co-pyrolysis of spent engine oil

1

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

2

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:

3

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 15-

12 ; 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 Dean, Faculty of Engineering & Technology Chemical Engineering Department, Jadavpur University Jadavpur University.

4

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

5

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

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

7

List of Figures

FIGURENO. DESCRIPTION PAGE NO

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

3

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

5

Fig 3 Schematic of Co-Pyrolysis of Biomass 8

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 9 Product yield at 30% oil + jute 34

Fig 10 Product yield at 25 %oil + jute 35



8




Fig 16 Product yield at6% oil + jute 38

Fig 17 SEM images 900 C 40



Fig 20 Represents the %Wt loss of residue v/s Time ( 1%)

41


42

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

42


43


43


44

9


44


45


45

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

46

FIG 31& 32 FTIR graph 50,51

Fig 33 LCA Boundraies 54

Fig 34 Incineration 55

Fig 35 SENSITIVITY ANALYSIS 56

10

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

LCA calculations 57, 58,59

11

CHAPTER 1

12

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],

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

14

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

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

16

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.

17

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

18

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

19

CHAPTER 2

20

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

21

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 PNS-

derived 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.

22

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 500o 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

23

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.

24

CHAPTER 3

25

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.

26

CHAPTER 4

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 lingo-

cellulosic 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

28

4.2 MECHANISM OF THE CO-PYROLYSIS PROCESS

The mechanisms of pyrolysis and co-pyrolysis are same except the fact that in co-

pyrolysis 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 10oC/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 0oC 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.

Mechanism of the co- pyrolysis:-

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

Fig. 5: Experimental Set up

30

CHAPTER 5

31

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.

32

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:

( )c vdw k k Wdt

(2)

Let, c vk k k (3)

Therefore,

dw kWdt

(4)

The profile of increase of weights of volatiles and char against time are given respectively by

the following expressions:

expv v v odw k W k W ktdt

(5)

expc c c odw k W k W ktdt

(6)

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

0W t W (7)

0v voW t W (8)

33

0c coW t W (9)

The solutions under isothermal conditions are as follows:

expoW t W kt (10)

1 expvv vo okW t W W ktk

(11)

1 expcc co okW t W W ktk

(12)

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

isothermal condition:

c co c

v vo v

W t W k WW t W k W

c

v

kk

c co

v vo

W t WW t W

(13)

However, according to the assumption (iii) :

c rW t W t and v o rW t W W t (14 & 15)

34

Therefore

c co r co

v vo o r

W t W W t WW t W W W t

(16)

r coc co v voo r

W t WW t W W t W

W W t

(17)

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

1 r coo v vo

o r

W t WW t W W t W

W W t

(18)

Regression analysis of Equation (7), (8) and (9) gives the values of the rate constants k, kv,

kc respectively, at different temperatures.

35

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:

( )c vdw k k Wdt

(19)

Let, c vk k k (20)

Therefore,

dw kWdt

(21)

The profile of increase of weights of volatiles and char against time are given respectively by

the following expressions:

vv

dw k Wdt

(22)

36

cc

dw k Wdt

(23)

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

conditions:

0W t W

0v voW t W

0c coW t W (24)

The solutions under isothermal conditions are as follows:

expoW t W kt (25)

1 expvv vo okW t W W ktk

(26)

1 expcc co okW t W W ktk

(27)

From the Arhenious law,

exp EK ART

(28)

A= Frequency factor

E = Activation Energy

By integrating we get,

lno

k Ek RT

(29)

37

ln ln oEk k

RT

(30)

expvEK A

RT

(31)

ln vo

k Ek RT

(32)

ln lnv oEk k

RT

(33)

expcEK A

RT

(34)

ln co

k Ek RT

(35)

ln lnc oEk k

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

21

nvi

vi vi gi ijj

ww v w D rt z z

(37)

38

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:

2 2 42 2 4CO CO H CH i inertTar v CO v CO v H v CH vTar

(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,

4.98. .93.97.10 .exp .j crack j g tar gPar

r v WRT

(39)

Where .g tar gW 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).

39

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

1 1s sd W k Wdt

(39)

Char

1 1s c c sd W k Wdt

(40)

Gas phase

Material balance equations for different gaseous components are as follows

2

2T

T T T v s crackWW v W D k W r

t z z

(41)

2

2CO

CO CO CO CO crackWW v W D v r

t z z

(42)

22 2 2 22

2CO

CO CO CO CO crack

WW v W D v r

t z z

(43)

40

44 4 4 42

2CH

CH CH CH CH crack

WW v W D v r

t z z

(44)

22 2 2 22

2H

H H H H crack

WW v W D v r

t z z

(45)

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

At t=0

(46)

(47)

41

CHAPTER 6

42

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.

43

Fig 6 Product yield at 50% oil + jute

Fig 7 Product yield at 35% oil + jute

0

5

10

15

20

25

30

35

573 673 773 873 973 1073 1173

PRO

DU

CT F

OR

MA

TIO

N (%

)

TEMPERATURE (K)

PRODUCT YIELD CHAR TAR Gas

0

10

20

30

40

50

60

70

80

90

573 673 773 873 973 1073 1173

Prod

uct

yiel

d

temperature (K)

Product yield at 50% oil + jute

CHAR

TAR

GAS

44

Fig 8Product yield at 30% oil + jute


05

1015202530354045

573 673 773 873 973 1073 1173

PRO

DU

CT F

OR

MA

TIO

N (%

)

TEMPERATURE (K)


05

1015202530354045

573 673 773 873 973 1073 1173

PRO

DU

CT F

ORM

ATI

ON

(%)

TEMPERATURE (K)


45



0

5

10

15

20

25

30

35

573 673 773 873 973 1073 1173

PRO

DU

CT F

ORM

ATI

ON

(%)

TEMPERATURE (K)


0

5

10

15

20

25

30

35

573 673 773 873 973 1073 1173

PRO

DU

CT F

ORM

ATI

ON

(%)

TEMPERATURE (K)


46



0

10

20

30

40

50

573 673 773 873 973 1073 1173

PRO

DU

CT F

OR

MA

TIO

N (%

)

TEMPERATURE (K)


0

5

10

15

20

25

30

35

573 673 773 873 973 1073 1173

PRO

DU

CT F

ORM

ATI

ON

(%)

TEMPERATURE (K)


47



0

5

10

15

20

25

30

573 673 773 873 973 1073 1173

PRO

DU

CT F

ORM

ATI

ON

(%)

TEMPERATURE (K)


0

5

10

15

20

25

30

573 673 773 873 973 1073 1173

PRO

DU

CT F

ORM

ATI

ON

(%)

TEMPERATURE (K)


48


05

1015202530354045

573 673 773 873 973 1073 1173

PRO

DU

CT F

OR

MA

TIO

N (%

)

TEMPERATURE (K)


49

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.

Figure 18: : SEM images 7000 C

Figure 19 :SEM images6000 C

Figure 17: SEM images 900o 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.

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.

6.95

7

7.05

7.1

7.15

7.2

7.25

600 700 800 900 1000 1100 1200

ph

Temperature (K)

pH vs Temperature (K)

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%)



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.

58

Table: 6.1: Calculation of A and E

Sl no. Feed ratio

(jute+ spent

engine oil)

Reaction

constant

Activation

Energy

E(KJ/mol))

Frequency

factor A

(min -1)

Correlation

Coefficient

1. 1% k

kv kc

6.3376

4.664

7.467

0.648

0.106

0.606

0.98

0.88

0.96

2. 2% k

kv kc

6.38

4.976

7.007

0.346

0.164

0.426

0.98

0.82

0.90

3. 3% k

kv kc

6.33

4.66

7.312

0.164

0.096

0.062

0.98

0.89

0.88

4. 4% k

kv kc

6.446

4.432

7.714

0.216

0.136

0.064

0.94

0.86

0.92

6 6%

k

kv kc

6.614

4.611

6.371

0.167

0.087

0.262

0.92

0.86

0.88

6 6% k

kv kc

7.023

8.776

6.72

0.484

0.126

0.047

0.97

0.87

0.88

7 7% k

kv kc

6.33

4.76

7.31

0.129

0.116

0.0136

0.96

0.86

0.88

8 8% k

kv kc

6.21

4.63

7.27

0.262

0.162

0.017

0.90

0.91

0.88

9 9% k

kv kc

6.32

6.21

7.02

0.332

0.116

0.013

0.97

0.89

0.81

59

10 10% k

kv kc

3.86

3.76

4.66

0.133

0.112

0.016

0.92

0.87

0.88

11 16% k

kv kc

2.876

3.66

4.321

0.212

0.364

0.062

0.87

0.86

0.76

12 20% k

kv kc

6.12

6.32

7.17

0.089

0.148

0.126

0.92

0.94

0.87

13 26% k

kv kc

6.141

7.42

7.06

0.112

0.076

0.144

0.97

0.89

0.93

14 30% k

kv kc

7.682

6.33

7.16

0.133

0.074

0.048

0.88

0.91

0.87

16 36% k

kv kc

7.322

6.316

4.32

0.766

0.328

0.186

0.96

0.97

0.86

16 40% k

kv kc

4.88

6.61

4.87

0.662

0.019

0.026

0.91

0.97

0.93

17 46% k

kv kc

8.71

7.76

7.86

0.462

0.016

0.096

0.97

0.87

0.89

18 60% k

kv kc

7.866

3.717

6.436

0.329

0.116

0.136

0.98

0.81

0.82

60

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)

61

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

62

Table 6.2: FTIR ANALYSIS RESULTS

63

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

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

equation

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

following equation

)1(]**)1(})*{([* 11 TcpWHTcpWME swVwwdrying

)2(0.44**)/1(*)]**/(1[*,2 ccCEEactualdryingdying CNMWGCVDPPECO

)3()1()()1( HwMTTCWME dspypswpy

64

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

)4(**

*

/

//

foilpyrocharpyro

oilpyrocharpyrooilpyroCharpyro

EGCVWME

)5(0.44*]*

[*

/

/

//2

oilpyrocharpyro

oilpyrocharpyro

oilpyrocharpyrooilpyrocharpyro

CNMWW

MCO

65

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

using following equations

Incineration

Fig 34: Incineration

)6(*)]**(**[(

44 fCHCH

COCOGasGas

EGCVXGCVXWME

)7(0.44*)(**42 CHCO

Gas

GasGas XXMW

WMCO

)8(** ffeedstockfeedstock EGCVME

)9(44**/2 Nfeedstock CMWMCO

66

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

Fig. 35: Parametric Sensitivity Analysis

0 10 20 30 40 50 60 70 80

1INCINERATION

OPTION 2

OPTION 1

67

Calculation sheet

Table 6.a

M C.V DISTANCE E drying CO2 dry Etruck E Gj

100

100

100

100

44800 50 41700.68 115059.6822 224000000 224

40 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 w 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 98.1553

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

Table 6.c

M Wp.o gcv Ef E p.o Mw cnc CO2 temp energy

100 18.7 17.9924 0.3 10093.74 18 0.426 1947.293 400 3028.121

100 27.98 19.538 0.3 16400.2 26.5 0.455 2113.81 500 4920.059

100 24.87 21.62 0.3 16130.68 24.02 0.478 2177.626 600 4839.205

100 23.02 28.45 0.3 19647.57 13.02 0.495 3850.811 700 5894.271

100 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 0.5412 2280.043 900 4974.583

68

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

ep.gas Ef

CV

Coal Mc

M

w

MOLES OF

COAL

CO2

emmited

CO2 p.c

avoid

ed

%avoide

d pp

15321

.6

71505

.91 8000

8.938

238

19

31

0.004629

27887.30

38

1170.

2

0.267

171 26.7171

17836

.2

83241

.55 8000

10.40

519

19

31

0.005388

32464.20

27

1263.

004

0.312

012 31.2012

17403

.77

81223

.39 8000

10.15

292

19

31

0.005258

31677.12

02

1433.

228

0.302

439

30.2438

9

22505

.54

10503

3.3 8000

13.12

917

19

31

0.006799

40962.99

94

1533.

33

0.394

297

39.4296

7

22816

.02

10648

2.4 8000

13.31

029

19

31

0.006893

41528.11

7

1604.

006

0.399

241

39.9241

1

32500

.26

15167

8.7 8000

18.95

984

19

31 0.009819

59154.69

82

1680.

975

0.574

737

57.4737

2

69

Table 6.f

e po Ef

cv

disel Md Mw

moles

of disel

CO2

emmited

CO2

p.o

avoide

d

%

avoide

d dg

10093.

74

3313.7

74

4480

0

0.0739

68 167

0.0004

43

23373.93

92

1947.2

93

0.2142

66

21.426

65

16400.

2

5384.1

85

4480

0

0.1201

83 167

0.0007

2

37977.73

17

2113.8

1

0.3586

39

35.863

92

16130.

68

5295.7

03

4480

0

0.1182

08 167

0.0007

08

37353.61

87

2177.6

26

0.3517

6

35.175

99

19647.

57

6450.2

97

4480

0

0.1439

8 167

0.0008

62

45497.63

23

3850.8

11

0.4164

68

41.646

82

18887.

56

6200.7

86

4480

0

0.1384

1 167

0.0008

29

43737.68

36

2262.0

84

0.4147

56

41.475

6

16581.

94

5443.8

52

4480

0

0.1215

15 167

0.0007

28

38398.60

21

2280.0

43

0.3611

86

36.118

56

%avoided dg %avoided pp % avoided option 1 option2 CO2 inc.

21.42665 26.7171 45.6772 48.14375 72.3943 25.3215

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

70

CHAPTER 7

71

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.

72

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 .

73

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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;11:313-

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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

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biomass and high ensity polyethylene 2014,78:704-10.

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bio oil and char. 2000;100:6069-75

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75

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),

76

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

77

APPENDIX 2

Calculation sheet:-

time s wt S+H+others S+H

% wt

loss Wv(t) WR+WC % WT RESIDUE

0 100 2235.2 2218.7 0 0 0 100

5 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 WC(t) W(t) W(t)/t Tavg Wtavg Wv(t)/t Wc(t)/t

1 0 1 0.040781 2.5 0.898046 0.0334 0.007381441

1 0.036907 0.796093 0.039316 7.5 0.697802 0.0322 0.007116239

1 0.072488 0.599512 0.023932 12.5 0.539683 0.0196 0.004331624

1 0.094147 0.479853 0.014164 17.5 0.444444 0.0116 0.002563614

1 0.106965 0.409035 0.010989 22.5 0.381563 0.009 0.001989011

1 0.11691 0.35409 0.005372 27.5 0.340659 0.0044 0.000972405

1 0.121772 0.327228 0.014652 32.5 0.290598 0.012 0.002652015

1 0.135032 0.253968 0.011722 37.5 0.224664 0.0096 0.002121612

1 0.14564 0.19536 0.017338 42.5 0.152015 0.0142 0.003138217

78

1 0.161331 0.108669 0.002198 47.5 0.103175 0.0018 0.000397802

1 0.16332 0.09768 0.010256 52.5 0.072039 0.0084 0.00185641

1 0.172602 0.046398 0.00928 57.5 0.023199 0.0076 0.001679609

1 0.181 0

A,E calculation sheet

T K 1/T K ln K Kv ln Kv Kc ln Kc

573 0.001745 0.052

-

2.95651 0.039

-

3.24419 0.013

-

4.34281

673 0.001486 0.057 -2.8647 0.042

-

3.17009 0.015

-

4.19971

773 0.001294 0.067

-

2.70306 0.0436 -3.1327 0.024 -3.7297

873 0.001145 0.0719

-

2.63248 0.048

-

3.03655 0.024 -3.7297

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 0.027

-

3.61192

1173 0.000853 0.0923

-

2.38271 0.0651

-

2.73183 0.027

-

3.61192

check k Ktrue ln K Kv True ln Kv Kc True 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 5.17065 1.642998

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

0.0921 3.76149546 1.324817 6.601376944 1.887278 7.614396 2.030041

79

Calculation sheet:-

% wt loss of the residue vs time

573 673 773 873 973 1073 1173

300 400 500 600 700 800 900

0 0 0 0 0 0 0 0

5 8.166666667 7.288888889 7.454545455 8.75 19.62174941 16.7 12

10 14 10.84444444 16.09090909 15.5 37.23404255 32.8 20.77777778

15 21.25 15.2 24.27272727 22.25 50.70921986 42.6 31.88888889

20 25.5 21.24444444 38.72727273 28 55.55555556 48.4 43.77777778

25 28.91666667 27.28888889 55.54545455 32.16666667 70.21276596 52.9 52.33333333

30 32.25 29.95555556 65.18181818 42.16666667 77.30496454 55.1 63.22222222

35 34.58333333 33.6 69.90909091 50.83333333 82.15130024 61.1 70.44444444

40 38.75 37.15555556 73.36363636 57.16666667 90.66193853 65.9 77.11111111

45 42.91666667 40 77.27272727 67.41666667 91.4893617 73 84.11111111

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

60 49.25 46.4 92.36363636 82.58333333 96.3356974 81.9 98.22222222

y = -645.4x - 1.867R = 0.981

y = -547.1x - 2.352R = 0.896

y = -880.1x - 2.778R = 0.889-5

-4.5

-4

-3.5

-3

-2.5

-2

-1.5

-1

-0.5

0

0 0.0005 0.001 0.0015 0.002

ln K

, ln

Kv, l

n Kc

1/T

ln K, ln Kv, ln Kc vs 1/T

k

Kv

Kc

co-pyrolysis of spent engine oil

Documents

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life cycle analysis

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