy.

Tidal energy is environment friendly energy and doesn't produce greenhouse

gases. As 71% of Earths surface is covered by water, there is scope to generate this
energy on largescale. The energy density of tidal energy is relatively higher than
other renewable energy sources.

Biomass is a renewable energy resource derived from the carbonaceous waste of

various human and natural activities. It is derived from numerous sources, including

14

the by-products from the timber industry, agricultural crops, raw material from the
forest, major parts of household waste and wood.

Fig. 2 Renewable electricity generation by fuel type in the Reference case, 2000-2040
(billion kilowatt hours)

1.1 Waste-to-energy or energy-from-waste

The process of generating energy in the form of electricity and/or heat from
the waste.There arevarious thermal andnon-thermaltechnologies present which are as
follows:
Thermal technologies:

Incineration: -A waste treatment technology, which includes the combustion of

waste for recovering of energy. Incineration coupled with high temperature waste
treatments are recognized as thermal treatments. During the process of incineration,
the waste material that is treated is converted in to IBM, gases, particles and heat.
These products are later used for generation of electricity. The gases, flue gases are
first treated for eradication of pollutants before going in to atmosphere.Incinerators

reduce the volume of the original waste by 95-96 %, depending upon composition
and degree of recovery of materials such as metals from the ash for recycling.

Gasification: It is a process that converts organic or fossil fuel based carbonaceous

materials into carbon monoxide, hydrogen and carbon dioxide. It produces
combustible gas, hydrogen, synthetic fuels.

Thermal depolymerization (TDP) is a depolymerisation process using hydrous

pyrolysis for the reduction of complex organic materials (usually waste products of
various sorts, often biomass and plastic) into light crude oil. Produces synthetic
crude oil, which can be further refined.

Plasma

arc

gasification or

plasma

gasification process

(PGP)

(produces

rich syngas including hydrogen and carbon monoxide usable for fuel cells or
generating electricity to drive the plasma arch, usable vitrified silicate and metal
ingots, salt and sulphur)
Non-thermal technologies:

Anaerobic digestion (Biogas rich in methane) is a series of biological processes in

which microorganisms break down biodegradable material in the absence of oxygen.
One of the end products is biogas, which is combusted to generate electricity and
heat, or can be processed into renewable natural gas and transportation fuels.

Fermentation (examples are ethanol, lactic acid, hydrogen)is a metabolic process

that converts sugar to acids, gases or alcohol. It occurs in yeast and bacteria, but also
in oxygen-starved muscle cells, as in the case oflactic acid fermentation.

1.2 Co-Pyrolysis:
Co-pyrolysis as a process is simple and effective way of developing a technique to produce
the ideal synthetic liquid fuel which might replace the conventional fuel. Co-pyrolysis is a
process which involves two or more different materials as a feedstock. Many studies have
shown that the co-pyrolysis of biomass has successfully improved the oil quantity and quality
without any improvement in the system process. Co-pyrolysis has shown promise for future
application in industry as it is highly cost effective.

16

The co-pyrolysis has gained popularity because of the synergistic effect which comes from
the reaction of different materials during the process. This synergetic effect between the
materials is the key behind the improved product yield. If these oils are mixed together, an
unstable mixture forms, which breaks (phase separation) after a short period of time. If
pyrolysis of biomass occurs independently or separately, more energy is required and the cost
for oil production will significantly increase. The co-pyrolysis technique is found to be more
reliable to produce homogenous pyrolysis oil than the blending oil method. The interaction of
radicals during the co-pyrolysis reaction can promote the formation of a stable pyrolysis oil
that avoids phase separation.

The main benefit of using co-pyrolysis method is the fact that the co-pyrolysis process uses
up waste material as the feedstock and this in turn reduces significantly the volume of waste.
It also has the added benefits of reducing the landfill needed for waste disposal, saving costs
for waste treatment, and solving a number of environmental problems. Since the disposal of
waste in landfills is undesirable, this method could be proposed as an alternative waste
management procedure for the future that will have a significant impact on waste reduction
and may enhance energy security. In addition, from an economic point of view, co-pyrolysis
has been found to be a promising option for a biomass conversion technique to produce
pyrolysis oil. Kuppens investigated the economic consequences of the synergetic effects of
flash co-pyrolysis. They concluded that the use of co-pyrolysis techniques is more profitable
than pyrolysis of biomass alone and that it also has potential for commercial development.

The oil (liquid fuel, tar) produced by the pyrolysis of biomass has potential for use as a
substitute for fossil fuels. However, the oil needs to be upgraded since it contains high levels
of oxygen around 35%-60% which causes low caloric value, corrosion problems, and
instability. Therefore despite being eco-friendly it has lower combustion efficiency than the
fossil fuels. To reduce the oxygen content in this liquid fuel is the primary concern.
Generally, upgrading the pyrolysis oil involves the addition of a catalyst (catalytic cracking),
solvent and large amount hydrogen (hydro-deoxygenation), which can cost more than the oil
itself. In this regard, the co-pyrolysis technique offers simplicity and effectiveness in order to

17

produce high grade pyrolysis oil. Catalytic cracking comes with its own set of problems like
the high production of coke during the process, adds to the running time of the process as the
catalyst is consumable and decrease the quality of the fuel obtained.

Overall, studies have shown that the use of co-pyrolysis is able to improve the characteristics
of pyrolysis oil, e.g. increase the oil yield, reduce the water content, and increase the caloric
value of oil. Besides, the use of this technique also contributed to reduce the production cost
and solve some issues on waste management.

Fig3.Schematic of Co-Pyrolysis of Biomass

18

CHAPTER 2

19

2.1 LITERATURE SURVEY

Lin et.al (2014) studied co-pyrolysis using raw materials like oil palm solid wastes
and paper sludge. The main objective of the research was to study the co-pyrolysis
thermal behaviour of oil-palm solid wastes, paper sludge and their respective blends
under N2 atmosphere at different heating rates via thermo-gravimetric. The
investigations were carried at a room temperature of 1000 C in N2 atmosphere. The
observation was that the synergistic interaction between oil palm solid and paper
sludge would improve thermo chemical pyrolysis reactivity of the blends at low
temperature. Thus the reactivity and the yield of the raw materials would increase at
lower temperatures.

Zhang et.al (2013) used pine sawdust and the sub-bituminous coal to study fast
pyrolysis and co-pyrolysis. The experiments were conducted in a free fall reactor
and the blending ratios used were 0, 0.25, 0.50, 0.75 and 1.00 (wt./wt.). The fast
pyrolysis occurred when the coal and/or biomass particles have fallen down through
the hot zone of the reactor which is at a steady state of the reactor temperature of
700 C. The volatiles were passed through the gassolid separator initially to
remove solid particles and further flowed through five condensers in series to
remove the condensable volatiles. In the case with char bed, the tar yield increases
significantly while the char yield decreases compared to the result without char bed.
The presence of char bed leads to a decrease in asphaltene content of co-pyrolysis
tar, thus improving the quality of tar.

Song et.al (2014) investigated the effects of pyrolysis temperature and blending
ratio on the yield and composition of pyrolysis products (gas, tar, and char).It was
observed that CO and CO2 were the main gases of pyrolysis under 400 C. The yield
of hydrogen increased with further increasing the co-pyrolysis temperature. In tar,
co-pyrolysis resulted in a decrease in concentrations of benzene, naphthalene and
hydrocarbons, while the phenols and guaiacols contents increased. FTIR results

20

showed that OH, aliphatic CH, CO, and CAO functional groups gradually
disappeared at high temperatures.

Ucar et al. (2014) studied the co-pyrolysis of Pine saw dust and Scrap tires ,the
experiments were performed at 500 C under an inert atmosphere which was
provided by the use of nitrogen gas in a fixed bed reactor.the reactor was heated
from ambient temperature to 500 C and held at this temperature for 1 h. The volatile
products were swept to the collection flasks by nitrogen gas.The gas products were
collected in a gas bag. The liquid and solid products were quantified separately. The
co-pyrolysis of PNS with ST led to increased bio-oil yields in comparison with
PNS-derived oil yields. Bio-oils from PNS/ST blends at different ratios contained
higher amounts of carbon and lower amounts of oxygen than that of the PNSderived oil. Bio-oils were upgraded with the addition of scrap tires into the biomass.
Taking into account the Study it was ocnclued that the copyrolysis of biomass with
scrap tires is a viable way to produce an upgrade of bio-oils and chars as well as
pyrolysis gases.

Li et al. (2014) investigated the co pyrolysis of Shenfu bituminous coal and rice
straw at temperature of 700C, 800C and 900C. It was observed that Tar and gas
yields increased with the increasing biomass ratio due to the high volatile matter in
Rice Straw. Char yields decrease with the increasing temperature. Gas yields
increase at a higher temperature. Because of the high volatile matter in rice straw,
the total gas volumes of the blends increase with the increase of biomass ratio.
Besides, with the increasing temperature, gas volume yields increase because of the
higher reaction rate and more completely de-volatilization effect. The main
components of co-pyrolysis tar are similar with their parents tar, while their
concentrations were different. The results show that at the higher temperature, tar
cracked and led to a higher gas yields.

21

S. Ro et.al (2014) worked to investigate both the energetics of co-pyrolyzing swine

solids with spent plastic mulch films (SPM) and the characteristics of its gas, liquid,
and solid by-products. Gas, liquid, and solid products from co-pyrolysis of swine
solids (SS) with spent plastic mulch films (SPM) at around 718 to 741 K were
analysed along with their thermal decomposition kinetics and energetics. The liquid
product was rich in hydrocarbon could have application in chemical industry.
Biochar yield from the mixed feedstock (2:1 SPM + SS) was about 28%; andin case
of SS alone exhibited a 39% biochar yield.

Soncini et al. (2012) subject of study was co pyrolysis of low rank coal and biomass.
This study provides the information that hydrogen donation from biomass promotes
non-additive tar production on rapid co-pyrolysis with low rank coals, additional
studies could provide further proof of this mechanism. In particular, analysis of
heavier tar compounds from co pyrolysis would shed some light on whether the
synergistic portion of the tar production does in fact originate with the coal
feedstock. Likewise, a detailed analysis of the resulting char structures may indicate
whether secondary char formation is reduced in co pyrolysis, as suggested by this
studys data. Finally, increasing pyrolysis pressures, increasing particle sizes, or
decreasing sweep gas flow rates may give a sense for the effect of tar cracking on the
overall co-pyrolysis product distributions, and suggest kinetic rates for these
reactions.

Li-gang et.al (2011) investigated the effects of feedstock on the co-pyrolysis of

biomass and coal were investigated in a free-fall reactor from 500 o C to 700 o C and
a biomass blending ratio from 0% to 100% . Results indicated that the type of
feedstock greatly influences the product yields and the CO2 reactivity of char from
the co-pyrolysis.

Aboyade et.al (2013) studied the slow heating co-pyrolysis of coal and agricultural
waste in a slow pressurized packed bed pyrolysis. Results showed that the yield and

22

composition of tar and other volatile products were mostly influenced by mix ratio,
while temperature and pressure had a low to negligible significance under the range
of conditions investigated.

23

CHAPTER 3

24

3. AIMS AND OBJECTIVES

The main aims and objectives of the project are as follows: To study the pyrolysis kinetics of individual feed stocks.
To study the kinetics of co-pyrolysis of jute & spent engine oil
To study the operation of hydrolyser (semi batch) under both isothermal & non
isothermal conditions.
To optimize or to minimize the oxygen content of pyro oil using pyrolysis
temperature and ratio of spent engine oil & jute as a parameter.
To conduct life cycle analysis for 1 ton /day co-pyrolysis plant operating under
optimum conditions of pyrolysis temperature & ratio of spent engine oil and jute
using different process schemes.

25

CHAPTER 4

26

4.1 MATERIAL AND METHODS

The raw materials used is jute and spent engine oil. Spent engine oil is typically
refers to as used motor oil that have been collected from oil changed workshops,
garages, & industry.1296kl/year spent engine oil in generated.Jute is an important
industry fiber. India produces about 110 tons of jute waste every year.

Fig 4 (a) & (b). Spent engine oil and jute (raw materials)

This project aims at converting waste jute material and the spent engine oil into
renewable source of energy by a thermo-chemical conversion. Among the lingocellulosic wastes generated in India jute contributes to a major part of it. Jute is used
extensively in almost all commodities from jute sacks for packaging to jute saris.
After utilization many of these jute sacks face disposal problem. Therefore suitable
waste to energy technology should be utilized to generate energy from waste jute
sacks. Pyrolysis is a thermal degradation process which may be utilized for the
generation of non-conventional energy resources from waste materials.
A lubricant (engine oil) can be defined as an oil products that separates the metal
parts of an engine, reduce friction and keep it clean

4.2 MECHANISM OF THE CO-PYROLYSIS PROCESS

The mechanisms of pyrolysis and co-pyrolysis are same except the fact that in copyrolysis instead of a single raw material, two or more raw materials are used as feed
together.There are three basic steps required for the co-pyrolysis process: preparation of
samples, co-pyrolysis, and condensation or collection of products. The feed stocks uses
are spent engine oil and jute. Prior to co-pyrolysis, the samples are dried the drying
process is performed in hot air oven.The process is carried out in a 50 mm diameter and
640 mm long stainless steel pyrolyser.. An inert atmosphere is obtained by purging N2
gas, at a rate of 0.833 L/min throughout the experiment to sweep the volatiles produced
during pyrolysis. The isothermal pyrolysis conditions were maintained by using a PID
temperature controller, (Honeywell DC-1040). Pyrolysis temperature was varied from
400 C to 900 C. To increase the yield of the products spent engine oil was added to the
waste jute material in various concentrations. The waste jute was blended with spent
engine oil (1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 20%, 25%, 30%, 35%, 40%,
45%, 50% of the jute taken) and the pyrolysis for the different blending rations were
done for 400, 500, 600, 700, 800 and 900. Heating rate was maintained at 10 oC/min.
After the desired temperature is attained the pyrolyser is placed in the furnace.The
volatile product, coming out from the reactor is directed to a condensing system,
consisting of a condenser and a Ice-bath assembly. The exit point of the pyrolyser is
connected with the condenser and the condenser is connected with the Ice-bath system.
15oC temperature is maintained in the condenser and 0 oC is maintained at the Ice-bath
system consists a series of U-Tube containers. The condensable volatiles are collected
from the condensing unit and non-condensable gaseous products are driven out. The
pyrolyser was hung by a S.S chain attached with a weighing machine for continuous
monitoring of the residual mass of solid in the pyrolyser. The pH of the condensates i.e.
the pyrolysis oil was obtained for all experimental runs. The morphological analysis of
raw sample and char samples obtained at 5000C and 7000C were also analysed using
Scanning Electron Microscope.

28

Mechanism of the co- pyrolysis:-

Reactant (Jute)

Char + Bio-Oil (tar) + Volatile Matter (gases)

Fig. 5: Experimental Set up

CHAPTER 5

30

5.1 THEORETICAL ANALYSIS

Pyrolysis of lingo-cellulosic materials ensues by the complex reactions in series, parallel or
combination of both. A simple model has been proposed by Bandyapadhay et al. (1999), all
the volatile products have been lumped to form a single product called volatiles and solid
products have been lumped to form char. The reaction pathway of pyrolysis has been given
below:

Following there assumptions and reaction model the kinetic study of pyrolysis of jute and
secondary cracking of bio- oil was done.
The following assumptions have been made for kinetic modeling:
i. The first step of the scheme, i.e. the Active complex formation is instantaneous. Thus, the
reaction is considered to be in equilibrium.
ii. All the reactions occurring in the scheme are of first order with respect to the solid
reactant.
iii. The solid residual obtained at infinite time, at any temperature in the pyrolysis zone is
entirely comprised of char.
iv. Solid residue obtained at any time other than t = is made up of unreacted solid reactant
and solid product char.
v. As the operation is a semi-batch one, the probability of occurrence of all the secondary
reactions has been assumed to be zero.
vi. Absolute inert atmosphere prevails during pyrolysis.

31

vii. Heat and mass transfer resistance in the samples may be negligible. This may be justified
by a very high specific surface area of the sample and very small size of the crucibles used.
viii. Any transport limitation within the experimental and the analytical part of the system
may be neglected. This has been done by proper designing of the system.

The weight loss profile of the solid reactant W with time may be given by:

dw
( kc k v )W
dt

(2)

kc kv k

(3)

Let,

Therefore,

dw
kW
dt

(4)

The profile of increase of weights of volatiles and char against time are given respectively by
the following expressions:

dwv
k vW k vWo exp kt
dt

(5)

dwc
k cW k cWo exp kt
dt

(6)

Equation (3), (4) and (5) have been solved analytically with the following initial conditions:

W t 0 W

(7)

Wv t 0 Wvo

(8)

32

Wc t 0 Wco

(9)

The solutions under isothermal conditions are as follows:

W t Wo exp kt

(10)

k
Wv t Wvo v Wo 1 exp kt
k

(11)

k
Wc t Wco c Wo 1 exp kt
k

(12)

The differentiation of solid reactant from char has been done using assumption (iii). Under
isothermal condition:

Wc t Wco kcW

W
t

v
vo

kvW

k c Wc t Wco

k v Wv t Wvo

(13)

However, according to the assumption (iii) :

Wc t Wr t and Wv t Wo Wr t

33

(14 & 15)

Therefore

Wc t Wco Wr t Wco

W
t

W
vo
v
Wo Wr t

(16)

W t Wco
Wc t Wco r
Wv t Wvo
W

W
t

r
o

(17)

The weight of the unreacted reactant at any time t is given by:

W t Wco
W t Wo Wv t Wvo 1 r

Wo Wr t

(18)

Regression analysis of Equation (7), (8) and (9) gives the values of the rate constants k, kv,
kc respectively, at different temperatures.

34

5.2. KINETICS OF SECONDARY CRACKING

The reaction pathway of the secondary cracking of primary pyro-oil of sesame oil cake is
almost same to the primary pyrolysis. The scheme is introduced below:

The weight loss profile of the solid reactant W with time may be given by:

dw
( k c k v )W
dt

Let,

(19)

kc kv k

(20)

Therefore,

dw
kW
dt

(21)

The profile of increase of weights of volatiles and char against time are given respectively by
the following expressions:

dwv
k vW
dt

(22)

35

dwc
k cW
dt

(23)

Equation (16), (17) and (18) have been solved analytically with the following initial
conditions:

W t 0 W
Wv t 0 Wvo
Wc t 0 Wco

(24)

The solutions under isothermal conditions are as follows:

W t Wo exp kt

(25)

k
Wv t Wvo v Wo 1 exp kt
k

(26)

k
Wc t Wco c Wo 1 exp kt
k

(27)

From the Arhenious law,

E
K A exp

RT

(28)

A= Frequency factor
E = Activation Energy
By integrating we get,

k
E
ln
RT
ko

(29)

36

ln k ln k o

E
RT

(30)

E
K v A exp

RT

(31)

k
E
ln v
RT
ko

(32)

E
RT

(33)

ln k v ln k o

E
K c A exp

RT

(34)

k
ln c
ko

(35)

RT

ln k c ln ko

E
RT

(36)

5.3. MATHEMATICAL MODELLING OF PYROLYSER

Based on the reaction kinetics determined in the previous section a mathematical model has
been developed to predict the gas phase composition of the pyrolysis products.

The mass balance equation for any volatile component i under dynamic condition is as
follows, where i = tar or CO or CO2 or H2 or CH4.

2 wvi

vi

vi
gi
2
t
z
z

n
rij
j 1

37

(37)

The term on the left hand side of the above equation represents accumulation, 1st , 2nd and
3rd terms on the right hand side of the equation represent convective flow component,
dispersive flow component and the reactive part consisting of reactions (j) of all types,
namely homogeneous and heterogeneous involving the component i . Among the volatile
components, namely tar, CO, CO2, H2 and CH4, tar generated from pyrolysis of jute a
heterogeneous reaction and is decomposed through a homogeneous tar cracking reaction. Tar
cracking reaction may be represented as follows:

Tar vCOCO vCO2 CO2 vH 2 H 2 vCH4 CH 4 viTarinert

(38)

All other gaseous components are only involved in the homogeneous tar cracking reaction.
The stoichio metric coefficients, vi, for different components are determined by following
(Boroson and Howard, 1989). The rate equation referred below for tar cracking reaction is
as follows.

The rate of formation of any product, j, through cracking of volatiles is given as follows,

93.97
rj .crack v j .104.98.exp
. Wg .tar g
RT
Par

Where Wg .tar g

(39)

is the concentration of tar in the gas phase.

All alkanes and alkenes have been lumped as methane . Stoichiometric coefficients have been
reported by (Boroson and Howard, 1989).

38

5.4 Pyrolyser Model

Mass balance equations for unreacted feed material, char and different gaseous components
in the pyrolyser have been developed with the following assumptions.
1. Reactor is operated under isothermal condition.
2. Cracking reaction of volatiles takes place only in the gas phase.
3. Gaseous molecules formed through cracking of volatiles do not interact among themselves.
Mass balance equations for different components under dynamic condition are as follows,

Solid phase
Unreacted Biomass

d
1 sW k 1 sW
dt

(39)

Char

d
1 sWc kc 1 sW
dt

(40)

Gas phase
Material balance equations for different gaseous components are as follows

2WT

WT vWT DT 2 kv sW rcrack
t
z
z

(41)

2WCO

WCO vWCO DCO 2 vCO rcrack

t
z
z

(42)

2WCO2

WCO2
vWCO2 DCO2
vCO2 rcrack
t
z
z 2

39

(43)

 2WCH 4

WCH 4
vWCH 4 DCH 4
vCH 4 rcrack
t
z
z 2

(44)

2WH 2

WH 2
vWH 2 DH 2
vH 2 rcrack
t
z
z 2

(45)

Equation 32 35 have been solved using the following boundary conditions,

At t=0

(46)

(47)

40

CHAPTER 6

41

6. RESULTS AND DISCUSSIONS

The co-pyrolysis experiments conducted at a temperature range of 673K to 1173K at varied
feed ratios for a duration of 60 minutes. The product obtained were solid residue called char,
condensable liquid product called tar and the non-condensable gas. Under the present
experimental the results showed a clear influence of ratio to spent engine oil in the feed the
pyro oil formation has increased.. The tar is obtained from the condensing unit; it was
investigated from the experiments that the yield of tar is maximum at 873K at the feed ratio
of 60:60.The plots given below shows the product yield i.e. char, tar and volatile matter
formation at temperature range of 300 C to 900 C. The plot shows the product yield of
products at different temperature and at different feed ratios. It has been observed that the
pyro-oil formation is maximum at 600 C; the char formation is maximum at 900C and the
volatile matter

maximum at 900C.The char yield decreased with a rise in pyrolysis

temperature 573K to 1173K. The increase in gaseous products may be due to the secondary
cracking of the pyrolysis vapours at higher temperature.

42

90

Product yield at 50% oil + jute

80
Product yield

70
60
50
40

CHAR

30

TAR

20

GAS

10
0
573

673

773

873

973

1073

1173

temperature (K)

Fig 6 Product yield at 50% oil + jute

PRODUCT YIELD
CHAR

TAR

Gas

PRODUCT FORMATION (%)

35
30
25
20
15
10
5
0
573

673

773

873

973

1073

TEMPERATURE (K)

Fig 7 Product yield at 35% oil + jute

43

1173

PRODUCT YIELD
PRODUCT FORMATION (%)

CHAR

TAR

Gas

45
40
35
30
25
20
15
10
5
0
573

673

773

873

973

1073

1173

TEMPERATURE (K)

Fig 8Product yield at 30% oil + jute

PRODUCT YIELD
PRODUCT FORMATION (%)

CHAR

TAR

Gas

45
40
35
30
25
20
15
10
5
0
573

673

773

873

973

1073

TEMPERATURE (K)

Fig 9Product yield at 25% oil + jute

44

1173

PRODUCT YIELD
PRODUCT FORMATION (%)

CHAR

TAR

Gas

35
30
25
20
15
10
5
0
573

673

773

873

973

1073

1173

TEMPERATURE (K)

Fig 10Product yield at 20% oil + jute

PRODUCT YIELD
PRODUCT FORMATION (%)

CHAR

TAR

Gas

35
30
25
20
15
10
5
0
573

673

773

873

973

1073

TEMPERATURE (K)

Fig 11Product yield at 1% oil + jute

45

1173

PRODUCT YIELD
TAR

Gas

50
40
30
20
10
0
573

673

773

873

973

1073

1173

TEMPERATURE (K)

Fig 12Product yield at 2% oil + jute

PRODUCT YIELD
CHAR

TAR

Gas

35
PRODUCT FORMATION (%)

PRODUCT FORMATION (%)

CHAR

30
25
20
15
10
5
0
573

673

773

873

973

1073

TEMPERATURE (K)

Fig 13Product yield at 3% oil + jute

46

1173

PRODUCT YIELD
CHAR

TAR

Gas

PRODUCT FORMATION (%)

30
25
20
15
10
5
0
573

673

773

873

973

1073

1173

TEMPERATURE (K)

Fig 14Product yield at 4% oil + jute

PRODUCT YIELD
PRODUCT FORMATION (%)

CHAR

TAR

Gas

30
25
20
15
10
5
0
573

673

773

873

973

1073

TEMPERATURE (K)

Fig 15Product yield at 5% oil + jute

47

1173

PRODUCT YIELD
PRODUCT FORMATION (%)

CHAR

TAR

Gas

45
40
35
30
25
20
15
10
5
0
573

673

773

873

973

1073

TEMPERATURE (K)

Fig 16Product yield at 6% oil + jute

48

1173

6.1.1 SEM ANALYSIS

Micrographs of SEM (Scanning Electron Microscope) analyses with magnification of 17KV
X 2000 of char after pyrolysis at the temperatures of 773K, 973K,1173k,) for 1 hour are
shown in the Figures17,18,and 19 are given below. Micrographs are examined to
characterize the shape and the size of the char particles, as well as their porous surface
structure.From a phenomenological point of view, a gradual release of different volatile
compounds occurs as the temperature increases during pyrolysis. It appears that at a
temperature of 900 C, the devolatilization is more intense making the char more porous.
Pyrolysis temperature influences the size and shape of particle through a general increase in
size and proportion of voids and a decreasing cell wall thickness.

49

Figure 17: SEM images 900o C

Figure 18: : SEM images 7000 C

Figure 19 :SEM images6000 C

6.1.2 pH of tar
The tar from the process are dark brown viscous liquid .The pH of tar was found to be basic
in nature.

pH vs Temperature (K)
7.25
7.2

ph

7.15
7.1
7.05
7
6.95
600

700

800

900

1000

1100

1200

Temperature (K)

Figure 20

6.1.3 Primary Kinetics:

% of wt. residue:
The weight of the tar at any instance of time at any temperature is calculated by weighing the
condensable part of the volatile obtained on the experiment. The amount of residue is
calculated from the expression below. The % of wt. residue has been plotted against time for
the different temperatures (673K-1173K).
W(t) = Wo (Wv(t) -Wvo)*[1+

It has been observed from the figures above that the weight of the residue has shown gradual
decrease with the increase in time.

Fig20: Represents the %Wt loss of residue v/s Time ( 1%)

Fig 21: Represents the %Wt loss of residue v/s Time ( 2%)

Fig 22 :Represents the % Wt loss of residue v/s Time ( 3%)

Fig 23:Represents the % Wt loss of residue v/s Time ( 5%)

Fig 24:Represents the %Wt loss of residue v/s Time ( 6%)

Fig 25:Represents the %Wt loss of residue v/s Time ( 7%)

Fig 26:Represents the %Wt loss of residue v/s Time ( 9%)

Fig 27: Represents the %Wt loss of residue v/s Time ( 20%)

Fig 28: Represents the %Wt loss of residue v/s Time ( 25%)

Fig 29: Represents the %Wt loss of residue v/s Time ( 35%)

Fig 30:Represents the %Wt loss of residue v/s Time ( 50%)

6.1.4 A, E calculation
Wv, Wc, % of wt. loss of the sample has been calculated from the experimental results. k, kv
kc at different pyrolysis temperature has been determined from the graph W/t or Wv/t
or Wc/t v/s Wtavg . In table 6.1: the values of natural logarithms of rate constants k, kv and
kc have been plotted against the inverse of temperature. From the nature of the plot, it is clear
that although the linear increase of ln k with 1/T is obtained up to 973K, beyond this
temperature range, the values of k falls below or little diverted from the straight line.
The Activation Energy (E) and Frequency factor (A) of k, kv and kc has been determined
from the experimental results, and shown in the table. Then compared the true k, kv and kc
determined from Arrhenius Equation with the experimental k, kv and kc.

Table: 6.1: Calculation of A and E

Sl no.

1.

2.

3.

4.

Feed ratio

Activation

Frequency

Correlation

(jute+ spent constant

Energy

factor A

Coefficient

engine oil)

E(KJ/mol))

(min -1)

6.3376

0.648

0.98

kv

4.664

0.106

0.88

kc

7.467

0.606

0.96

6.38

0.346

0.98

kv

4.976

0.164

0.82

kc

7.007

0.426

0.90

6.33

0.164

0.98

kv

4.66

0.096

0.89

kc

7.312

0.062

0.88

6.446

0.216

0.94

kv

4.432

0.136

0.86

kc

7.714

0.064

0.92

6.614

0.167

0.92

kv

4.611

0.087

0.86

kc

6.371

0.262

0.88

7.023

0.484

0.97

kv

8.776

0.126

0.87

kc

6.72

0.047

0.88

6.33

0.129

0.96

kv

4.76

0.116

0.86

kc

7.31

0.0136

0.88

6.21

0.262

0.90

kv

4.63

0.162

0.91

kc

7.27

0.017

0.88

6.32

0.332

0.97

kv

6.21

0.116

0.89

kc

7.02

0.013

0.81

1%

2%

3%

4%

6%

6%

7%

8%

9%

Reaction

58

10

11

12

13

14

16

16

17

18

10%

16%

20%

26%

30%

36%

40%

46%

60%

3.86

0.133

0.92

kv

3.76

0.112

0.87

kc

4.66

0.016

0.88

2.876

0.212

0.87

kv

3.66

0.364

0.86

kc

4.321

0.062

0.76

6.12

0.089

0.92

kv

6.32

0.148

0.94

kc

7.17

0.126

0.87

6.141

0.112

0.97

kv

7.42

0.076

0.89

kc

7.06

0.144

0.93

7.682

0.133

0.88

kv

6.33

0.074

0.91

kc

7.16

0.048

0.87

7.322

0.766

0.96

kv

6.316

0.328

0.97

kc

4.32

0.186

0.86

4.88

0.662

0.91

kv

6.61

0.019

0.97

kc

4.87

0.026

0.93

8.71

0.462

0.97

kv

7.76

0.016

0.87

kc

7.86

0.096

0.89

7.866

0.329

0.98

kv

3.717

0.116

0.81

kc

6.436

0.136

0.82

59

6.1.4 FTIR analysis of pyro oil

Characterization with respect to chemical bonds present in the pyro-oil has been done using
FTIR analysis. The functional groups of the pyro-oil obtained at temperature of 973k
(50;50)was analyzed by Fourier Transform Infrared (FTIR) spectroscopy to identify the basic
compositional groups shown in Fig 31

Fig 31: FTIR OF PYRO-OIL AT 700C (50% spent engine oil)

60

Fig 32 : FTIR OF PYRO-OIL AT 700C (50% spent engine oil)

61

Table 6.2: FTIR ANALYSIS RESULTS

62

6.1.5 Life Cycle Analysis

After pyrolysis process the pyrogas and pyro char are combusted on-site for heat applications.
The pyro oil is transported to a power plant and DG set, there it combusted for heat
generation. The ghg avoided for pyro oil, pyro char and pyro gas determined by using the
equations1,2,3,4, 5,6,7,8 and 9 given below..Two pyrolysis option that is pyrolysis plants
with utilization of pyro-gas and pyro-char for steam generation to supply energy for pyrolysis
and (1) in-house electricity generation from pyro-oil utilizing in DG set (2) pyro-oil used for
generation of electricity in power plant.

The heat requirement for drying has been calculated by using the following equation

Edrying M*[Ww{(cpw *T1) HV}(1Ww)*cps *T1 ]

(1)

The GHG emission for drying of sample has been calculated using this following
equation

CO2 dying Edrying,actual*[1/(PPE *DE *GCVC )]*(1/ MWc )*CNc *44.0

(2)

The energy requirement for pyrolysis experiment has been estimated by using the
following equation

Epy M(1Ww)Cps(Tpy Tds) M(1 w)H

63

(3)

Utilization of Pyro-Char, Pyro-Oil and Pyro-Gas in DG set

Utilization of pyro-oil in power plant

Fig 33: LCA Boundaries

The energy generated and GHG emission of combustion of pyro-char and oil have
been evaluated by using following equations

E pyro Char / pyro oil M * W pyro char / pyro oil

* GCV pyro char / pyro oil * E f

CO 2 pyro char / pyro oil M * [

* CN

W pyro char / pyro oil

MW

pyro char / pyro oil

64

( 4)

pyro char / pyro oil

] * 44 . 0

(5 )

The energy generated and GHG emission of combustion of pyro-gas has been evaluated by
using following equations

E Gas [( M * W
X

CO

2 Gas

CH

Gas

*(X

* GCV

M * W Gas
MW Gas

* (X

CO

* GCV
)] * E

CH

CO

CH

CO

) * 44 . 0

(6 )

(7 )

Incineration

Fig 34: Incineration

E feedstock M * GCV feedstock * E f

CO2 M / MWfeedstock * CN * 44

65

(8 )

(9)

Table 6.a, 6.b, 6.c, 6.d, 6.e, 6f. represents the calculation data sheet of the Energy required
and theCO2 emission of 100 ton/day pyrolysis plant .
The parametric sensitivity of the system has also been studied. It shows that as the distance
between the plant and feed store is varied the energy utilized and CO2 emissions are
increased. The system

INCINERATION

OPTION 2
OPTION 1

10

20

30

40

50

60

70

Fig. 35: Parametric Sensitivity Analysis

66

80

Calculation sheet
Table 6.a
M

C.V

DISTANCE E drying

44800

50

41700.68

100

40

100
100

100

CO2 dry

Etruck

115059.6822

E Gj

224000000

224

41700.68

179200000

179.2

30

41700.68

134400000

134.4

20

41700.68

89600000

89.6

Table 6.b
m

Ww

1-Ww

Cps

Tpy Tpy-Tds

1-w

Hv

Epyrolysis

CO2 ton

100 0.137

0.863 4.18

400

365 0.137 0.863 2257.9

326524.7 88.39023

100 0.137

0.863 4.18

500

465 0.137 0.863 2257.9

362598.1

100 0.137

0.863 4.18

600

565 0.137 0.863 2257.9

398671.5 107.9204

100 0.137

0.863 4.18

700

665 0.137 0.863 2257.9

434744.9 117.6854

100 0.137

0.863 4.18

800

765 0.137 0.863 2257.9

470818.3 127.4505

100 0.137

0.863 4.18

900

865 0.137 0.863 2257.9

506891.7 137.2156

98.1553

Table 6.c
M
100

Wp.o

gcv

18.7 17.9924

100

27.98

19.538

100

24.87

100
100

Ef

E p.o

Mw

0.3 10093.74
0.3

cnc
18

CO2

temp energy

0.426 1947.293

400 3028.121

0.455

2113.81

500 4920.059

16400.2

26.5

21.62

0.3 16130.68

24.02

0.478 2177.626

600 4839.205

23.02

28.45

0.3 19647.57

13.02

0.495 3850.811

700 5894.271

20.87

30.167

0.3 18887.56

20.87 0.51411 2262.084

800 5666.268

100 17.522

31.545

0.3 16581.94

18.3

67

0.5412 2280.043

900 4974.583

Table 6.d
M ton

W(Gas)

MW(Gas)

XCO

XCH4

CO2 gas

100

20.534

19.99

0.20621

0.04246

1123.924

100

17.511

16.78

0.223

0.04667

1238.238

100

26.3

26.01

0.2218

0.04568

1190.034

100

26.501

26.321

0.20598

0.04241

1100.39

100

24.412

23.982

0.22186

0.04568

1198.283

100

25.987

25.178

0.20621

0.0426

1129.94

Table 6.e
CV
ep.gas Ef

Coal

Mc

MOLES OF

CO2

CO2

avoid

%avoide

COAL

emmited

p.c

ed

d pp

27887.30
15321 71505
.6

.91

8000

8.938

19

238

31

0.004629 38

1170.

0.267

171

1263.

0.312

004

012

31.2012

1433.

0.302

30.2438

228

439

1533.

0.394

39.4296

33

297

1604.

0.399

39.9241

006

241

1680.

0.574

57.4737

975

737

26.7171

32464.20
17836 83241
.2

.55

8000

10.40

19

519

31

0.005388

27

31677.12
17403 81223
.77

.39

8000

10.15

19

292

31

0.005258

02

40962.99
22505 10503
.54

3.3

8000

13.12

19

917

31

0.006799

94

41528.11
22816 10648
.02

2.4

8000

32500 15167
.26

8.7

8000

13.31

19

029

31

18.95

19

59154.69

31 0.009819

82

984

0.006893

68

Table 6.f
%
cv
e po

Ef

10093.

74

0.1201

85

83

5295.7 4480

0.1182

03

08

6450.2 4480

0.1439

97

6200.7 4480

0.1384

56
16581.

0.0739

5384.1 4480

57
18887.

Mw of disel

68

68
19647.

Md

2
16130.

disel

3313.7 4480

74
16400.

moles

86

5443.8 4480

0.1215

94

52

%avoided dg

15

%avoided pp

CO2

CO2

avoide

avoide

emmited

p.o

d dg

0.0004

23373.93

1947.2

0.2142

21.426

43

92

93

66

65

0.0007

37977.73

2113.8

0.3586

35.863

17

39

92

0.0007

37353.61

2177.6

0.3517

35.175

08

87

26

99

0.0008

45497.63

3850.8

0.4164

41.646

62

23

11

68

82

0.0008

43737.68

2262.0

0.4147

41.475

29

36

84

56

0.0007

38398.60

2280.0

0.3611

36.118

28

21

43

86

56

167

167

167

167

167

167

% avoided

option 1

option2

21.42665

26.7171

45.6772

48.14375

72.3943

35.86392

31.2012

12.25663

67.06512

43.45783

35.17599

30.24389

18.4125

65.41988

48.65639

41.64682

39.42967

2.7412

81.07649

42.17087

41.4756

39.92411

9.7256

81.39971

49.64971

36.11856

57.47372

25.7164

93.59228

83.19012

69

CO2 inc.
25.3215

CHAPTER 7

70

7. Conclusions

In this study, jute and spent engine oil, wastes were co-pyrolysed in a semi batch
reactor in a temperature range of 300-900C. In case of jute and spent engine oil the
yields of bio-oil initially increased and then decreased, char yield decreased, the
gaseous yield decreased initially then increased with increase in temperature.

FTIR analysis of tar was also established and SEM images of char were also
obtained.

A mathematical modeling of the pyrolyser is developed in the present study.

Pyrolysis of bio-oil combusted to generate power, replacing fossil fuels as feedstock.

It can also be upgraded to yield chemicals and fuel products such as gasoline and
diesel .Combusting pyrolysis oil as a liquid biofuel to generate power can reduce the
climate changing greenhouse emissions significantly because the CO2 emission at the
pyrolysis oil combustion stage is considered carbon neutral as CO2 is sequestered
during feedstock growth. In this LCA study, life cycle GHG avoided were estimated
for power generation from pyrolysis oil combustion relative to fossil fuels
combustion, depending on the biomass.

71

7.1 Future Prospects

Biomass provides a clean, renewable source that could dramatically improve
the environment, economy and energy security.

The pyro-oil obtained in this study should be investigated how to use it in a

diesel engine in economically.

The product of secondary cracking can be further cracked following tertiary

cracking.

The future studies can be directed towards investigation on optimization of

the process by using catalyst .

72

REFERENCES:
1. Shafiee S, Topal E,When will fossil fuels reserves be diminished? Energy Policy: 2009;
37:181-9
2. Manzano-Augliaro F, Alcyde A, Montona PG, Zapata-Sierra A, Gil C Scientific
production of renewable energies worldwide: An overview. Renew Sust. Energy Rev
2013,18:134-43.
3. Moreira JXC, Global Biomass potential. Mitig Adapt Strat Global Change 2006;11:31333
4. Ahtikkoski A. Heikkila J, Alenius V, Economic Viability of using biomass energy from
young strands, 2008; 32:998-96
5. A review on co-pyrolysis of biomass: An optimal technique to obtain high grade
pyrolysis oil-Faisal Abnisa and Wahn Mohd Ashri Wan Daud
6. Martinez JD, Vesses A, Mastral AM: Co Pyrolysis of Waste scrap tires: upgrading of
liquid bio fuel, 2014:119-263-71
7. Onal E, Uzzul BB, Putun AE, Bio oil production via co-pyrolysis of almond shell as
biomass and high ensity polyethylene 2014,78:704-10.
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Assistance of Flash Co Pyrolysis of short rotation coppice and biopolymer waste polymer
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9. Gulian M, Faruiz K, Mar SR, Monique F, Jacques LD. Attrition free pyrolysis to form
bio oil and char. 2000;100:6069-75
10. Bridgewater AV, Meier D, Radlein D,. An overview of fast pyrolysis of biomass.
1999,30:1479-93
11. http://www.altenergy.org/renewables/solar.html
12. https://www.americanbiogascouncil.org/biogas_what.asp
13. http://en.wikipedia.org/wiki/Fermentation
14. Yucheng Cao , Life cycle assessment of two emerging sewage sludge-to-

energysystems:,Evaluating energy and greenhouse gas emissions implications,

BioresourceTechnology 127 (2013) 8191

73

15. Master Thesis Studies on production of liquid fuel from lignocellulosic wastes along

with life cycle analysis Rima Biswas 2014

16. Master thesis Studies on thermochemical conversion of lignocellulosics ---

experiments and modelling Biswarop Mondal 2013

74

APPENDIX 1
Ea = activation energy(kJ/mol)
A = frequency factor (min-1)
k = rate constant ( min-1)
kc = rate constant of char formation
kd = deactivation rate constant
kv = rate constant for volatile formation
R = rate constant
t = time (min)
T = temperature (K)
wc(t) = weight of char at any time during pyrolysis
w(t) = weight of solid reactant at any time during pyrolysis
wv(t) = weight of volatile at any time during pyrolysis
wr(t) = weight of residue
M = mass of the feedstock (ton)
Cpw

= water fraction in the feedstock (wt%)

Cpw = heat capacity of water (4.18 kJ/kg0C)

Cp = heat capacity of the feedstock kJ/(kg 0C)
T = difference between the temperature of the feedstock and drying
temperature (0C)

Hv = latent heat of vaporization of water (2257.9 kJ/kg),

75

E dyring= energy consumption for feedstock drying (GJ)

CO2 = ghg emission for drying (ton)
E pyrolysis= energy consumption for pyrolysis (GJ)
PPe = power plant efficiency (%)
De= DG set efficiency (%)
GCVc = Gross calorific value (MJ/kg)
Mwc = molecular weight
CNc = no of carbon
Xco = mole fraction of carbon monoxide
XcH4 = mole fraction of carbon-di -oxide

Subscripts

c = char
0 = initial condition
r = residue
v = volatile
t = Tar

Superscript:

o = Degree of temperature

76

APPENDIX 2

Calculation sheet:% wt
time

s wt

S+H+others

loss

Wv(t)

WR+WC

% WT RESIDUE

2235.2

2218.7

100

2218.5

2202

16.7

0.167

0.833

83.3

10

2202.4

2185.9

32.8

0.328

0.672

67.2

15

2192.6

2176.1

42.6

0.426

0.574

57.4

20

2186.8

2170.3

48.4

0.484

0.516

51.6

25

2182.3

2165.8

52.9

0.529

0.471

47.1

30

2180.1

2163.6

55.1

0.551

0.449

44.9

35

2174.1

2157.6

61.1

0.611

0.389

38.9

40

2169.3

2152.8

65.9

0.659

0.341

34.1

45

2162.2

2145.7

73

0.73

0.27

27

50

2161.3

2144.8

73.9

0.739

0.261

26.1

55

2157.1

2140.6

78.1

0.781

0.219

21.9

60

2153.3

2136.8

81.9

0.819

0.181

18.1

W0

100

S+H

WC(t)

W(t)

W(t)/t

Tavg

Wtavg

Wv(t)/t

Wc(t)/t

0.040781

2.5

0.898046

0.0334

0.007381441

0.036907

0.796093

0.039316

7.5

0.697802

0.0322

0.007116239

0.072488

0.599512

0.023932

12.5

0.539683

0.0196

0.004331624

0.094147

0.479853

0.014164

17.5

0.444444

0.0116

0.002563614

0.106965

0.409035

0.010989

22.5

0.381563

0.009

0.001989011

0.11691

0.35409

0.005372

27.5

0.340659

0.0044

0.000972405

0.121772

0.327228

0.014652

32.5

0.290598

0.012

0.002652015

0.135032

0.253968

0.011722

37.5

0.224664

0.0096

0.002121612

0.14564

0.19536

0.017338

42.5

0.152015

0.0142

0.003138217

77

0.161331

0.108669

0.002198

47.5

0.103175

0.0018

0.000397802

0.16332

0.09768

0.010256

52.5

0.072039

0.0084

0.00185641

0.172602

0.046398

0.00928

57.5

0.023199

0.0076

0.001679609

0.181

A,E calculation sheet

TK

1/T

ln K

Kv

ln Kv

573 0.001745

0.052

2.95651

Kc

ln Kc

0.039

3.24419

0.013

4.34281

673 0.001486

0.057

-2.8647

0.042

3.17009

0.015

4.19971

0.0436

-3.1327

0.024

-3.7297

0.024

-3.7297

773 0.001294

0.067

2.70306
-

873 0.001145

0.0719

2.63248

0.048

3.03655

973 0.001028

0.0785

2.54466

0.0527

2.94314

0.025

3.68888

1073 0.000932

0.085

-2.4651

0.058

2.84731

1173 0.000853

check k

Ktrue

0.0923

ln K

2.38271

0.027

3.61192

0.0651

Kv True

2.73183

ln Kv

0.027

Kc True

3.61192

ln Kc

0.052 2.125365833

0.753944

4.053624854 1.399612

4.368197

1.47435

0.057 2.508730728

0.919777

4.670536686 1.541274

4.368197

1.47435

0.0676 2.836876425

1.042704

5.187665665 1.646284

0.072 3.118862531

1.137468

5.625087021 1.727236

5.888551

1.77301

0.0777 3.362733701

1.212754

5.998738651 1.791549

6.529287

1.876298

0.085 3.575150753

1.274007

6.320981843 1.843875

7.101694

1.960333

1.324817

6.601376944 1.887278

7.614396

2.030041

0.0921

3.76149546

78

5.17065 1.642998

ln K, ln Kv, ln Kc

ln K, ln Kv, ln Kc vs 1/T
0
-0.5 0
-1
-1.5
-2
-2.5
-3
-3.5
-4
-4.5
-5

0.0005

0.001

0.0015

0.002

y = -645.4x - 1.867
R = 0.981

k
Kv
Kc

y = -880.1x - 2.778
R = 0.889
1/T

y = -547.1x - 2.352
R = 0.896

Calculation sheet:% wt loss of the residue vs time

573

673

773

873

973

1073

1173

300

400

500

600

700

800

900

5 8.166666667

7.288888889

7.454545455

8.75 19.62174941

16.7

12

14 10.84444444

16.09090909

15.5 37.23404255

32.8 20.77777778

15.2 24.27272727

22.25 50.70921986

42.6 31.88888889

28 55.55555556

48.4 43.77777778

10
15
20

21.25

25.5 21.24444444

25 28.91666667
30

27.28888889

55.54545455

32.16666667

70.21276596

52.9 52.33333333

32.25 29.95555556

65.18181818

42.16666667

77.30496454

55.1 63.22222222

33.6 69.90909091

50.83333333

82.15130024

61.1 70.44444444

73.36363636

57.16666667

90.66193853

65.9 77.11111111

40 77.27272727

67.41666667

91.4893617

73 84.11111111

35 34.58333333
40

38.72727273

38.75 37.15555556

45 42.91666667
50 45.41666667

42.31111111

82.36363636

71.66666667

93.14420804

73.9 89.33333333

55 47.33333333

44.17777778

86.45454545

77.58333333

95.50827423

78.1 96.55555556

46.4 92.36363636

82.58333333

96.3356974

81.9 98.22222222

60

49.25

79