INVESTIGATION OF NEW METHODS FOR THE CONVERSION OF …

INVESTIGATION OF NEW METHODS FOR THE

CONVERSION OF BIOMASS IN TO USEFUL FUEL AND

HYDROCARBONS

By

KHADIM HUSSAIN

A dissertation submitted in Partial fulfillment of the requirement for the

degree of

Doctor of Philosophy

in

Chemistry

DEPARTMENT OF CHEMISTRY HAZARA UNIVERSITY

MANSEHR

ii

iii

Author’s Declaration

I Mr. Khadim Hussain hereby state that my PhD thesis titled ―Investigation of new methods for

the conversion of biomass into useful Fuel and hydrocarbons.‖ is my own work and has not been

submitted previously by me for taking any degree from this University ―Hazara University

Mansehra‖ or anywhere else in the country/world.

At any time if my statement is found to be incorrect even after my Graduate the university has

the right to withdraw my PhD degree.

Signature:

Author’s Name: Khadim Hussain

Date-14-05 -2018

iv

Plagiarism Undertaking

I solemnly declare that research work presented in the thesis titled ―Investigation of new methods

for the conversion of biomass into useful Fuel and hydrocarbons.‖ is solely my research work

with no significant contribution from any other person. Small contribution/help wherever taken

has been duly acknowledged and that complete thesis has been written by me.

I understand the zero tolerance policy of the HEC and university ―Hazara University Mansehra‖

towards plagiarism.

Therefore I as Author of the above titled thesis declare that no portion of my thesis has been

plagiarized and any material used as reference is properly referred/cited.

I undertake that if I am found guilty of any formal plagiarism in the above titled thesis even after

award of PhD degree, the University reserves the rights to withdraw/revoke my PhD degree and

that HEC and the University has right to publish my name on the HEC/University Website on

which names of students are placed who submitted plagiarized thesis.

Author Signature:

Name: Khadim Hussain

v

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ACKNOWLEDGEMENTS

It is a great honor for me to express sincere gratitude to my supervisor Dr. Nadia Bashir

Associate Professor Department of Chemistry Hazara University Mansehra Pakistan. Her

invaluable guidance and thought provoking attitude resulted in my curiosity for research. Her

preserved supervision nourished my confidence, prepared for hard work and gave a sense of

devotion to the cause. Dr.Mohsan Nawaz Chairman Department of Chemistry Hazara

University did more than kindness in materializing this work. He provided all the possible

facilities needed for this work. I am also indebted to Dr Hussain Gulab Associate Professor and

Dr. khaild Saeed Chairman Department of Chemistry Bacha Khan University Charsadda for his

help and cooperation in the analysis of the samples and some other related experiments. Thanks

are also due to Professor Dr. Zahid Hussain Department of Department of Chemistry Abdul

Wali Khan University Mardan for help in designing and customization of Microwave device and

his theoretical input. I am also thankful to my younger brother Mr, Sadam Hussain M. phil

Scholar Department of Electronics Quaid –i-Azam International University Islamabad for help in

the modification of microwave oven for this work. Last but not the least I am thankful to my

Father who is the real architect of my career. He did his best for all these .His support and

encouragement enabled me to do so. The dream of my late mother became true with the

completion of this work. Her soul will be very happy because she is around us in our dreams

heart and all ours.

Khadim Hussain

viii

ABSTRACT

New methods for the liquefaction of Biomass were investigated and explored. These methods are

based on the heat produced by microwave metal interaction. It utilizes microwave energy for the

decomposition of biomass. The metal acts as antenna as well as heat generating medium. In this

work three metals were used as the antenna. These are iron, copper and aluminium. The effect of

the shape of antenna on the yield and efficiency of the process were investigated. Biomass was

pyrolysed in all these antennas containing reactors in the microwave oven. These reactions were

carried out both in the presence and absence of catalyst. Three types of catalysts i.e. Cement,

kaolin and clinkered were used. These catalysts were intended to increase the yield and facilitate

the pyrolysis process. The use of these catalysts also reduces consumption of energy. Each of the

catalyst was used in different metal antenna in separate experiments. The amount of each of

catalyst was optimized in the range of 1:1-1:10 ratio for obtaining maximum yield and

conversion. The results for the process were found according to the predictions. In each case

biomass was converted into aqueous and oily liquids, gases and char like residue by the

microwave metal interaction pyrolysis. The volatile products were collected in cold traps while

the amount of gases was determined by difference. The oily product of the pyrolysis was

analysed using GC/MS and some chemical tests. It was observed that the nature of active species

of the pyrolysis determines the nature of products and these itself depends upon the microwave

flux and heat generated in addition to the activity of catalyst as well as catalytic activity of the

metals.

ix

List of publications

The thesis is based on work reported in the following papers, referred by Roman numerals in the

text.

i. Z. Hussain, N. Bashir, M. I. Khan, K. Hussain, S. A. Sulaiman, M. Y. Naz, K. A.

Ibrahim, and N. M. AbdEl-Salam Production of Highly Upgraded Bio-oils through Two-

Step Catalytic Pyrolysis of Water HyacinthEnergy Fuels, 2017, 31 (11), pp 12100–12107

Other Publications

i. Khadim Hussain, Zahid Hussain, Hussain Gulab, Fazal Mabood, Khalid Mohammad

Khan, Shahnaz Perveen and Mohammad Hassan Bin Khalid (2016). Production of fuel

by co-pyrolysis of Makarwal coal and waste polypropylene through a hybrid heating

system of convection and microwaves. International journal of Energy Research. 40 No

11, S 1532–1540.

ii. Hussain Gulab, Khadim Hussain, Shahi Malik, Zahid Hussain, Zarbad Shah (2016).

Catalytic co‐pyrolysis of Eischhornia Crassipes biomaѕѕ and polyethylene using waste Fe

and CaCO3 catalysts. International Journal of Energy. 40, No 7, 940–951.

iii. Fazal Mabood, Zahid Hussain, H. Haq, M. B. Arian, R. Boqué, K. M. Khan,

iv. Gulab, Hussain; Jan, Fazal Akbar; Hussain, Khadim; Khan, M. Tahir; Hussain, Syed

Hamid(2015) A case study evaluating water and salts removal capabilities of different

brands of commercially available demulsifiers from slope oil emulsions. Academic

Journal Petroleum & Coal; Vol. 57 Issue 5, p470

http://pubs.acs.org/author/Hussain%2C+Z

http://pubs.acs.org/author/Bashir%2C+N

http://pubs.acs.org/author/Khan%2C+M+I

http://pubs.acs.org/author/Hussain%2C+K

http://pubs.acs.org/author/Sulaiman%2C+S+A

http://pubs.acs.org/author/Naz%2C+M+Y

http://pubs.acs.org/author/Ibrahim%2C+K+A



http://pubs.acs.org/author/AbdEl-Salam%2C+N+M

x

v. Zahid Hussain, Khalid Mohammad Khan and Khadim Hussain (2014). Microwave metal

Interaction pyrolysis of waste polystyrene in copper coil reactor. Part A: Recovery,

Utilization, and Environmental Effects. Volume 36, (18).

vi. Zahid Hussain, Khadim Hussain, Khalid Mohammed Khan and Shahnaz Perveen (2013).

The Disposal of Waste Low Density Polyethylene by Co- Liquefaction with Coal by

MicrowaveMetal Interaction Pyrolysis in a Copper Coil Reactor. J. Chem. Soc. Pak 35,

(1).

vii. Zahid Hussain, Khalid Mohammad Khan and Khadim Hussain (2012). The conversion of

waste polystyrene into useful hydrocarbons by Microwave metal interaction pyrolysis.

Fuel processing technology 94(1).

viii. Nadia Basheer, Khadim Hussain, Khalid Mohammad Khan, and Zahid Hussain (2012). A

New Method for the Co-Liquefaction of Coal and Waste Tyre Rubber into Useful

Products Using Microwave Metal Interaction Pyrolysis. J. Chem. Soc. Pak, 34 (1).

ix. Zahid Hussain, Khalid Mohammad Khan, Khadim Hussain, Sadam Hussain and Shahnaz

perveen (2011). Microwave spark emission spectroscopy for the analysis of cations: A

simple form of atomic emission spectroscopy. Chinese Chemical Letters Vol 22 Issue 9.

x. Zahid Hussain, Khalid Mohammad Khan, Nadia Basheer and Khadim Hussain (2011).

Co Liquifaction of Makarwal Coal and Waste polystyrene By Microwave metal

interaction pyrolysis in copper coil reactor. Journal of Analytical and Pyrolysis Vol 90,

Issue 1.

xi. Zahid Hussain, Khalid Mohammad Khan, Khadim Hussain and Shahnaz perveen (2010).

Preparation of a novel rechargeable storage battery using protein for the storage of

Electricity. J. Chem. Soc. Pak Chem. Soc. Pak Vol 32, No 6.

xii. Nadia Basheer, Khadim Hussain, Khalid Mohammad Khan, and Zahid Hussain (2010).

Liquifaction of Makarwal Coal by Microwave metal interaction pyrolysis. J. Chem. Soc.

Pak 32, 6.

xiii. Nadia Basheer ,Zahid Hussain , Khadim Hussain ,Khalid Mohammed Khan and Shahnaz

perveen, (2010). Gas chromatographic-Mass Spectrometric Analysis of the

xi

Products Obtained by Microwave-Metal Interaction Pyrolysis of Coal. J. Chem. Soc. Pak,

31, 6.

xiv. Zahid Hussain, Khalid Mohammad Khan and Khadim Hussain (2010). Microwave Metal

Interaction pyrolysis of polystyrene. Journal of Analytical and Pyrolysis volume 89 issue

1.

xii

TABLE OF CONTENTS

S.No CONTENTS PAGE

Certificate

ii

Author’s Declaration

Iii

Plagiarism Undertaking

Iv

Certificate of Approval

V

Declaration Vi

Acknowledgements

Vii

Abstract Viii

List of publicat ions

ix

Table of contents xii

Chapter I 1

Introduction 1

1.1 Biomass and biomass energy 1

1.2 Biomass types 2

1.3 Biomass utilization and conversions to Fuel oil and gas 2

1.4 Microwave assisted heating 3

1.5 The present work and its Theoretical Basis 4

1.6 Water hyacinth 4

1.7 Reasons for the selection of Water Hyacinth as a biomass 5

1.8 Scope of the present work

6

1.9 Microwaves and microwave heating 6

1.10 Aims of the present work 7

Chapter II 8

Literature Review 8

xiii

Chapter III 26

Experimental 26

3 Microwavemetal interaction pyrolysis of biomass using different metals

antennas

26

Preparation of sample 26

Instruments 26

Material / Chemicals 27

Reactor 27

Modification in microwave oven 29

3.1 Microwave metal interaction pyrolysis of biomass using iron coil antenna 30

Procedure 30

3.2 Optimization studies for microwave metal interaction pyrolysis of biomass using

cement as catalyst in iron coil antenna

31

3.2.1 Investigation of the optimum ratio of biomass and cement catalyst for the

microwave metal interaction pyrolysis of biomass using Iron coil as antenna

31

Procedure 31

3.2.2 Investigation of the optimum time for the microwave metal interaction Pyrolysis

of Biomass (Eichhornia crassipes) using cement as catalyst:

32

Procedure 32

3.2.3 Optimization of gauge of the wire for Iron coil antenna for the microwave

assisted catalytic pyrolysis of biomass

33

Procedure 33

3.3 Optimization studies for microwave - metal (Iron)interaction pyrolysis of

biomass using kaolin as catalyst

34

3.3.1 Investigation of the optimum ratio of biomass and Kaolin catalyst for the


34

Procedure 34


of Biomass (Eichhornia crassipes) using kaolin as catalyst

35

Procedure 35

3.3.3 Optimization of gauge of the wire for Iron coil used as antenna for the

microwave assisted catalytic pyrolysis of biomass using kaolin as catalyst

36

Procedure 36

3.4 Optimization studies using clinker as catalyst 37

xiv

3.4.1 Investigation of the optimum ratio of biomass and clinker catalyst for the


37

Procedure 37


of Biomass (Eichhornia crassipes) using clinker as catalyst

38

Procedure 38

3.4.3 Optimization of gauge of the wire for Iron coil used as antenna for the

microwave assisted catalytic pyrolysis of biomass using clinker as catalyst

39

Procedure 39

3.5 Microwave metal interaction pyrolysis of biomass using copper coil antenna 39

Instruments and reactor 39

Material/chemicals 39

Procedure 40

3.6 Optimization studies using copper coil antenna for different catalyst 40


microwave metal interaction pyrolysis of biomass using copper coil as antenna

40


Procedure 41


of Biomass (Eichhornia crassipes) using cement as catalyst

42

Procedure 42

3.6.3 Optimization of gauge of the wire for copper coil as antenna for the microwave


43

Procedure 43

3.7 Investigation of the optimum ratio of biomass and kaolin catalyst for the


44

Procedure 44


of Biomass (Eichhornia crassipes) using kaolin as catalyst

45

Procedure 45

3.7.2 Optimization of gauge of the wire for copper coil used as antenna for the


46

Procedure 46

3.7.3 Investigation of the optimum ratio of biomass and clinker catalyst with copper

coil as antenna

46

xv

Procedure 46



47

Procedure 47

3.7.5 Optimization of gauge of the wire for copper coil used as antenna and clinker as

catalyst for the microwave assisted catalytic pyrolysis of biomass

48

Procedure 48

3.8 Microwave metal interaction pyrolysis of biomass using aluminium coil antenna 49

Procedure 49

3.9 Optimization studies for different catalysts using aluminium coil as antenna 49


microwave metal interaction pyrolysis of biomass using Aluminium coil as

antenna

49


Procedure 50


of Biomass (Eichhornia crassipes) using cement as catalyst

51

Procedure 51

3.10.3 Optimization of gauge of the wire for Aluminium coil used as antenna for the

microwave assisted catalytic pyrolysis of biomass

52

Procedure 52

3.11 Optimization studies using kaolin as catalyst 53

3.12.1 Investigation of the optimum ratio of biomass and kaolin catalyst for the

microwave metal interaction of biomass using Aluminum coil as antenna

53


of Biomass (Eichhornia crassipes) using kaolin as catalyst.

53

Procedure 53

3.12.3 Investigation of the effect of gauge of Aluminium wire on microwave assisted

catalytic pyrolysis of biomass

54

Procedure 54

3.13 Optimization studies for clinker catalyst 55

3.14.1 Investigation of the optimum ratio of biomass and clinker catalyst for the

microwave metal interaction pyrolysis of biomass using Aluminium coil as

antenna

55

Procedure 55

xvi



56

Procedure 56



57

Procedure 57

3.15 Characterization studies 57

Chapter IV 58

Results and Discussion 58

4 The idea of catalytic and microwave metal interaction pyrolysis of biomass 58

4.1 Cement weight optimization using iron antenna 58

4.2 Time optimization for cement catalyzed and iron antenna (microwave metal

interaction Pyrolysis)

61

4.3 Optimization of the gauge of wire for Iron coil 63

4.4 Investigation of the optimum ratio of biomass and Kaolin catalyst for the


63

4.5 Time optimization for kaolin catalyzed microwave metal interaction pyrolysis 66

4.6 Optimization of gauge of the wire for Iron coil used as antenna for the


68

4.7 Clinkered brick powder weight optimization for the microwave metal interaction

pyrolysis of biomass using Iron coil as antenna

68

4.8 Time optimization for clinkered catalyzed and iron antenna (microwave metal

interaction pyrolysis)

71

4.9 Optimization of gauge of the wire for Iron coil used as antenna for the

microwave assisted catalytic pyrolysis of biomass using clinker as catalyst

73

4.10 Chemical composition of the bio –oil obtained by microwave metal interaction

pyrolysis of biomass in an iron coil antenna

73

4.11 Effect of cement catalyst on product distribution of the pyrolystae obtained by

the microwave assisted pyrolysis

78

4.12 Effect of kaolin catalyst on product distribution of the pyrolystae obtained by the

microwave assisted pyrolysis in iron coil

82

4.13 Effect of clinkered brick catalyst on product distribution of the pyrolystae

obtained by the microwave assisted pyrolysis in iron coil

87

4.14 Cement weight optimization using copper antenna 92

4.15 Time optimization for cement catalyzed and copper antenna (microwave metal


95

4.16 Optimization of the gauge of wire for copper coil antenna 97

xvii



98

4.18 Time optimization for kaolin catalyzed and copper antenna (microwave metal


100


pyrolysis of biomass using copper coil as antenna

102

4.20 Time optimization for clinker catalyzed and copper antenna (microwave metal


104

4.21 Optimization of gauge of the wire for copper coil used as antenna and clinker as


106

4.22 Characterization of oil obtained after pyrolysis of biomass using copper coil

antenna

106



111


microwave assisted pyrolysis

115


obtained by the microwave assisted pyrolysis

120

4.26 Relative weight of catalyst (cement) and biomass optimization 126

4.27 Time optimization for cement catalyzed and aluminium coil antenna for

microwave metal interaction Pyrolysis

129

4.28 Optimization of the gauge of wire for aluminium coil 131


microwave metal interaction pyrolysis of biomass using aluminium coil as

antenna

131

4.30 Time optimization for kaolin catalyzed and aluminium coil antenna for

microwave metal interaction Pyrolysis

134

4.31 Optimization of the gauge of wire for aluminium coil 136


pyrolysis of biomass using aluminium coil as antenna

136

4.33 Time optimization for clinker catalyzed microwave metal interaction Pyrolysis

in aluminium coil

138

4.34 Optimization of gauge of the wire for aluminium coil used as antenna for the


140

4.35 GC-Ms analysis of the bio -oil obtained by microwave assisted pyrolysis of

biomass in an Aluminium coil

140



144


obtained by the microwave assisted pyrolysis

148


microwave assisted pyrolysis in Aluminium coil

151

xviii

Chapter –V 156

5.1 Conclusion & outlook 156

5.2 Future Directions 156

5.3 Comparison 157

Chapter vi 158

References 158

1

CHAPTER I

INTRODUCTION

1.1 Biomass and Biomass Energy

Since the oil crisis in Europe and America in 1970s greater focus has been seen on the search for

alternate sources of fuel. One of the best candidates of alternative fuel is biomass which is a

renewable resource. Biomass is the name of all matter produced by the living things in the form

of wood, grass, leaves and waste of the animals. Biomass is deemed as the cleaner source of

energy due to its renewability. The word biomass is used for cellulosic, hemocellulosic,

lignocellulosic, and proteinous materials which is obtained from living things [1]. Biomass is one

of the potential sources of renewable energy [2] for its wide distribution and in addressing CO2

management. It also contain energy contents almost comparable to fossil fuels; 10 tons of dry

barksmay give as much heat as obtained from 7 tons of coal. Biomass are classified into two

classes; primary biomass and waste biomass.Biomass is used as source of energy since from the

discovery of fire by the human. It was used by the cavemen for cooking and warming. Later on it

was also used for metallurgical operations and in the modern ages for electricity generation

through steam production. Despite of its use as primary source of energy its conventional use is

limited due to smoke and production of aldehydic compounds which may cause serious

respiratory effects. The direct combustion is non-compatible with most of the present day

machinery specifically vehicles which are using oil and gas as fuel. In the last many years greater

focus has been seen on the conversion of biomass into oil and gases using various processes.

These processes include thermal cracking, thermo-chemical and thermo catalytic cracking [3-6].

Thermo-catalytic cracking of biomass may give liquid and gaseous fuel.Biomass produces fuel

gases and liquid fuel on thermal cracking [7-9]. It can also be converted into fuel compounds like

methanol ethanol through thermal process [10].The products of pyrolysis of biomass may

contain larger quantities of water that is why its use as fuel is limited, however there are

reported methods for improvement in the pyrolytic conversion of biomass into fuel oil [1,2,11-

12]. The difference in chemical reactivity of hemicellulose, cellulose and lignin [13 -15] can be

exploited to extract value-added chemicals by thermal processing of biomass via pyrolysis. It is a

versatile thermal conversion technology that consists of several varieties, depending on the

desired products [16].

2

1.2 Biomass types

Biomass can be Primary biomass or Waste biomass.

Primary biomass is further divide into terrestrial and aquatic biomasses. Forests, Grasses,

Energy crops and cultivated crops are included in terrestrial biomass while water plants and

algae are examples of aquatic biomass.

1.3 Biomass utilization and conversions to Fuel oil and gas

Biomass combustion

In most parts of the world biomass is used as fuel through direct combustion. The energy

produced is heat energy which can be used for heating purposes, as well as cooking and warming

[17]. It is the most common use of biomass ranging from home to industry. The heat obtained

from domestic combustion of biomass is utilized for cooking and heating. Biomass like wood

and bagas is also used for industrial heating applications using larger furnaces and boilers.

Chemical conversion

Biomass may be converted into fuel products like methanol and olefins through chemical

processes [18]. The first step of this conversion involves gasification. Biomass is more difficult

to feed into a pressure vessel than coal or any liquid. The gas which is formed is called a

producer gas. This procedure gas is used as fuel or feed stock for the preparation of chemicals.

The chemical conversion may also involve Trans-esterification resulting the formation of

biodiesel. Another process of the chemical change of biomass is the formation of ethylene and

propylene by the use of catalyst like alumina and zeolite. This process is also promising due to

the fuel and industrial feed stock like nature of these chemicals.

Biochemical conversion

The biomass is also converted into fuel and value added products through the action of enzymes

and other biological agents which is called biochemical conversion. This process is takes with

the help of bacteria, fungi and algae [19]. Enzymes produced by bacterial and nonbacterial

micro-organisms are used to break down biomass into simpler compounds and the process is

3

named as biochemical conversion. This process of breakdown is also called digestion which may

either be; anaerobic digestion, aerobic digestion or fermentation.

Biomass Pyrolysis

Biomass may also be converted into useful oil and gas through pyrolysis. Where pyrolysis of

biomass can be defined as the thermal decomposition of the cellulosic and non cellulosic

material of the biomass into smaller compounds in the absence or limited supply of oxygen. It

converts the biomass into liquid, gas and most compact solid fuel. This process results the

formation of liquid fuels having low calorific value although active research is going on to make

good the quality of bio fuel. The gaseous fuel obtained may contain larger quantities of the

combustible gases which can be used both for domestic and industrial heating. Wood charcoal

obtained during this process is a well-known solid fuel.

Biomass conversion to Fuel oil and gas through Pyrolysis

Biomass conversion technologies are of greater focus in the scientific community with special

emphasis on cost. Biomass can be converted into liquid fuel and fuel like substances by various

processes [3-6]. Biomass produces fuel gases and liquid fuel on thermal and thermo-catalytic

cracking [7-9]. Catalytic pyrolysis is one of the best option and recently Hussain and coworkers

converted biomass into highly flammable and hydrocarbon rich fuel through catalytic pyrolysis

[20]. In comparison to the conventional pyrolysis microwave assisted pyrolysis is considered as a

faster method of pyrolysis and is considered as economical.

1.4 Microwave assisted heating

Microwave heating is a faster and volumetric heating. Microwave heating is carried out using

dielectric substances which are microwave absorbers. Among the solid materials these include

carbon, char and oxides of the metals. The second type of microwave heating is a hybrid type of

microwave heating based on microwave absorption and reflections by the metals which generate

heat according to the nature of the metal under consideration [21]. This is characterized by both

volumetric and surface heating as compared to conventional and microwave absorptive heating

that is microwave metal interaction pyrolysis is faster than others. A compared to conventional

heating, microwave heating has many advantages [22];

4

1. Higher rates of heating

2. Contactless heating Selective heating may be achieved

3. Strict control of the heating or drying process.

4. Reduced equipment size and waste.

1.5 The present work and its Theoretical Basis

Microwave metal interaction pyrolysis was previously used for the conversion of plastics, rubber

and co-liquefaction of the coal and plastics [21, 23-25] is a new approach to the faster and

economical heating. This uses metallic coils as heat generating and microwave reflecting

antennae. The temperature inside and around the coil may reach in the range of melting point of

the metal used for the preparation of antennae. The melting point of some of the metals may

range in the temperature where water can be decomposed into oxygen and hydrogen by the use

of proper catalyst. Further at this high temperature and in the presence of microwave radiations

of appropriate frequency some gases like carbon dioxide can be converted into high temperature

plasma [26]. Biomass pyrolysis may produce larger quantities of water ranging up to 40% of the

dry mass of the biomass in addition to some carbon dioxide. The presence of water and

oxygenated compounds present in the pyrolysate of biomass discourage the direct use of this as

fuel or value added chemical. In the present work attempts will be made to reduce the amount of

water and highly oxygenated compounds in the pyrolysate of biomass by conversion of the water

into hydrogen using catalyst and heating by the microwave metal interaction process. This will

convert the pyrolysate into highly combustible liquid fuel as already reported in two step

pyrolysis by Hussain and coworkers [27]. The present work is focused on the preparation of

highly upgraded oil from water hyacinth as through microwave metal interaction pyrolysis.

1.6 Water hyacinth

Water hyacinth is the name of Eichhornia crassipes. It is a floating plant of fleshy nature which

occurs in on rivers, lakes and ditches. Water hyacinth cannot survive in ice cold conditions for

long time. However under the unfavorable conditions its roots attach to the mud and ensure its

survival for several days. It is characterized for its invasive nature and may be considered as

threat to the water bodies. It may also pose a threat to the aquatic life by blocking the sunlight

and oxygen depletion. It is the native plant of Brazil but now it occurs throughout the world. The

shiny green leaves of water hyacinth are considered as having less quantity of lignin and

5

considered as rich source of the cellulose. This aquatic plant may get a maximum height of about

one meter above the surface of water. Water hyacinth is a fast growing plant which doubles their

population in two weeks. It was estimated that about fifty kilograms of water hyacinth are

produced per square meter of the water body [28]. It is because of the large quantity of cellulose

it may act as a good source of biomass. That is why it was selected as biomass in the present

work. It was converted into useful fuel through its catalytic pyrolysis.

Figure1. Water Hyacinth (Eichhornia Crassipies).

1.7 Reasons for the selection of Water Hyacinth as a biomass

i. The plant is found abundantly and locally in district Swabi and easily available the year

around.

ii. Since it is very soft it can be picked out or cut with little effort.

iii. It is sundried in two weeks.

iv. It is easily turned into powder form by a common grinder.

v. The plant is currently not in use of any industry for any useful production in Pakistan.

Our aim is to highlight the potential industrial uses of Water Hyacinth.

vi. The state owned companies like Pakistan State Oil (PSO) depends on cultivated seeds

like sunflower and rapeseeds etc. to make biodiesel. The aim of this research work is to

further economize the oil production by using a wild, useless plant instead of cultivated

plants.

6

1.8 Scope of the present work

The present work is aimed to convert biomass into upgraded bio oil. This is part of the efforts to

search for alternate sources of energy in order to avoid the problems associated with the fossil

fuels and the deemed shortage of oil and gas due to the rapid depletion of these sources of

energy. Biomass has the potential to be converted to oil called bio oil. However at present the oil

produced from biomass contains large quantities of water and needs up gradation before use.

Pyrolysis is the competent candidate for the conversion of biomass into combustible gas, bi oil

and bio-char. The nature of product and relative amount of oil and gas fraction can be controlled

by the proper selection of biomass and pyrolysis conditions [23, 24].

1.9Microwaves and microwave heating

Microwaves are electromagnetic radiations having wave lengths from 1 mm to 1 m and its

frequency is in the range of 300 MHz–300 GHz. The frequency of domestic microwaves is in

2.45 GHz and its wave length is 12.2 cm. Microwave heating is volumetric heating due to which

it is faster and energy efficient. It is usually named as dielectric heating due the fact that it

usually heats up the dielectric materials. Dipole of the material realign approximately 2.5 billion

in one second. This heats up the microwave dielectric material. However all materials are not

dielectric and does not heat up by this way. For example metals also heat up in the microwaves

but their heating is due to the discharge effect or reflective heating is there. When the microwave

falls on such materials it may either disturb the charge distribution or produce some electric and

magnetic effects as a result of which there is heat generation. There are materials which are

transparent to the microwaves and may allow these electromagnetic radiations to pass through

unaltered without generating heat.

7

1.10 Aims and Objectives of present work

The objectives of the present work are

i. To provide a renewable substitute of the fossil fuel through pyrolysis of biomass. This

may produce bio-oil and gas as alternative of mineral oil and gas.

ii. Investigation of novel method for the liquefaction of biomass.

iii. Investigation of cost effective method for the conversion of biomass into liquid fuel.

iv. Investigation of faster method for the conversion of biomass into bio oil.

v. Investigation of new catalysts in the liquefaction of biomass.

vi. Optimization of the temperature and time for the pyrolysis reaction.

vii. To maximize the liquid product yield and decrease the solid residue and gases.

viii. Application of microwave energy for the conversion of biomass into upgrade bio oil.

ix. Contribution to the international efforts for developing cleaner alternate fuel.

x. Contribution to national efforts for overcoming the energy crisis.

xi. Evaluation of the activity of catalyst for improving the nature of products of biomass

pyrolysis

xii. Utilization of natural resource for addressing the shortage of energy.

xiii. Resources recovery and generation

xiv. Conversion of biomass into oil and fuel gas using faster and economical methods of

microwave heating.

8

CHAPTER II

LITERATURE REVIEW

Milne [29] et al 1990 reported the effect of zeolite (HZSM – 41) on thermal catalytic

conversion of biomass including vegetable, oil seed, algae and industrial waste materials. The

catalyst were believed to influence the yield of product as well as selectivity of the product.

Adjaye [30] et al 1995studied the effect mordenite, Silicalite and Silica -alumina on the valuable

chemicals obtained from biomass under microbed reactor. The reaction were taking place at 290

-410 °Cunder atmospheric pressure. The obtained product was a mixture of char, coke, gas, tar

and water. The catalysts were believed to influence the yield of product, selectivity and the

nature of product fractions.

Williams [31] et al 1995 studied the upgradation of bio-oil formed by pyrolysis of biomass in a

fluidized bed reactor. The bio-oil was treated with different type of zeolite catalysts, and

activated alumina at low pressure. The reaction was also carried out without catalyst for

comparison. The composition of the oil without catalyst and with catalyst upgrading was

analyzed by LC fractionation, and GC-MS analysis. The aromatic and oxygen containing

aromatic compounds were analyzed quantitatively. They foundminorchanges in the quantity and

quality of bio-oil after the catalysis.The catalysts were found effective in lowering the oxygen

content of the bio-oil. However, a significant concentrations of oxygenated compounds were still

present in the upgraded oil. The ZSM-5 catalysts gives the goodamount of hydrocarbon products

than Y-zeolite and activated alumina catalysts. The amount of carcinogenic polycyclic aromatic

hydrocarbons (PAH) were high by using all the catalysts. The formation of coke was high for Y-

zeolite and alumina compared to the Na-ZSM-5 and H-ZSM-5 catalysts.

Bridgwater [32] et al 1996investigated the effect of zeolites on thermal catalytic pyrolysis of

biomass .The catalyst were believed to influence the yield of product as well as the selectivity of

the product. The process were based on the production of bio –oil and also up –grading them into

high grade fuel.

Zanzi [33]et al 1996studied the fast pyrolsis of wood and agricultural waste in a free fall reactor

at a high temperature (800°C-1000°C). They investigated the kinetics, pyrolysis temperature,

particle size and residence time on the product distribution, gas composition and the reactivity of

9

char. They used birch and white quebraco as wood and straw pellets, baggas, and sugarcane

leaves as agricultural waste. Coal was also pyrolized for comparison with biomass.Pyrolysis at

high temperature produced lessamount of tar and high amount of gaseous products.This was

because of thermal cracking of tar at high temperature. The high heating rate decreasedchar

yield. The particle size of biomass significantly affected the pyrolysis because of its effect on the

heating rate of biomass in the reactor. In this research author was interested to find out the effect

of fast pyrolysis and the reactivity of char. The char consists of active carbon which has larger

internal surface area and a high capacity of adsorbing liquids and gases. The formation of less

yield of char and high reactivity was required. The thermal cracking of char was effected by

heating rates, short residence time at higher temperature and also small particle size of biomass.

Arauzo [34] et al 1997 checked the effect of Nickel and magnesium aluminate on the yield of

product using fluidized bed reactor. The selectivity of the yield of product were greatly depended

on the used of the nature of catalyst.

Minowa [35] et al 1998 studded the effect of sodium carbonate and nickel on the hot compressed

water pyrolysis of biomass using cellulose. The catalyst were believed to influence the selectivity

of the yield of product as well as their nature.

Antal [36]et al 2000 investigated gasification of biomass under supercritical water using feed

stock of corn potato starch gel and wood straw .These were rapidly heated at high temperature

above the critical pressure of water. Organic portion of which were vaporized and then catalyzed

by packed bed of carbon. The obtained gases is a mixture of H2, CO, CO2 and CH4 along with

trace quantity of ethane.

Miura [37]et al 2000 studied pyrolysis of biomass using microwaves and piece of lumber. The

pyrolyzed product (Charred and tar) were obtained at different proportions by the application of

microwave on fixed range and time.

Minkova [38] et al 2000carrid out pyrolysis of biomass samples of different origin in a flow of

steam or in a mixture of steam and carbon dioxide in a horizontally rotating stainless steel

reactor. The feed stock used were waste from Birch wood, olive stone, baggas, pellets of straw

and Miscanthus. The feed stock were heated for 2 hours with heating rate of 10°Cper minute

to750°C at atmospheric pressure. The results obtained with treatment in inert atmosphere in a

10

stationary reactor were compared. The pyrolysis in rotating reactor and the steam or mixture of

steam and CO2 proved to be good for the production of energy rich gaseous products and

activated carbons. The reason was that both these factors favored the efficient removal of

volatiles from the carbonizing biomass.

Coll [39] et al2001 studded steam reforming model compounds of biomass gasification. Using

five model compounds and its reaction rates, temperature and show their effect on the yield of

product (gas and tar).

Razvigorova [40] et al 2001 studied slow pyrolysis of biomass with a flow of water steam in a

fixed bed reactor. The wastes of different origin (Birch wood, Olive stones, baggas, pellitized

Straw, andmiscanthus) were used as biomass. The pyrolysis temperature was between 700-

800°C and the duration of reaction was 1 or 2 hours. The study was focused on the investigation

of effect of nature of biomass and water vapors on the product of pyrolysis. Column

chromatography was used to separate the liquid product. The acid-base neutralization capacity

of the solid product and their surface area was investigated byreaction with EtoNa , HCland the

iodine adsorption capacityrespectively. The inert nitrogen atmosphere and experimental data

were compared . It was seen that the properties of product were effected by presence of steam.

The presence of steam significantly increased the liquid product yield. The steam play role to the

formation of solid residue (active carbon)withgood adsorption capacities and high surface area.

Similarly, nature of biomass also affected on yield and product qauality. Olive waste, birch and

bagass gave higher yield of solid residue with high adsorption properties while straw and

Miscanthus were found more suitable for conversion into liquid and gas products.

Domi [41] et al 2003investigated the graphite effect on microwave assisted pyrolysis of

biomass using sewage sludge. The pyrolysis process was performed at high heat and yield of

product depend upon temperature ranges. The obtained product was analyzed for various

properties by GC –MS and correlated with microwave absorption.

Lede [42]2003exploited Ablation method for the high speed pyrolysis of biomass. Two ablative

methods of biomass pyrolysis were used and compared, namely contact ablative pyrolysis and

radiant ablative pyrolysis. In the first method, biomass is pressed against a hot surface and in the

second method, biomass intercepts a concentrated radiation. The comparison was made on the

basis of the values of ablation thickness and velocity and of product fractions and compositions.

11

The results were very different in spite of the fact that biomass was subjected to similar heat flux

densities in both methods. This research showed the advantages, drawbacks and

complementarities of each technology.

Menedez [43] et al 2004 compared the amount of gas produced in microwave assisted pyrolysis

with conventional method using sewage sludge as biomass. It was found that large amount of

gases produced in microwave pyrolysis.

Dominguez [44] et al 2005investigated the microwave absorbers (graphite and char) effect on the

microwave assisted pyrolysis of biomass using sewage sludge. The process were greatly depend

upon reaction conditions (Temperature and time).The obtained product were analyzed by GC –

MS and characterized the nature of product.

Zhang [45] et al 2005studied the Co -Mo -P effect of on the pyrolysis of biomass using fluidized

bed reactor. The process were believed to produce the product under controlled condition.

Dominguez [46] et al 2005investigated the effect of microwave absorbers including char and

graphite on the microwave assisted pyrolysis of biomass using sewage sludge as biomass. The

selectivity of the product depend upon by the used of microwave absorbers. The quantity of 1 –

alkenes is more than alkane when graphite was used as microwave absorbers. The oil product

yield from microwave assisted pyrolysis of biomass was aliphatic in nature. The obtain product

was analyzed by GC –MS.

Dominguez [47] et al 2006 compared microwave assisted pyrolysis with conventional method

using sewage sludge as biomass. Microwave absorbing materials (char and graphite) were

greatly affected the yield of product. The amount of product during the process was very high

and environment friendly. The obtained product were analyzed by FT -IR, GC-MS and

characterized based on its functional group and were correlated with microwave absorption.

Zeng [48] et al2006studiedrice husk and saw dust conversion into liquid fuel.Saw dust, rice

husks and mixture of these were pyrolyzed at 420 and 540C0temperature and liquid fuel was

obtained. The dataobtained shows the dependence of amount of liquid fuel on nature of

feedstock and heating temperture. The yields of product for rice husks, sawdust and their

mixture were ranging from 56%- 60% at different temperatures.The GC–MS results and other

methods shows that the nature of liquid fuel was a complex.The liquid fuel having low caloric

12

value, without any upgrading could be used as a fuel for combustion in a boiler or in a

furnace.While for vehicles the fuel could be refined.

Lliopoulou [49] et al 2007compared the effect of Al –MCM -41 (mesoporous aluminosilicate)

and MCM -41 (siliceous) on the yield of catalytic pyrolysis of biomass as well as the quality and

the nature. Using Al -MCM-41 as catalyst it increases the amount of phenol product. Selectivity

of the product also depend the ratio of Si/Al in Al –MCM -41.

Gurin [50] et al 2007investigated the effect of ionic liquids on the micro channal heat exchanger

and micro channal reactor .The process were carried out under supercritical condition using

biomass solution.

Dominguez[51]et al 2007 compared microwave assisted pyrolysis of biomass with conventional

method by using coffee hull as biomass. The product yield of the procee is directly related with

temperature as well as pyrolysis method. The quantity of gas is greater as compared to electric

process.

Yu [52] et al 2007investigated various behaviors of pyrolysed oil obtained at the result of

microwave assisted pyrolysis of biomass using corn Stover as biomass .To identified the oil

characteristics their viscosity, PH, heating values , amount of water were determined.

Dominguez [53] et al2007 investigated the formation of syngas from biogas on the microwave

assisted pyrolysis .This was possible by the decomposition of CH4 resulting H2 and carbon as

well as splitting of CO2 to produced CO both carried out by microwave and conventional

heating. The decomposition of CH4 reduced catalytic activity but when mixture of CH4/CO2 is

combinely used then it reduced this problem.

Menedez [54] et al 2007 compared microwave heating with conventional method using coffee

hulls as biomass. These processes were carried out under different temperature ranges by carried

out the reaction between CO2and char.

Jacques [55] et al 2007 investigated the cyclone reactor fast pyrolysis of biomass. The

pyroliquefaction of biomass weredone at 627°C-710°C in order to enhance bio-oil production.

The liquid product yield reached 74% while those of char and gases were 10% and 16%

respectively. The bio-oil was condensed and trapped at different temperatures. Three main

13

fractions were separated namely heavy oils, light oils and aerosols. Each fraction showed

different physicochemical properties e.g. viscosity, density and pH.

El –Rub [56] et al 2008compared biomass char with the char of other materials using fixed bed

tubular reactor under controlled temperature and atmospheric pressure. The process were found

that biomass char used to convert various types of chemicals (naphthalene ) with low cost. It was

found that biomass char were continuously produced during thermal heating.

Xu [57] et al 2008 investigated the K2CO3 and alkaline earth metal effect on the liquefaction of

biomass including pulp /paper sludge powder. The process were carried out under controlled

condition of temperature and atmospheric pressure .The catalyst were believed to influence the

selectivity of the yield of product (heavy oil & water soluble). The obtained product were

analyzed by GC -MS and correlated with catalytic activity.

Huang [58] et al 2008studded total recovery of resources and energy from microwave assisted

pyrolysis of biomass including rice straw dust as biomass .The process depend upon particle size

as well on the microwave power.

Ates [59]et al 2008 investigated the temperature effect on the biomass pyrolysis including wheat

straw and oat straw. Based on temperature ranges various proportions of product were formed.

The obtained product were characterized by 1HNMR and GC–MS.

Carlson [60] et al 2008 investigated the effect of zeolite (ZsM) on catalytic fast pyrolysis of

biomass in a single catalytic reactor. The catalyst were believed to influence the yield of product

as well as to reduced the time for the process.

Chen [61] et al 2008investigated the effect of NaOH,Na2CO3,Na2SiO3,NaCl, TiO3,HZSM -5

,H3PO4and Fe2(SO4)3[inorganic additives ] on the microwave assisted pyrolysis of biomass

using pine wood sawdust. These additives were found to increased the yield of liquid product but

decreased the amount of gases.

Heeres [62] et al 2008 Pyrolized Poplar,beech, Spruce and Straw biomass for the production of

chemicals through Staged degasification. The Staged degasification was carried out in 2

consecutive stagesbetween 250°C-300 °C and 350°C-400°C. The fractionswhich were formed at

250°Cto300°C, mainly contained hemicellulosic degradation compounds.The composition of the

14

productwhich were obtained at 350°C-400°C, were mostlycontaining for cellulose.The lignin

based fractions were present in both stages. A product yield upto 5%wt of dry biomass were

obtained for compounds like Furfural,acetic acid,Acetol andLevoglucosan.

Baeyens [63]et al 2008studied the Fluidized bedfast pyrolysis of biomass to improve the

pyrolysis yields usingdifferential scanning calorimetry (DSC) and thermogravimetric analysis

(TGA) experiments. It was shown that for most kinds of biomass, the reaction rate constant was

>0.5 s−1. The batch experiments in Labscale and CFB pilot scale experiment showed that an oil

yieldsin range 60% & 70 wt% could be obtaniedat operating temperature(510±10°C).

Carlson [64]et al 2009 investigated the effect of ZSM -5 , Silicate , beta , Y - Zeolite and

Silica- alumina on the pyrolysis of biomass . It was found that, the biomass were first

decomposed and then converted into a mixture of gases under the action of catalyst. The

catalysts were believed to influence the selectivity of product as well as their amount.

Wan [65] et al 2009 investigated the effect of metal-oxides, salts and acids on the microwave

assisted pyrolysis of biomass using corn Stover and aspen as biomass. The catalyst was believed

to influence the yield of fractions (bio oil, gas and charcoal) as well as nature of products of

fractions by enhanced microwave absorption. And in situe catalysis. The obtained products were

analyzed by GC-MS and correlated with catalytic activity and microwave absorption.

Weipeng Lu [66] et al2009by deoxy liquefaction ofwater hyacinth prepared HCF (high caloric

fuel) and the composition of this fuel wereinvestigate. They used different temperature ranges for

thisstudiesi.e573K, 623K, 673K, and 723K with the heating rate of 60Kper minute. The

reactionswereperformed in the closed reactor. At 623K the product obtained was12.6%wt. of

HCF with43.8MJ/kg of heating value. The more dominant compounds in this HCF were

alkanes,derivatives of Benzene andderivatives ofPhenol. The major gaseous product was 93.2%

mol in CO2 which that wh released oxygen in this form. The elemental analysis of solid char

explained that the content of hydrogen in residue were not enough to produce more HCF. The

reported method was found suitable method for removalof oxygen and utilization of carbon and

hydrogen in WH to higherquantitity.

Lunshof [67] et al 2009 pyrolized Poplar, spruce beech and straw biomass for the production of

chemicals through hybrid staged degasification. The hybrid staged degasification was a

synergistic combination of hot pressurized water treatment (aquathermo-lysis) and fast pyrolysis

15

in for fractionation of biomass and its conversion to valuable chemicals. This process was

developed to produce furfural from the hemi-cellulose, while the subsequent pyrolysis of the

biomass char was selectively converted into levo-glucosan. Up to 8 %wtof furfural, 3% wt of

Hydroxymethyl- furfural and 11% wtof levo-glucosan were produced by this process.

Van der Laan [68] et al 2009 pyrolized two different kinds of Lignin in a bubbling fluidized bed

reactor at 400°C. they reported the potential of feedstock as a renewable source for high value

Phenolic chemicals and petrochemicals such as octane enhancer for transportation fuel. The

pyrolysis of type I lignin resulted in 13 wt% while that of type II resulted in 20% wt of phenolic

fraction. The major components of this fraction were Guaiacols, Syringols, alkyl Phenols and

catechols. Morever, it was investigated that by pyrolysis of lignin oil could be converted into

cyclo-alkanes, alkyl substituted cyclo-hexanols, cyclo-hexanol and linear alkanes by a short

hydrodeoxigenation reaction with Ru-C (used Ruthenium& Carbon) as a catalyst. This showed

that ruthenium on carbon was a very effective catalyst for the lignine hydrogenation in pyrolyzis

oil to produces phenolics of low molecular weight.

Ellens [69] et al 2009 pyrolized corn stover, corn fiber and Red oak in a radiatively heated, free-

fall, fast pyrolysis reactor. The optimizations were carried out by varying four operating

conditions in the novel reactor. These were temperature of reactor, particle size of biomass, flow

rate of carrier gas and feed rateofbiomass. The highest biooil yields of 72% wtwere achieved at

a heater-set-point of 600°C, with300 µparticle sizes, 4sL/min carrier gas flow rates and

biomass(Red oak) feed rates of 1.75 kg/hr. The optimized conditions for highest biooil yields

required a heater-set-point temperature of 572°C, with 240 µ size ofred oak biomass

powderfeed at 2 kg/hr. The rate of carrier gas flow were not having significant effect over the

tested range of 1 – 5 sL per min.

Jayeeta [70]et al 2009 investigated the effects of catalyst Cu/Al2O3 catalysts of three varied

compositions (10, 20 and 30 wt% copper loading) on the pyrolysis of paper biomass up to 800°C

by TGA experiments. The thermogram showed that selected catalysts devolatilized the biomass

at low (below 200°C) and moderate temperature (200–400°C). The copper loading order 30 > 20

> 10 wt%effectstemperature reduction.The catalysts with 10 and 20 wt% copper showed almost

same activity.In the presence of 30 wt% copperloaded catalyst the dehydration reaction was

enhanced almost 40%. With increase in the copper loading from 10 to 30 wt% the amount of

residue at the end of the reaction also decreased. Above 400°C,at higher temperature, the catalyst

16

with great amount of copper was more effective due to the increases in depolymerization

reaction aftercellulose de-hydration.

Zhang [71] et al 2010investigated the effect of ionic liquid and catalyst (crcl3 ) on the microwave

assisted pyrolysis of biomass including corn stalk ,rice straw and pine wood. The process were

carried out under controlled temperature and produced less cost and valuable chemicals.

Jun [72]et al 2010investigated the effect of ionic solvent (1 –butyl - 3 –methylimidazolium

chloride and 1–butyl -3-methylimidazolium tetrafluoroborate) on the microwave assisted

pyrolysis of biomass including rice straw and sawdust. The catalyst was believed to influence the

yield of product. The obtained product were analyzed by GC –MS and correlated with catalytic

activity and microwave absorption.

Moen [73] et al 2010investigated the effect of oxides, chlorides and nitrate of metals on the

microwave assisted pyrolysis of biomass using aspen as biomass. The catalyst was believed to

influence the yield of product as well their selectivity depending upon the nature of biomass

.metal oxides used for the pyrolysis of heavy oil. Addition of chlorides related with liquid. While

gasses were obtained using nitrate as catalyst.

Huang [74] et al 2010 investigated the production of fuel gas on the induced microwave assisted

pyrolysis using rice straw as biomass. The obtained product of gas were mainly composed H2,

CO2, CO along with some other chemicals.

Zhang [75] et al2010investigated the impact of catalyst on the yield of product from microwave

assisted pyrolysis of biomass using aspen as biomass. The steam produced during the process

pass to the catalyst under controlled temperature and condensed .The obtained products were

then analyzed using GC – MS.

Lu [76] et al 2010investigated the effect of nano –metal oxide (Ca, MgO, TiO2, Fe2O3, NiO and

ZnO) on the microwave assisted pyrolysis of biomass include poplar wood. The selectivity of the

product depends upon the nature of catalyst. Using CaO increased formation of cyclopentanone

and hydrocarbon. But decrease phenol and anhydro-sugar. The obtained product were analyzed

by Py - GC/MS.

17

Carlson [77] et al 2010 studied fast catalytic pyrolysis of Pine wood saw dust and furan (as

refrence biomass compound) with ZSM-5 based catalysts. They used three different reactors i.e a

bench scale bubbling fluidized bed reactor, a fixed bed reactor and a semi-batch pyroprobe

reactor.In the fluidized bed reactorhighest aromatic yield from sawdust of 14 % carbon was

obtained athigh temperature (600°C) and low biomass weight hourly space velocities (less than

0.5 hr-1).With a carbon yield of 5.4 %olefins were also produced.The biomass weight,the reactor

temperature and hourly space velocity greatly controlled both the aromatic yield and selectivity.

However, When olefins were recycled with biomass the aromatic yield increased up to 20 %

Carbon of biomass.

Patwardhan [78] et al 2010 investigated the effect of mineral salts on the chemical speciation

resulting from primary pyrolysis of cellulose. The microcrystalline powder of cellulose, with

particle size of 50 μm was used. while various concentrations of inorganic salts (NaCl, KCl,

MgCl2, CaCl2, Ca(OH)2, Ca(NO3)2, CaCO3 and CaHPO4) and switchgrass ash were mixed

with pure cellulose. Effects of minerals were the formation of

a) formic acid, glycolaldehyde and acetol as low molecular weight species.

b) Luran ring derivatives.

c) Anhydro sugar levo-glucosan.

They also investigated the pyrolysis speciation of pure and ash doped cellulose in a reaction

temperature ranging from 350-600°C.The temperatures and Mineral salts accelerated the

formation of low molecular weight species from cellulose.

Manon [79] et al 2010 carried out TGA and DSC experiments to determineendothermicity and

the reaction kinetics of the biomass pyrolysis reaction. The results showed that, the rate of

reaction constant and the heat of reaction were necessary parameters to design of a pyrolysis

reactor.The first order reaction rate constant was large and >0.5 s−1for most of biomass.While

the heat of reaction was in range of 207- 434 kJ kg−1. They suggested the following optimum

reaction conditions for biomass pyrolysis

(i) Particles sizeof Biomass should be less than 200 μm.

(ii) Heating rate of at least about 80 K min−1.

(iii) The reactor environment where the internal resistance to heat penetration

should be smaller than the external resistance to heat transfer.

18

Zhao [80] et al 2010studied anew method for hydrogen production from the biomass. The of

biomass pyrolysis and secondary decomposition of gaseous intermediate for hydrogen-rich gas

production was combined. The N2 and CO2 dilution to the energy density of gaseous products

were avoided. The conditions for hydrogen production were optimized .To find out the effects of

operating parameters on this twostep pyrolysis of biomass were analyzed through simulation of

thermodynamic equilibrium and experiments using Ni-cordierite catalyst. The results indicated

that the optimized conditions, including pyrolysis temperature 650°C, 18 minutes of residence

time, the second steppyrolysis temperature 850°C. The molar ratio ofsteam to carbonwas 2.All

the criteria for high hydrogen content and energy efficiencies were satisfied.The hydrogen

content of above 60% and hydrogen amount of around 65 g / kg biomass wasobtained using

optimumparameters. The Hydrogenrich gas was used in downstream fuel cells for the

implementation of distributed energy supply.And was also useful for production of pure

hydrogen.

Femandez [81] et al 2011 compared the pyrolysis of waste biomass materials (sewage sludge,

coffee hulls and glycerol) under conventional and microwaves heating. Using Sewage sludge

coffee hull and glycerol as waste materials. These materials were characterized by the

production of syngas. The production of syngas from these materials are different depend upon

their nature. Glycerol give largest amount of syngas, coffee hull intermediate sewage sludge

yield lowest concentration of the gas. But the amount of gas is greater in case of microwave

heating

Salema [82] et al 2011 investigated microwave assisted pyrolysis of biomass using oil palm as

biomass. Char was used as microwave absorbing material which absorb microwave radiations to

facilitate the process .The yield of pyrolyzing product depend upon biomass–microwave

absorbing materials. The product was analyzed for various characteristic properties.

Lei [83] et al 2011 investigated the effect of various parameters (reaction time, temperature and

power) on the yield of microwave assisted pyrolysis of biomass using distillers dried grain

soluble as biomass. And found that yield of product were changes with these parameters. The

obtained products were analyzed by GC-MS.

19

Yemis [84]et al 2011investigated the effect of acid on the microwave assisted pyrolysis of

biomass including xylose, xylan and straw. The catalyst were believed to influence the yield of

product as well as the effect of variables (Temperature, Time, pH).

Zhou [85] et al 2011investigated the effect of metal oxides and atmospheric conditions on the

microwave assisted pyrolysis of biomass include corn stove. The catalyst were belied to

influence the yield of product as well as reduced time for the completion of reaction. In order to

increase the range of temperature and thus less quantity of energy wereused for the process of

pyrolysis

Bu [86] et al 2011 investigated activated carbon effect as catalyst on the microwave assisted

pyrolysis of biomass using lignin .The catalyst were believed to effect the yield of fractions

(phenol, bio-oil ) as well as the nature of product of fraction by enhancing microwave

absorption. The obtained product were characterized by GC–MS and correlated with catalytic

activity and microwave absorption.

Chen [87]et al 2011checked the effect of sulfuric acid on the structure of biomass under

microwave assisted pyrolysis including sugar cane bagasse and lignocellulose. It was found that

the process were carried out under different temperature ranges and observe its effect on biomass

(lignocellulose bagasse) structure.

De Wild [88] et al 2011 pyrolyzed lignocelluloses for the production of chemicals. The focus

was to separate the three major constituents of lignocelluloses i.e. cellulose hemicelluloses and

lignin and then to convert each one into different chemicals. The efficiency of Staged

degasification and hybrid staged degasification was compared in the study. Staged degasification

was a step wise thermal processing (pyrolysis) while the hybrid staged degasification was a

combination of thermo-chemical reaction in which the media of reaction is different.the two

media were liquid phase treatment in water and gasphase pyrolysis. The first process gave below

1% yield of furfural and levoglucosan while the later gave above 5% yield of the same products.

Srinivasan [89] et al 2012 investigated the effect of H+ZSM -5 and different temperature ranges

on thermal pyrolysis of biomass. The catalysts were believed to influence the yield as well as the

nature of product.

20

Dutta [90] et al 2012 investigated the effect of metal chloride salt[ Zr (CO )and CrCl3 on the

microwave assisted pyrolysis of biomass including cellulose a sugar cane bagasse. The catalyst

were believed to influence the yield of product [5 –hydroxy methyl furfural (HMF) and 5 –

ethoxy methyl - 2 – furfural (EMF) and bio fuel].

Salema [91] et al 2012 investigated the effect of the ratio of biomass –activated carbon on the

microwave assisted pyrolysis of biomass using oil palm shell as biomass. The ratio of biomass –

activated carbon was believed to influence the yield of product. The product was bio-oil and

phenol contents. The highest bio-oil yield and phenol contents were obtained at the ratio of

10.5.The obtained products were analyzed by using GC –MS, FT-IR and 1H NMR.

Hu [92] et al 2012 investigated the effect of microwave range on the pyrolysis of microalgae

(Chlorella sp.) as biomass. The yield of product was maximum by using microwaves in the range

of 750 w.

Bu [93] et al 2012 investigated the catalytic effect of activated carbon on the microwave assisted

pyrolysis of biomass using lignocellulose as biomass. The use of activated carbon as catalyst

cause the decomposition of biomass .which yield high concentration of the product also the

concentration of the product was increase by the use of Zn powder in the presence of formic acid

/ethanol. The obtained product was analyzed by GC –MS and correlated with catalytic activity

and microwave absorption.

Shuttle worth [94] et al 2012 compared low temperature microwave assisted pyrolysis of

biomass with convential by using different types of feed stocks as biomass. The amount of

pyrolyzing gas was greater in case of low temperature pyrolysis than that of convential method.

The major components of the gas contain CO2, CO, CH4 along with small proportion of other

chemicals.

Wang [95] et al 2012 investigated heating properties of microwave on the pyrolysis of

microwave assisted pyrolysis of biomass by using corn Stover. Exothermic reaction occur during

the process due to which microwave assisted pyrolysis was a volumetric heating phenomena.

21

Zhao [96] at al 2012studded the effect of temperature on the microwave assisted pyrolysis of

biomass and characterized its various properties. The amount of gas increases when temperature

is increase.

Salema [97] et al 2012 investigated the effect of microwave absorbing materials(activated

carbon) on the microwave assisted pyrolysis of biomass using oil palm empty fruit bunch pellets

as biomass. The yield of product was directly related with temperature as well as microwave

absorbers. More product were obtained using microwave absorber compared with out .The

obtained products were analyzed by GC –MS and FT –IR.

Ren [98] et al 2012 studded the effect of reaction temperature and time on microwave assisted

pyrolysis of biomass including Douglas fir saw dust pellet as biomass. The yield of product were

developed both on the reaction temperature as well as time. The obtained products were analyzed

by GC –MS.

Wang [99] et al 2012 investigated the effect of ZsM -5 zeolite on the microwave assisted

pyrolysis of biomass using Douglas fir pellet as biomass. The catalyst was believed to influence

the yield of product by enhanced microwave absorption and in situe catalysis. The obtained

products were analyzed by GC –MS and correlated with catalytic activity and microwave

absorption.

Chen [100] et al 2012 investigated the effect of torrified biomass on the microwave assisted

pyrolysis of biomass using sugarcane bagasse. Under controlled temperature biomass were

torrified either by water or dilute sulfuric acid. Time and acid concentration were greatly

influence on the yield as well as their calorific values.

Yin [101] et al 2012 investigated 2nd generation biofuel production from waste materials of

biomass both on conventional and microwave assisted pyrolysis .These methods were used in

order to produced large yield of product .In microwave assisted pyrolysis more yield of product

were obtained than conventional one.

Patil [102] et al 2012 compared microwave assisted pyrolysis with supercritical methanol

method for the conversion of biomass ( algae ) into useful product and show the effect of

22

process parameters (reaction temperature and time ) both on the yield as well as the nature of the

product. The obtained product were analyzed by FT – IR and TGA techniques.

Arshad [103]et al 2012 used an overhead stirrer to pyrolyse biomass(oil palm shell) under

microwave (MW) irradiation. To investigate the effect on the temperature profile, product yield

and phenol content of the biooil,the ratio of biomass to activated carbon were varied. It was

interesting that they controlled the MW pyrolysis temperatureby changing the biomass to carbon

ratio. At a biomass to carbon ratio of 1 0.5,they obtained the highest biooil yield and phenol

content in biooil.They performed the chemical analysis of bio-oil using FT-IR, GC–MS and 1H

NMR techniques. The spectra indicated the composition of biooil mainly consisted on

aliphatic, aromatic,and compounds with high amounts of phenol. The pyrolysis

usingmicrowave with a stirrer were successful in producing highphenol content in biooil when

compared to other methods.

Ying [104]et al2012prepared bio-oil in a fast pyrolysis reactorfrom pine sawdust. They used a

series of catalyst (ruthenium) for the upgrading of biooil. They evaluated the catalytic activity

by the reaction of the reference compound i.e acetic acid using 3 MPa hydrogen pressure. They

studied the effects of Ru-loading and second metal addition on the catalytic activity. They

observed that the catalyst 0.5Ru/γ-Al2O3 with 0.5%Co addition shows the highest activity.It

gave the highest acetic acid conversion which is 30.98%. The properties of the pyrolysed bio-oil

were improvedafter upgrading over this catalyst. The esterscontent were increased by 2 folds in

the upgraded oil than in the raw one. The GC–MS analysis revealed that its not only the

hydrogenation,but esterification was also happening in the biooil over the CoRu/γ-Al2O3

catalyst. They concluded that the properties of bio-oil could also be improved by hydrotreating

and esterfication of carboxyl groups.

Liu [105] et al 2013investigated the effect of ZrCl4 and metal chloride on the microwave

assisted pyrolysis of biomass including carbohydrate. Indirect conversion of cellulosic materials

into HMF using metal chloride and then by direct converted under microwave assisted pyrolysis.

Abubakar[106] et al 2013investigated the effect of stirrer speed on the microwave assisted

pyrolysis of biomass using oil palm shell as biomass .The microwave absorber(activated carbon )

and stirrer speed were believed to influence the yield of product. The obtained product was

analyzed by GC –MS.

23

Beneroso [107] et al 2013 studied the production of syngas and H2 under microwave induced

pyrolysis of biomass including microalgae(scenedesmus almeriensis) .During the process large

amount of syngas along with hydrogen were produced. The product obtained from microwave

induced pyrolysis were compared with conventional pyrolysis.

Bu [108] et al 2013 investigated the effect of microwave absorbers (activated carbon) on the

microwave assisted pyrolysis of Douglas fir saw dust pellets. The catalyst were believed to

influence the yield of product as well as on their chemical composition. These catalysts were

used so many times after racialization.

Salema [109] et al 2013 investigate the effect of microwave heating on dielectric properties of

biomass including oil palm and biochar Co - axial probe. Were used to measure deictic

properties.

Fan [110] et al 2013 investigated. The effect of microwave heating on pyrolysis of cellulosic

materials under different temperature ranges. The obtained product were analyzed by HPLC,

C13NMR, FT –IR and CHN.

Wang [111] et al 2013 studied pyrolysis of biomass under fluidized bed reactor using

microalgae remnants (chlorella vulgris ) Lipid were obtained from the extraction of microalgae

and its residue were used as pyrolysed material .That produced a product which is a mixture of

various valuable solvents and chemicals.

Hussain [112]. et al 2013pyrolized the biomass using a temperature of 4000C ,time of 60

minute and 30% catalyst to biomass total weight. They used the optimum condition for second

steps reaction with changed concentration.that was the reason they obtained dense pyrolysate in

second step. The pyrolyser was made up of steel in which reaction was carried out. They

obtained 7% oil ,29% fuel gases, 14% water, and 50% char by this process. The product were

analyzed with GC-MS for the characterization of obtained products. They observed from spectra

that products obtained were mostly hydrocarbons.

Mohammad [113] et al 2014investigated copyrolysis of pine sawdust and switch grass biomass

with coal for the production of char. They investigated the influence of heat on the physical and

chemical properties of producedchar from biomass and coal at 1 atm pressure in a

24

N2atmosphere. The dependence of product physical properties like surface area on pyrolysis

temperature was shown by results. The adsorption capacity of char obtained from the Co-

pyrolysis of pine sawdust and switch grass at 750°C was different. The pine sawdust char had the

highest N2andCO2uptake, while that of switch grass had very lessnitrogen uptake, but high CO2

uptake. The copyrolysis in a TGA analyzer showed that devolatilization of the blended samples

of biomass and coal occurred independently.

Borges [114] et ,al 2014 investigated the effect of microwave absorbent on fast microwave

assisted pyrolysis of biomass using wood saw dust and corn Stover as biomass Silicon carbide

was used as microwave absorbent to increase the yield of the product. The obtain product was

analyzed and co related with microwave absorbent.

Wu [115]et al 2014 compared traditional and MV assisted pyrolysis based on yield as well as

influence of temperature, heating rate and power of microwave on microwave assisted pyrolysis.

Large amount of gases were released during conventional pyrolysis which were mainly

composed of a mixture of CO/CO2.while a mixture of H2/CH4 were produced during the

microwave assisted pyrolysis.

Xie [116] et al 2014 studied the effect of catalyst (HZSM -5) on the microwave assisted

pyrolysis of biomass including sewage sludge. The catalyst were influence the yield of product.

The yield of product greatly depend on temperature .The obtained product were analyzed by

XRD.

Borges [117] et al 2014investigated the effect of SiC (MW absorbent) and HzsM -5 (catalyst )

on the MV assisted pyrolysis of biomass including chlorella sp. Strain and

nannochloropisstrain.The catalyst were believed to influence the yield of product as well as with

different range of temperature .

Zhifeng Hu [118] et al 2015 produced syn gas from water hyacinth biomass inquartz tube

reactor. During this study he analyzed the fractional yield. He found that the particle size have

great effect on the water hyacinth pyrolysis. He selected particles size of dp‹ 200 µm for the

syngas production among the four sizes he studied. Different types of catalyst with different

temperature range were used byZhifeng Hu.The temperature of 9000C was the optimum

temperature. He found this temperature best for production of high concentration of synga. The

25

quality of syngas was enhanced by optimizing differnt catalyst. The best catalyst found was KCl,

followed by CaO and MgO.

26

CHAPTER –IIII

EXPERIMENTAL

3 MICROWAVE METAL INTERACTION PYROLYSIS OF BIOMASS USING

DIFFERENT METALS ANTENNAS

Three different metals were selected for this study

(i) Iron

(ii) Copper

(iii) Aluminum

All the coils were made from the wires which were purchased from the local Market and

used without further treatment. The copper wire has a purity of 99.9% and purchased from

the local market and made by Ravi wire industries of Pakistan. Aluminum wire claimed by

manufacturer as of 99.5% purity and made by Anping Gal Metal Wire Co., Ltd. This is a

Chinese metal wire industry. Iron wire of Carbon steel was also purchased from the local

merchant of the same company. Each of the wire has a thickness from 1-2.5 mm. The

internal diameter of coil was 50 mm and its height was 4.5 cm.

Similarly, three different catalysts were selected like

(i) Cement

(ii) Kaolin

(iii) Clinker

In this study Portland cement of Cherat cement Factory of Pakistan was used as catalyst in

addition to pharmaceutical grade kaolin of BDH England and clinker or burnt brick powder,

Burnt bricks were obtained from a brick kiln in Mardan area of KPK Pakistan. These bricks

gets almost vitrified due to overheating, the temperature for which is expected in the range of

1500-1800 oC. The bricks were crushed into fine powder and sieved using a mesh of 500

µm.

Different optimization studies were carried out for these three different metal antennas using

different catalyst .

27

Preparation of sample

Water hyacinth was selected as biomass. Biomass was collected in large amount from a pond of

district swabi (Khyber pakhtonkhawa, Pakistan). It was first washed with clean water to remove

soil from it and then cut down in to small pieces with the help of scissor. It was dried in the

presence of sun .The dried biomass was grinded to fine powder and this fine powder was used in

further studies.

Instruments

Domestic Microwave oven of sharp corporation having 2450 MHZ frequency and 1000 watt

power, GC-MS 600H jeol, Agilent 6890N gas chromatograph equipped with a fused capillary

column (HP.5L=30m, I.d = 0.32mm film thickness 0.25um) with Polydimethylsiloxane as

stationary phase were used.

Material / Chemicals Fine powder of biomass, commercial grade wires of selected metals (1.9

mm diameter) was used for the preparation of coil to be used as antenna for microwaves while

analytical reagent grade methanol was used as the solvent.

Reactor

The reactor for this work was made of the baked clay which is used as glass for drinking water

by the public. The selection of this was due to its low cost, resistance to the heat and its

compatible shape. The internal diameter of the reactor was 70mm and its length was10.5cm.The

lid has a side tube of 60cm.

28

Figure3.1 Diagram of Pyrex lid for the Baked Clay reactor.

Figure3.2 Baked Clay Reactor

29

MODIFICATION IN MICROWAVE OVEN

A domestic microwave oven of the Sharp Corporation Japan was slightly modified for this

reaction. A window of 50x50 dimensions was made in the side wall of the oven to connect the

side tube of the reactor with cooling assembly. The side wall of this oven was manipulated by

making and cutting a window 50x50 mm dimensions. This window allows the connection of side

tube of the baked clay reactor to cooling assembly and chemical traps. The baked clay reactor is

cylindrical in shape having a height of 10.5 cm. While its internal diameter 0.7 cm. The

mechanical strength of this reactor was enhanced by wrapping Teflon tape around the baked clay

vessel. This cylindrical container was closed with a Pyrex lid. This lid is associated with a side

tube having a length 30.5 cm and an internal diameter of 0.25 cm for distilling out the products

of pyrolysis. A modified microwave oven assembly is shown in figure 3.4.

Figure 3.3Figure Schematic diagram for the microwave metal interaction pyrolysis assembly

.

30

3.1 MICROWAVE METAL INTERACTION PYROLYSIS OF BIOMASS USING IRON

COIL ANTENNA

Procedure

Microwave metal interaction pyrolysis of biomass was first carried out using iron coil (1.9mm

gauge) as antenna without addition of catalyst. The coil was placed in the reactor on a clay disc.

This disc has a circumference of 60 mm. The idea behind the use of this disc was to avoid the

overheating of the bottom of reactor to protect breakage by heating. This was followed by

loading the coil with biomass powder. Some biomass was also placed around the coil for

maximum utilization of the generated heat. The reactor was closed with Pyrex lid and placed in

the microwave oven while passing the side tube through window of microwave oven. This was

followed by connecting the side tube with cold and chemical traps. Microwaves were applied in

pulses of two minutes to avoid damage of baked clay reactor due to over heating. Fuming

vapours were observed in the earlier 3 minutes after turning on the microwave oven. These

vapours displaces the small quantity of air entraped in the reactor and then the reaction takes

place in an air free atmosphere.The resuts are given in table 3.1. The oil obtained from this

pyrolysis was characterized using GC-MS and used as reference for furthur studies.

Table 3.1 Microwave metal interaction pyrolysis of Biomass without catalyst.

Metal % Wt. of

water

% Wt. of oil % Wt. Of gas % Wt. of residue % Efficiency

Iron 20.00 ±.90 12.00 ±.90 44.00±.90 24.00±.90 76.00 ±0.90

31

3.2OPTIMIZATION STUDIES FOR MICROWAVE METAL INETRACTION

PYROLYSIS OF BIOMASS USING CEMENT AS CATALYST IN IRON COIL

ANTENNA.

3.2.1 Investigation of the optimum ratio of biomass and cement catalyst for the microwave

metal interaction pyrolysis of biomass using Iron coil as antenna

Procedure

The mass of biomass was varied in the range of 1.0-10. While the mass of catalyst was kept

constant to investigate the effect of catalyst on this microwave assisted reaction. Each of the

experiment was conducted by heating that mixture for 15 minutes in the Iron coil inside the

baked clay reactor and placed on baked clay disc. The height of the coil was 1.4 cm its internal

diameter was 4.3 mm and external diameter was 4.8mm while the gauge of wire of coil

was1.9mm. Efficiency of the process was calculated by using following formula.

Table 3.2 Biomass to catalyst weight optimization for the cement catalyzed reaction

Biomass To

catalyst ratio

(BC) (g)

% Wt. of

water

% Wt. of

oil

% Wt. Of

gas

% Wt. of residue % Efficiency

11 25 5 35 35 65

21 25 5 37 33 67

31 24 5 41 30 70

41 25 7 41 28 72

51 25 7 44 24 76

61 25 7 46 23 77

71 25 7 52 16 84

81 25 9 55 14 86

91 25 9 57 10 90

101 25 9 56 10 90

32

3.2.2 Investigation of the optimum time for the microwave metal interaction Pyrolysis of

Biomass (Eichhornia crassipes) using cement as catalyst.

Procedure

Optimum time for the microwave metal interaction pyrolysis of biomass was investigated in the

range of 5-50 minutes. Each of the time optimization experiment were conducted using a mixture

of fine powder of the biomass and cement catalyst in 81 ratio (B C) and in triplicate. This

mixture was heated in an Iron coil reactor. The height of the coil was 1.4 cm its internal diameter

was 4.3 mm and external diameter was 4.8mm while the gauge of wire of coil was 1.9 mm. The

Results are given in table 3.3

Table 3.3 Time optimization for the cement catalyzed pyrolysis of biomass using iron coil

antenna

Time (min) %Wt. Of

Water

% Wt. of oil % Wt. of

Gas

% Wt. of

Residue

%Efficiency

5.0 5.0 0.0 5 90 10

10.0 15 0.5 55 30 70

15.0 18 2.0 52 28 72

20.0 20 3.0 57 20 80

25.0 22 5.0 54 20 80

30.0 22 5.0 55 18 82

35.0 22 5.0 58 15 85

40.0 22 5.0 58 15 85

45.0 22 5.0 58 15 85

50.0 22 5.0 58 15 85

33

3.2.3 Optimization of gauge of the wire for Iron coil antenna for the microwave assisted

Catalytic pyrolysis of biomass.

Iron coil antennas

Iron wires of different gauages (1.6mm, 2.7mm, 3.3mm) were used to form the iron coil antenna.

Procedure

The variation in relative amount of the fractions of microwave assisted catalytic pyrolysis of

biomass was investigated with variation in gauge of wire of Iron coil ( 1.6mm, 2.7mm and 3.3

mm). Each of the coil was used for heating a mixture of the fine powder of biomass and cement

catalyst in 81 ratio (B C) for 25 minutes. For each of the experiment the mixture was loaded to

the Iron coil inside the baked clay reactor and placed on a baked clay disc. The height of each of

the coil was 1.4cm, its internal diameter was 4.3 mm and external diameter was 4.8 mm. The

only difference between coils for each of the experiment was gauge of Iron wire. Results are

given in table 3.4.

Table 3.4 Investigation of the effect of gauge of Iron wire on microwave assisted catalytic

Pyrolysis of biomass using cement as catalyst

Gauge of wire (

mm)

% average wt. of

water

% average wt. of

oil

% average wt. of

gas

%average wt. Of

residue

1.6 15.00 3.00 67.00 15.00

2.7 19.00 5.00 61.00 16.00

3.3 16.00 9.00 58.00 17.00

34

3.3 OPTIMIZATION STUDIES FOR MICROWAVE-METAL (IRON) INTERACTION

PYROLYSIS OF BIOMASS USING KAOLINE AS CATALYST.

3.3.1Investigation of the optimum ratio of biomass and Kaolin catalyst for the microwave

metal interaction pyrolysis of biomass using Iron coil as antenna.

PROCEDURE

Optimum amount of catalyst was investigated by varying the ratio of biomass to catalyst in the

range of 11to10 ratios. Each of the experiment was conducted by heating that mixture for 15

minutes in the Iron coil through microwaves. The height of the coil was 1.4 cm its internal

diameter was 4.3 mm and external diameter was 4.8mm while the gauge of wire of coil was 1.9

mm. The product of pyrolysis were through condenser and cold traps. The Results are given in

table 3.5.

Table 3.5 Biomass to catalyst weight optimization for the Kaolin catalyzed reaction

Biomass To

catalyst ratio

(BC)

% Wt. of

water

% Wt. of oil % Wt. Of

gas

% Wt. of

residue

% Efficiency

11 25 4 32 39 61

21 25 4 33 38 62

31 25 4 36 35 65

41 25 7 35 33 67

51 25 7 39 30 70

61 25 7 41 27 73

71 25 9 41 25 75

81 25 9 44 22 78

91 25 9 52 19 81

101 25 9 59 13 87

35


Biomass (Eichhornia crassipes) using kaolin as catalyst

Procedure


range of 5-50 minutes. Each of the time optimization experiment was conducted using a mixture

of fine powder of the biomass and kaolin catalyst in 71 ratio (B C). this mixture was heated in an

Iron coil reactor. For each of the experiment the mixture was loaded to the Iron coil inside the

baked clay reactor and placed on baked clay disc microwave irradiation. The height of the coil

was 1.4 cm its internal diameter was 4.3 mm and external diameter was 4.8mm while the gauge

of wire of coil was 1.9 mm. Results are given in table 3.6.

Table 3.6 Time optimization for the kaolin catalyzed reaction

Time (min) %Wt. Of

Water


Gas

% Wt. of

Residue

%Efficiency

5.0 9.00 0.3 9.00 82.00 18.00

10.0 13.00 3.00 62.00 22.00 70.00

15.0 14.00 5.00 61.00 20.00 78.00

20.0 14.00 5.00 65.00 16.00 75.00

25.0 14.00 7.00 65.00 14.00 84.00

30.0 14.00 7.00 65.00 14.00 84.00

35.0 14.00 7.00 65.00 14.00 86.00

40.0 14.00 7.00 65.00 14.00 88.00

45.0 14.00 7.00 65.00 14.00 85.00

50.0 14.00 7.00 65.00 14.00 87.00

36

3.3.3 Optimization of gauge of the wire for Iron coil used as antenna for the microwave

assisted catalytic pyrolysis of biomass using kaolin as catalyst.

Procedure

The variation in relative amount of the products of microwave assisted catalytic pyrolysis of

biomass was investigated with variation in gauge of wire for coil using Iron coil made of wires

having a gauge of 1.6mm ,2.7mm ,and 3.3 mm. Each of the coil was used for heating a mixture

of the fine powder of biomass and cement catalyst in 7:1 ratio (B C) for 15 minutes. The height

of each of coil was 1.4cm, its internal diameter was 4.3 mm and external diameter was 4.8 mm.

The only difference between coils for each of the experiment was gauge of Iron wire. Results are

given in table 3.7.


pyrolysis of biomass using kaolin as catalyst

Gauge of wire (in

mm)

% average wt. of

water

% average wt. of

oil

% average wt. of

gas

%average wt. Of

residue

1.6 17.00 4.00 67.00 25.00

2.7 14.00 4.00 64.00 19.00

3.3 14.00 7.00 65.00 14.00

37

3.4OPTIMIZATION STUDIES USING CLINKER AS CATALYST.

3.4.1Investigation of the optimum ratio of biomass and clinker catalyst for the microwave

metal interaction pyrolysis of biomass using Iron coil as antenna

PROCEDURE

Biomass to catalyst ratio on relative fractions of the products was investigated by varying the

relative amount of biomass and catalyst as 11 to 101 ratios. Each of the experiment was

conducted in triplicate and by heating that mixture for 15 minutes in the Iron coil inside the

baked clay reactor. The height of the coil was 1.4 cm its internal diameter was 4.3 mm and

external diameter was 4.8mm while the gauge of wire of coil was 1.9 mm. The reactor was made

leak proof using Teflon tape. The reactor was placed in the modified microwave oven having a

window in the side wall through which the side tubes come out. The reaction was started

temperature and under ambient pressure. However the pressure and temperature changed during

the reaction.

Table 3.8 Biomass to catalyst weight optimization for the clinker catalyzed reaction

Biomass To

catalyst ratio

(BC)

% Wt. of

water % Wt. of

Oil

% Wt. Of gas % Wt. of

residue

% Efficiency

11 20 2 28 50 50

21 20 3 37 40 60

31 16 3 46 35 65

41 16 3 53 30 70

51 14 7 56 25 75

61 14 7 54 25 75

71 14 7 57 22 77

81 14 9 58 19 81

91 14 10 61 15 85

101 14 10 76 9 91

38


Biomass (Eichhornia crassipes) using clinker as catalyst

Procedure

Optimum time for the microwave metal interaction pyrolysis of biomass using clinker as catalyst

was investigated in the range of 5-50 minutes. Each of the time optimization experiment was

conducted using a mixture of fine powder of the biomass and clinker catalyst in 9:1 ratio (B C)

and in triplicate. For each of the experiment the mixture was loaded to the Iron coil inside the

baked clay reactor and placed on baked clay disc. The height of the coil was 1.4 cm its internal

diameter was 4.3 mm and external diameter was 4.8mm while the gauge of wire of coil was 1.9

mm. The reactor was made leak proof using Teflon tape. The reactor was placed in the modified

microwave oven having a window in the side wall through which the side tubes come out. The

time optimization experiments were conducted by heating the mixture of biomass and catalyst

for different time interval. Results are given in table 3.9.

Table 3.9 Time optimization for the clinker catalyzed pyrolysis.

Time (min) %Wt. Of

Water

% Wt. of

oil

% Wt. of

Gas

% Wt. of

Residue

%Efficiency

5.0 7.00 0.00 7.00 86.00 14.00

10.0 14.00 1.00 53.00 32.00 55.00

15.0 15.00 2.00 60.00 23.00 74.00

20.0 15.00 4.00 65.00 14.00 75.00

25.0 15.00 4.00 67.00 14.00 84.00

30.0 15.00 4.00 67.00 14.00 84.00

35.0 15.00 4.00 67.00 14.00 86.00

40.0 15.00 4.00 67.00 14.00 88.00

45.0 15.00 4.00 67.00 14.00 85.00

50.0 15.00 4.00 67.00 14.00 87.00

39

3.4.3 Optimization of gauge of the wire for Iron coil used as antenna for the microwave

assisted catalytic pyrolysis of biomass using clinker as catalyst

Procedure



having a gauge of1.6mm,2.7mm and 3.3 mm. Each of the coil was used for heating a mixture of

the fine powder of biomass and clinker catalyst in 91 ratio (B C) for 15 minutes. For each of the

experiment the mixture was loaded to the Iron coil inside the baked clay reactor and placed on a

baked clay disc. The height of each of the coil was 1.4 cm, its internal diameter was 4.3 mm and

external diameter was 4.8 mm. The only difference between coils for each of the experiment was

gauge of Iron wire. Results are given in table 3.10.


pyrolysis of biomass.

Gage of wire (in

mm)

% average wt. of

water

% average wt.

of oil

% average wt. of

gas

%average wt. Of

residue

1.6 18.00

5.00 56.00 22.00

2.7 13.00

5.00 64.00 19.00

3.3 13.00

7.00 62.00 19.00

3.5 MICROWAVE METAL INTERACTION PYROLYSIS OF BIOMASS USING

COPPERCOIL ANTENNA

Instruments and reactor

Instrument and reactor used in this study were same as use in case of Copper coil antenna.

Material/ chemicals

Fine powder of biomass, commercial grade copper was used for the preparation of coil to be

used as antenna for microwaves .while analytical reagent grade methanol was used as the

solvent.

40

Procedure

Microwave metal interaction pyrolysis of biomass was first carried out using copper coil

(2.5mmgauge) as antenna without addition of catalyst. The coil was placed in the reactor on a

clay disc. This disc has a circumference of 60 mm. The idea behind the use of this disc was to

avoid the overheating of the bottom of reactor to protect breakage by heating. This was followed

by loading the coil with biomass powder. Some biomass was also placed around the coil for


the microwave oven. While passing the side tube through window of microwave oven. This was





place in an air free atmosphere.The resuts are given in table 3.11. The oil obtained from this

pyrolysis was characterized using GC-MS and used as reference for furthur studies

Table3.11Microwave metal interaction pyrolysis of Biomass withouth catalyst.

Metal % Wt. of

water

% Wt. of oil % Wt. Of gas % Wt. of residue % Efficiency

Copper 15.0 ±0.80 10.00 ±0.80 35.0±0.80 40.00 ±0.80 60.00

3.6 OPTIMIZATION STUDIES USING COPPER COIL ANTENNA FOR DIFFERENT

CATALYST.

3.6.1Investigation of the optimum ratio of biomass and cement catalyst for the microwave

metal interaction pyrolysis of biomass using copper coil as antenna

Material / Chemicals

Fine powder of biomass, commercial grade Copper wire of 2.5 mm diameter was used for the

preparation of coil to be used as antenna for microwaves while analytical reagent grade methanol

was used as the solvent.

41

PROCEDURE

Effect of the amount of catalyst (Biomass to catalyst ratio) on relative fractions of the products of

catalytic pyrolysis of biomass was investigated by varying the relative amount of biomass and

catalyst in the range 11to110. Each of the experiment was conducted by heating that mixture for

30 minutes in the copper coil inside the baked clay reactor and placed on baked clay disc. The

height of the coil antenna was 4.3 cm its internal diameter was 4.3 mm and external diameter

was 4.8mm while the gauge of wire of coil was 2.5 mm. The reactor was made leak proof using

Teflon tape. The reactor was placed in the modified microwave oven having a window in the

side wall through which the side tubes are connected.

Table 3.12 Biomass to catalyst weight optimization for the cement catalyzed reaction

Biomass To

catalyst ratio

(BC)

% Wt. of

water


gas


11 15.00 17.00 33.00 35.00 65.00

21 15.00 17.00 33.00 35.00 65.00

31 15.00 18.00 34.00 34.00 66.00

41 15.00 18.00 33.00 34.00 66.00

51 15.00 20.00 31.00 33.00 67.00

61 15.00 19.00 33.00 33.00 67.00

71 15.00 18.00 34.00 32.00 67.00

81 15.00 18.00 35.00 32.00 68.00

91 15.00 17.00 36.00 32.00 68.00

101 15.00 17.00 36.00 32.00 68.00

42


Biomass (Eichhornia crassipes) using cement as catalyst

PROCEDURE


range of 10-50 minutes. Each of the time optimization experiment was conducted using a

mixture of fine powder of the biomass and cement catalyst in 61 ratio (B C). For each of the

experiment the mixture was loaded to the copper coil inside the baked clay reactor and placed on

baked clay disc. The height of the coil was 4.3 cm its internal diameter was 4.3 mm and external

diameter was 4.8mm while the gauge of wire of coil was 2.5 mm. The reactor was made leak

proof using Teflon tape. The reactor was placed in the modified microwave oven having a

window in the side wall through which the side tubes come out. The time optimization

experiments were conducted by heating the mixture of biomass and catalyst for different time

intervals. Results are given in table 3.13.

Table 3.13 Time optimization for the cement catalyzed pyrolysis of Biomass using copper

antenna.

Time (min) %Wt. Of

Water

% Wt. of

oil

% Wt. of

Gas

% Wt. of

Residue

%Efficiency

5.0 0.00 0.00 0.00 100 0.00

10.0 10.00 6.00 42.00 54.00 46.00

15.0 13.00 11.00 44.00 41.00 59.00

20.0 15.00 17.00 33.00 38.00 62.00

25.0 15.00 20.50 31.50 33.00 67.00

30.0 15.00 20.00 35.00 30.00 70.00

35.0 15.00 20.00 36.00 29.00 71.00

40.0 15.00 20.00 36.00 29.00 71.00

45.0 15.00 20.00 36.00 29.00 71.00

50.0 13.00 20.00 36.00 29.00 71.00

43

3.6.3 Optimization of gauge of the wire for copper coil as antenna for the microwave


PROCEDURE


biomass was investigated with variation in gauge of wire for coil using copper coil made of wires

having a gauge of 2.5, 1.7, 1.5 and 0.9 mm. Each of the coil was used for heating a mixture of

the fine powder of biomass and cement catalyst in 51 ratio (B C) for 25 minutes. For each of the

experiment the mixture was loaded to the copper coil inside the baked clay reactor and placed on

a baked clay disc. The height of each of the coil was 4.3 cm, its internal diameter was 4.3 mm

and external diameter was 4.8 mm. The only difference between coils for each of the experiment

was gauge of copper wire. Results are given in table 3.14.

Table 3.14 Investigation of the effect of gauge of copper wire using cement catalyst

Gauge of wire

(in mm)

% Average wt. of

water

% Average wt. of

oil

% Average wt. of

gas

% Average wt.

Of residue

0.90 15.00

17.00 32.00 36.00

1.50 15.00

17.00 32.00 36.00

1.70 15.00

18.00 32.00 35.00

2.50 15.00

20.00 32.00 33.00

44

3.7Investigation of the optimum ratio of biomass and kaolin catalyst for the microwave


PROCEDURE



catalyst in the range 11to110. Each of the experiment was conducted by heating that mixture for

24 minutes in the copper coil inside the baked clay reactor and placed on baked clay disc. The

height of the coil was 4.3 cm its internal diameter was 4.3 mm and external diameter was 4.8mm

while the gauge of wire of coil was 2.5 mm. The reactor was made leak proof using Teflon tape.

The reactor was placed in the modified microwave oven having a window in the side wall

through which the side tubes come out. The reaction was started just at room temperature and

under ambient pressure. However the pressure and temperature changed during the reaction.

Table 3.15 Biomass to catalyst weight optimization for the Kaolin catalyzed pyrolysis in

copper coil

Biomass To

catalyst ratio

(BC)

% Wt. of

water

% Wt. of oil % Wt. Of gas % Wt. of

residue

% Efficiency

11 17 12 58 13 87

21 16 13 48 23 77

31 15 15 46 24 76

41 15 16 44 25 75

51 15 15 42 28 72

61 15 13 43 29 71

71 15 13 43 29 72

81 15 11 44 30 70

91 15 11 44 30 70

101 15 11 44 30 73

45



PROCEDURE


range of 10-50 minutes. Each of the time optimization experiment was conducted using a

mixture of fine powder of the biomass and cement catalyst in 41 ratio (B C). This mixture was

heated in a copper coil reactor. For each of the experiment the mixture was loaded to the copper

coil inside the baked clay reactor and placed on baked clay disc. The height of the coil was 4.3

cm its internal diameter was 4.3 mm and external diameter was 4.8mm while the gauge of wire

of coil was 2.5 mm. The reactor was made leak proof using Teflon tape. The reactor was placed

in the modified microwave oven having a window in the side wall through which the side tubes

come out. The reaction was started just at room temperature and under ambient pressure.

However the pressure and temperature changed during the reaction. Results are given in table

3.16.

3.16 Time optimization for the Kaolin catalyzed reaction

Time(min)

% wt. of

water

% wt. of oil % wt. of gas % wt. of

residue

% efficiency

5.00 0.00 0.00 0.00 100.00 0.00

10.00 4.00 5.00 66.00 25.00 75.00

15.00 7.00 7.00 62.00 24.00 76.00

20.00 7.00 8.00 60.00 25.00 75.00

25.00 8.00 8.00 65.00 19.00 81.00

30.00 8.00 9.00 67.00 16.00 84.00

40.00 8.00 9.00 67.00 16.00 84.00

45.00 8.00 9.00 67.00 16.00 84.00

50.00 8.00 9.00 67.00 16.00 84.00

46

3.7.2 Optimization of gauge of the wire for copper coil used as antenna for the microwave

assisted catalytic pyrolysis of biomass using kaolin as catalyst

PROCEDURE



having a gauge of 2.5, 1.7, 1.5 and 0.9 mm were used in this study . Each of the coil was used for

heating a mixture of the fine powder of biomass and cement catalyst in 41 ratio (B C) for 30

minutes. For each of the experiment the mixture was loaded to the copper coil inside the baked

clay reactor and placed on a baked clay disc. The height of each of the coil was 4.3 cm, its

internal diameter was 4.3 mm and external diameter was 4.8 mm. Results are given in table 3.17.

Table 3.17 Investigation of the effect of gauge of copper wire on microwave assisted

catalytic pyrolysis of biomass using kaolin as catalyst

Gauge of wire (in

mm)

% average wt. of

water

% average wt. of

oil

% average wt. of

gas

%average wt. Of

residue

0.9 9

2.7 64 22

1.5 15

2.7 56 24

1.7 7.00

3 64 23

2.5 13.00

5 58 22

3.7.3Investigation of the optimum ratio of biomass and clinker catalyst with copper coil as

antenna

PROCEDURE



catalyst in the range 1:1to 1:10. Each of the experiment was conducted by heating that mixture

47

for 25minutes in the copper coil inside the baked clay reactor and placed on baked clay disc. The

height of the coil was 4.3 cm its internal diameter was 4.3 mm and external diameter was 4.8mm

while the gauge of wire of coil was 2.5 mm. Results are given in table3.18.

Table 3.18 Biomass to catalyst weight optimization for the clinker catalyzed reaction

Biomass To

catalyst ratio

(BC)

% Wt. of

water % Wt. of

Oil

% Wt. Of

gas


11 20 2 28 50 50

21 20 3 37 40 60

31 16 3 46 35 65

41 16 3 53 30 70

51 14 7 56 25 75

61 14 7 54 25 75

71 14 7 57 22 77

81 14 9 62 15 81

91 14 10 61 15 85

101 14 10 76 15 85



PROCEDURE



of fine powder of the biomass and clinker catalyst in 91 ratio (B C). This mixture was heated in a

copper coil reactor. Results are given in table 3.19.

48

Table 3.19 Time optimization for the clinker catalyzed reaction

Time(min) %Wt. Of

water

% Wt. Of oil %Wt. of gas % Wt. Of

residue

%Efficiency

5.0 8.00 1.00 6.00 85.00 15.00

10.0 8.00 4.00 44.00 45.00 55.00

15.0 13.00 8.00 44.00 36.00 64.00

20.0 13.00 8.00 50.00 30.00 70.00

25.0 10.00 8.00 52.00 30.00 70.00

30.0 13.00 8.00 53.00 26.00 74.00

35.0 8.00 9.00 58.00 26.00 74.00

40.0 8.00 9.00 58.00 26.00 74.00

45.0 8.00 9.00 58.00 26.00 74.00

50.0 8.00 9.00 58.00 26.00 74.00

3.7.5 Optimization of gauge of the wire for copper coil used as antenna and clinker as


PROCEDURE




the fine powder of biomass and clinker catalyst in 91 ratio (B C) for 35 minutes. Results are

given in table 3.20.

Table 3.20 Investigation of the effect of gauge of copper wire on microwave assisted


Gage of wire (in

mm)

% average wt. of

water

% average wt. of

oil

% average wt. of

gas

%average wt. Of

residue

0.9 12 2 62 22

1.5 12 2 64 19

1.7 12 3 66 16

2.5 12 6 64 16

49

3.8 MICROWAVE METAL INTERACTION PYROLYSIS OF BIOMASS USING

ALUMINIUM COIL ANTENNA

Procedure

Microwave metal interaction pyrolysis of biomass was first carried out using aluminium coil

(1.79mm gauge) as antenna without addition of catalyst. The coil was placed in the reactor on a

clay disc. This disc has a circumference of 60 mm. The idea behind the use of this disc was to

avoid the overheating of the bottom of reactor to protect breakage by heating. This was followed

by loading the coil with biomass powder. Some biomass was also placed around the coil for


the microwave oven while passing the side tube through window of microwave oven. This was





place in an air free atmosphere.The resuts are given in table 3.21.

Table3.21 Microwave metal interaction pyrolysis of Biomass without catalyst.

Metal % Wt. of

water


gas

% Wt. of residue % Effiency

Aluminium 15.00±0.90 6.00±0.90 51.00

±0.90

24.00 ±0.90 76.00 ± 0.90

3.9 OPTIMIZATION STUDIES FOR DIFFERENT CATALYSTS USING ALUMINIUM

COIL AS ANTENNA.

3.10.1Investigation of the optimum ratio of biomass and cement catalyst for the microwave

metal interaction pyrolysis of biomass using Aluminium coil as antenna.

Material / Chemicals

Fine powder of biomass, commercial grade Aluminium wire of 1.68 mm diameter was used for

the preparation of coil to be used as antenna for microwaves while analytical reagent grade

methanol was used as the solvent.

50

PROCEDURE



catalyst in the range 11to 110.Each of the experiment was conducted by heating that mixture for

20 minutes in reactor using aluminium coil antenna. The height of the coil was 6cm its internal

diameter was 4.3 mm and external diameter was 4.8mm while the gauge of wire of coil was

1.68mm. The reactor was made leak proof using Teflon tape. The reactor was placed in the

modified microwave oven having a window in the side wall through which the side tubes come

out. The reaction was started just at room temperature and under ambient pressure. However the

pressure and temperature changed during the reaction. The results are given in table 3.22.

Table 3.22 Biomass to catalyst weight optimization for the cement catalyzed reaction in

Aluminium coil

Biomass To

catalyst ratio

(BC)

% Wt. of

water

% Wt. of

oil

% Wt. Of

gas


11 15.00 6.00 46.00 33.00 67.00

21 15.00 7.00 56.00 22.00 78.00

31 15.00 8.00 62.00 15.00 85.00

41 15.00 10.00 60.00 15.00 85.00

51 15.00 10.00 61.00 14.00 86.00

61 15.00 6.00 65.00 14.00 86.00

71 15.00 6.00 65.00 13.00 87.00

81 15.00 6.00 67.00 13.00 87.00

91 15.00 6.00 67.00 13.00 87.00

101 15.00 6.00 67.00 13.00 87.00

51


Biomass (Eichhornia crassipes) using cement as catalyst

PROCEDURE



of fine powder of the biomass and cement catalyst in 51 ratio (B C). Results are given in table

3.23.

Table 3.23 Time optimization for the cement catalyzed pyrolysis of Biomass in aluminium

coil.

Time (min) %Wt. Of

Water

% Wt. of

oil

% Wt. of

Gas

% Wt. of

Residue

%Efficiency

5.0 6.6 0.0 40.1 53.3 46.7

10.0 13.3 4.6 48.8 33.3 66.7

15.0 15.0 7.0 44.8 33.2 66.8

20.0 15.0 8.0 57.0 20.0 80.0

25.0 15.0 10.0 55.0 20.0 80.0

30.0 15.0 10.0 58.4 16.6 83.4

35.0 15.0 10.0 58.4 16.6 83.4

40.0 15.0 10.0 58.4 16.6 83.4

45.0 15.0 10.0 58.4 16.6 83.4

50.0 15.0 10.0 58.4 16.6 83.4

52



PROCEDURE


biomass was investigated with variation in gauge of wire for coil using Aluminium coil made of

wires having a gauge of 1.5mm, 1.00mm,1.28mm and 0.7 mm. Each of the coil was used for

heating a mixture of the fine powder of biomass and cement catalyst in 51 ratio (B C) for

25minutes. For each of the experiment the mixture was loaded to the Aluminium coil inside the

baked clay reactor and placed on a baked clay disc.. Results are given in table 3.24.

Table 3.24 Investigation of the effect of gauge of Aluminium wire on microwave assisted


Gauge of wire

( mm)

% average wt. of

water

% average wt. of

oil

% average wt. of

gas

%averagewt.Of

residue

0.7 16.30 2.20 60.80 20.60

1.00 15.90 1.80 68.20 13.90

1.28 16.00 1.90 58.20 24.00

1.59 18.60 1.80 58.80 20.60

53

3.11 OPTIMIZATION STUDIES USING KAOLIN AS CATALYST.

3.12.1Investigation of the optimum ratio of biomass and kaolin catalyst for the microwave

metal interaction pyrolysis of biomass using Aluminium coil as antenna

Table 3.25 Biomass to catalyst weight optimization for the kaolin catalyzed reaction

Biomass To

catalyst ratio

(BC)

% Wt. of

water

% Wt. of

oil

% Wt. Of

gas


11 15.00 6.00 46.00 33.00 67.00

21 15.00 6.00 55.00 24.00 76.00

31 15.00 7.400 55.00 22.20 77.70

41 15.00 7.400 56.80 20.80 79.10

51 15.00 10.00 59.00 16.00 84.00

61 15.00 9.00 60.50 15.50 84.40

71 15.00 8.80 61.00 15.20 84.70

81 15.00 8.50 61.50 15.00 85.00

91 15.00 8.50 61.50 15.00 85.00

101 15.00 8.90 61.10 15.00 85.00



PROCEDURE



of fine powder of the biomass and kaolin catalyst in 51 ratio (B C. Results are given in table

3.26.

54

Table 3.26 Time optimization for the kaolin catalyzed pyrolysis of Biomass using

aluminium coil antenna

Time (min) %Wt. Of

Water

% Wt. of

oil

% Wt. of

Gas

% Wt. of

Residue

Efficiency

5.0 3.10 0.00 53.20 43.7 56.2

10.0 13.00 4.00 56.00 27.00 73.00

15.0 15.00 6.00 58.50 20.50 79.50

20.0 15.00 8.60 60.10 16.3 83.70

25.0 15.00 10.40 59.60 15.00 85.00

30.0 15.00 10.40 59.60 15.00 85.00

35.0 15.00 10.40 59.60 15.00 85.00

40.0 15.00 10.40 59.60 15.00 85.00

45.0 15.00 10.40 59.60 15.00 85.00

50.0 15.00 10.40 59.60 15.00 85.00

3.12.3 Investigation of the effect of gauge of Aluminium wire on microwave assisted


PROCEDURE


biomass was investigated with variation in gauge of wire for coil using aluminium coil made of

wires having a gauge of 1.5mm, 1.00mm, 1.28mm and 0.7 mm. Each of the coil was used for

heating a mixture of the fine powder of biomass and kaolin catalyst in 51ratio (B C) for

25minutes. Results are given in table 3.27.


catalytic pyrolysis of biomass using kaolin as catalyst

Gage of wire (in

mm)

% average wt. of

water

% average wt. of

oil

% average wt. of

gas

%average wt. Of

residue

0.7 12.8 2.8 64.5 20.00

1.00 9.6 0.6 54.9 22.20

1.28 16 1.4 61.4 21.20

1.95 15.2 1.4 63.4 20.00

55

3.13 OPTIMIZATION STUDIES FOR CLINKER CATALYST.

3.14.1Investigation of the optimum ratio of biomass and clinker catalyst for the microwave

metal interaction pyrolysis of biomass using Aluminium coil as antenna

PROCEDURE



catalyst in the range 11to110. The results are given in table 3.28.

Table 3.28 Biomass to catalyst weight optimization for the clinker catalyzed pyrolysis

Biomass to

catalyst ratio

% Wt. of

water

% Wt. of

oil

% Wt. Of

gas

% Wt. of

residue

% Efficiency

11 15.00 5.30 49.70 30.00 70.00

21 15.00 6.00 59.00 20.00 80.00

31 15.00 8.60 61.4 15.00 85.00

41 15.00 10.50 61.50 13.00 87.00

51 15.00 11.00 62.00 12.00 88.00

61 15.00 10.50 62.90 11.60 88.40

71 15.00 10.50 63.10 11.40 88.60

81 15.00 10.50 63.30 11.20 88.80

91 15.00 10.50 63.40 11.10 88.90

101 15.00 10.50 63.40 11.10 88.90

56



PROCEDURE



of fine powder of the biomass and clinker catalyst in 51 ratio (B C). Results are given in table

3.29.

Table 3.29 Time optimization for the clinker catalyzed reaction in aluminium coil

Time (min) %Wt. Of

Water


Gas

% Wt. of

Residue

Efficiency

5.0 6.20 0.00 10.50 83.30 16.60

10.0 13.80 4.10 54.10 28.00 72.00

15.0 14.00 6.20 60.20 19.60 83.30

20.0 15.00 7.50 60.90 16.60 83.30

25.0 15.00 10.30 61.20 13.50 86.50

30.0 15.00 10.50 62.00 12.50 87.50

35.0 15.00 10.50 62.00 12.50 87.50

40.0 15.00 10.50 62.00 12.50 87.50

45.0 15.00 10.30 62.20 12.50 87.50

50.0 15.00 10.30 62.20 12.50 87.50

57



Procedure




heating a mixture of the fine powder of biomass and kaolin catalyst in 51ratio (B C) for

25minutes. Results are given in table 3.30.


catalytic pyrolysis of biomass using clinker as catalyst

Gauge of wire ( mm) % average wt.

of water

% average wt. of

oil

% average

wt. of gas

%average wt.

Of residue

0.7 16.1 3.0 65.8 15

1.00 14.1 1.1 61.5 23.3

1.28 14.5 1.6 60.6 23.3

1.59 16.1 2.6 63.7 17.4

3.15 CHARACTERIZATION STUDIES

Oil fractions obtained after optimization studies for all the three metals using different catalysts

were characterized by using GC-MS. GC-MS model 600H jeol, Agilent 6890N gas

chromatograph equipped with a fused capillary column (HP.5L=30m, I.d = 0.32mm film

thickness 0.25um) with Polydimethylsiloxane as stationary phase were used for analysis.Results

are given in chapter 4.

58

CHAPTER –IV

RESULTS AND DISCUSSION

4 The Idea of catalytic and microwave metal interaction pyrolysis of biomass

Microwave heating is a faster and volumetric heating. However the heating of metal by

microwaves is a surface phenomenon and is due to the reflection of microwaves from the metals.

Microwaves may penetrate into a very small fraction of the metal. This small fraction of the

metal surface through which the microwaves penetrate is called the skin or skin depth[119].The

skin of metals vary according to the nature of metals [120]. When the microwaves falls on the

surface of metals it penetrates in the skin and then reflects. This interaction results heating and

sparking of the metal due to the variation in electronic and atomic moments [121]. This may

result as high temperature as the melting point of metals [122]. The amount of heat may vary

with variation in the microwave power and the surface area and incidence angle [123].

Microwave metal interaction pyrolysis is based on the idea to heat up metals to as high

temperature as the melting point of metals and utilize the generated heat for the decomposition of

biomass to bio oil and biogas. This utility of heat avoids the melting of metal. This is

characterized for high temperature and faster heating as compared to the conventional conviction

process. This is also responsible for kinetic selectivity. The faster heating avoids many of the

side and secondary reaction ensuring selectivity of the product. In this pyrolysis it is intended to

produce bio oil of upgraded nature which means lower oxygen contents, less water and greater

quantities of the organic combustible matter. This is carried out by the use of catalyst. Where the

clinker and clay catalyst catalyze the process for ensuring greater quantities of hydrocarbon rich

bio oil. The molecular holes and characteristic chemical structure and composition of the catalyst

lesser the quantity of water produced during the biomass degradation process.

4.1Cement weight optimization using iron antenna

Both the nature and relative quantity of Solid catalyst may play role in determining the nature of

products, yield of the process and the relative amount of the gaseous, aqueous, oil and residue

fractions [124]. The present work employs a system where there is no gas nor liquid to be used

as medium for fluidizing the medium. However the products produced during the process may

act as fluidizing medium. In the start this is a static process and later on a hybrid of static and

59

fluidized bed. In this case the relative amount of catalyst may be detrimental in yield and

relative amount of the fractions obtained by the microwave assisted thermo-catalytic degradation

of water hyacinth. Using iron coil as antenna for the microwave heating the relative mass of

water hyacinth and cement catalyst was varied in the range of 11to110. Results are given in

figure 4.1. In this case the progress of reaction was noted in terms of the % mass of oil and %

efficiency of the process. Which was determined using the following formula.

Variation in the amount of oil and % efficiency can be observed from the figure 4.1. It can be

seen from the figure that the amount of oil varies in a regular way in longer range of

concentrations interval. Three intervals of concentration can be observed in the graph. It can

further be observed that both the amount of oil and efficiencies are lower at high concentration of

catalyst relative to the amount of biomass. This is because of a number of reasons including the

aglomeration and settling down of catalyst at relatively high concentration of catalyst due to

which most of the catalyst is not available for reaction and the efficiency is less. There is more

charing and gassification that is why the amount of both gases and residue inreases while that of

bio oil decreases. This trend changes with change in relative concentration of the catalyst and the

catalyst remains bouyant by the produced vapours and gases at relatively lower concentrations of

the catalyst. That is why the greater surface of catalyst is available and the amount of oil

increases and that of residue decreases resulting increase in efficiency of the process. Unlike

simple thermocatalytic conversion of biomass [125], this catalytic and microwave metal

interaction pyrolysis of biomass have different mechanisim here the oxides of metals may act as

microwave absorber which enhances the heat contents of the system and ensures smoother

pyrolytic degradation. The structural features of the catalyst are responsible for stabilisation of

some of the reactive species and determining the chemical nature of the resulting oil and gaseous

products of pyrolysis of biomass.

60

1:1 2:1 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

5

6

7

8

9

% w

eigh

t of o

il

Biomass: catalyst ratio

Figure 4.1Optimization of the relative amount of catalyst.

61

4.2 Time optimization for cement catalyzed and iron antenna (microwave metal


Economy of a process may depend upon a number of factors including the input energy, cost of

the raw material as well as catalyst and speed of reaction. The input energy is one of the

important time dependent parameter. Longer process times are associated with greater

consumption of power and fuel. Reaction time optimization studies may ensure maximum yields

as well as save fuel and power. This study was conducted in time variation of 5-50 minutes. Each

of experiments were performed in triplicate and average of the these are reported in table 3.2

.Figure 4.2 shows that the amount of residue decreases with increase in the reaction time with an

appropriate increase in the amount of liquid and gaseous product. It can be seen from the table

that the process maximums yield of oil when the time of reaction is 25 minutes. Beyond this

there is no change in the amount of oil. While amount of gaseous product increases .The%

efficiency of process also increases by increasing the time. But the oil product remains same.

Therefore we select 25 minutes as optimum time for pyrolysis of biomass and this was selected

as the optimum time for reaction.

62

0 10 20 30 40 50

0

1

2

3

4

5%

we

igh

t o

f o

il

Time (minutes)

Figure 4.2 Time optimization for the cement catalyzed Biomass pyrolysis using iron

coil as antenna.

63

4.3 Optimization of the gauge of wire for Iron coil antenna

This process of the pyrolytic conversion of biomass into bio oil uses the interaction of

microwaves with metals. In this microwave metal interaction large quantity of heat is produced

which is utilized for the thermal degradation of biomass. The amount and sustainability of this

heat depends upon the nature of metal which is iron in this case. It also depends upon the shape

of the metal in which it is employed for example strip, wire and cylinder [126]. It has been

reported by our group that tightly coiled wires can produce larger quantities of heat for effective

pyrolysis as compared to strips and cylinders [127]. Here the amount of heat depends upon the

number of turns of coil and even the diameter of the coil which ensures repeated reflections and

skin penetrations [121]. Here we also expect that variation in gauge of the wire may also change

the amount of heat [128]. Variation in the gauge affect the amount of heat in two ways; variation

in the number of turns which varies the number of skins and even interactionsor it may also

changes the number of secondary interactions of microwave with the metal.Results are given in

table 3.3.

Microwave- metal (Iron) interaction pyrolysis of Biomass using kaolin as catalyst.

4.4Investigation of the optimum ratio of biomass and Kaolin catalyst for the microwave

metal interaction pyrolysis of biomass using Iron coil as antenna.

The nature of catalyst as well as the amount of catalyst is important for the thermo-catalytic

cracking of biomass [129]. Variation in the relative amount of catalyst may change both the

nature and relative amount of the fractions of various products [130]. In this case of microwave

metal interaction pyrolysis the catalyst may be considered as responsible for the absorption of

microwaves, for directing the microwaves and catalyzing the degradation of biomass as well as

formation of upgraded bio-oil. It is expected that the catalytic behavior of kaolin in this

microwave assisted reaction is different from ordinary thermo-catalytic degradation. Kaolin is

composed of the silicates which are associated with dipole moment. Absorption of the

microwave changes the polarity of these silicates resulting difference in catalytic behavior of the

kaolin. This kaolin catalyzed reaction is expected to produce upgraded bio oil of improved yield.

The catalyst weight optimization studies were conducted by varying the relative weight of water

hyacinth and catalyst in the range of 1:1to1:10.Each of the experiment was conducted by heating

that mixture for 15 minutes in the Iron coil through microwaves. Results are given in Figure 4.3.

64

Here the progress of reaction is reported in terms of the % mass of the oil and efficiency of the

reaction. It can be seen from the results that the yield of oil is following the same pattern as that

of cement catalyzed reaction with slight variations. This might be due to the presence of similar

chemical compounds present both in cement and kaolin [131]. Both of them are composed of

silicates. Slight variations in yield and significant difference in the chemical composition of bio-

oil can be attributed to the difference in crystalline structure as well as porosity and extensive

dehydrated nature of cement [132]. Unlike kaolin cement has significant number of pores,

molecular holes and almost anhydrous crystals which are responsible for the stabilization of

some of the most active free radicals, condensations, cyclisation and even splitting apart the

detached OH and H produced during the degradation of cellulosic matter in this process.

65

1:1 2:1 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

4

5

6

7

8

9

% w

eigh

t of o

il


Figure 4.3 Biomass to catalyst weight optimization for the Kaolin catalyzed pyrolysis.

66

4.5 Time optimization for kaolin catalyzed microwave metal interaction Pyrolysis

This study was conducted by varying the time between of 5-50 minutes. Each of these time

optimization experiments were performed in triplicate and results are given in table 3.6. and

shown in Figure 4.4. The amount of residue decreases with increase in the reaction time with an

appropriate increase in the amount of liquid and gaseous product. It can be seen from the figure

that the process yield maximum of oil when the time of reaction is 25 minutes. Beyond this there

is no change in the amount of oil and this was selected as the optimum time for reaction.

67

0 10 20 30 40 50

0

1

2

3

4

5

6

7

8

% w

eight

of o

il

Time (minutes)

Figure 4.4 Time optimization for kaolin catalyzed microwave metal interaction Pyrolysis

68

4.6 Optimization of gauge of the wire for Iron coil used as antenna for the microwave

assisted catalytic pyrolysis of biomass using kaolin as catalyst.



having a gauge of 1.6mm ,2.7mm ,and 3.3 mm. Each of the coil was used for heating a mixture

of the fine powder of biomass and cement catalyst in 7:1 ratio (B C) for 1:5 minutes. The height

of each of coil was 1.4cm, its internal diameter was 4.3 mm and external diameter was 4.8 mm.

Optimization studies for clikered (brick powder) catalyst using iron coil antenna.

4.7Clinkered brick powder weight optimization for the microwave metal interaction

pyrolysis of biomass using Iron coil as antenna

Bricks are baked at temperatures as high as1800C0 [133]. Some of these get overheated and

converts into a form called burnt or clinkered bricks. These form a material having properties

both like clinkered and vitreous material [134]. This material can be characterized for its unique

crystal structure and complex chemical composition like the composite material [135]. It is a

material formed by the extensive dehydration and is capable of retaining water, free radicals and

other active moieties [136]. It is believed that this material may reduce water contents of the bio

oil by avoiding the reaction between hydroxyl radicals with hydrogen [137]. This may encourage

the condensation, rearrangement, hydrogenation and de-oxygenation of the bio oil for the

formation of high quality liquid fuel. In order to have effective catalysis the relative biomass to

catalyst ratio was investigated by varying the weight of water hyacinth to clinker as; 11to110.

Each of the experiment was conducted in triplicate and by heating that mixture for 15 minutes in

the Iron coil inside the baked clay reactor. Results are shown in figure 4.5. It can be seen from

the table 3.8, that clinker powder have significantly different activity than kaolin and cement

catalyst. Unlike the two it forms less quantity of water. This might be due to the highly

anhydrous nature of catalyst which avoids interactions between water forming moieties. The

amount of oil was also found to vary with variation in the amount of catalyst. Just like kaolin and

cement catalyst both the yield of oil and % efficiency of the process was found greater at lower

concentration of the catalyst. This might be due to the possible agglomeration and settling down

of catalyst at high concentration and the suspended form of catalyst by the vapours and gases of

69

medium in the lower concentration. It was based on high efficiency of the process and high

concentration of oil 101 ratio was selected as the optimum for further work.

70

1:1 2:1 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

2

4

6

8

10%

we

igh

t of o

il


Figure 4.5 Biomass to catalyst weight optimization for the clinker catalyzed pyrolysis

using Iron coil antenna

71

4.8 Time optimization for clinkered catalyzed and iron antenna (microwave metal


Economy of a process may depend upon a number of factors including the input energy, cost of

the raw material as well as catalyst and speed of reaction. The input energy is one of the

important time dependent parameter. Longer process times are associated with greater

consumption of power and fuel. Reaction time optimization studies may ensure maximum yields

as well as save fuel and power. This study was conducted in the range of 5-50 minute. Each of

these time optimization experiments were performed three times and average of the three was

reported table in 3.9 Figure 4.5 that the amount of residue decreases with increase in the reaction

time with an appropriate increase in the amount of liquid and gaseous product. It can be seen

from the table that the process maximum yield of oil when the time of reaction is 20 minutes.

Beyond this there is no change in the amount of oil and this was selected as the optimum time for

reaction.

72

0 10 20 30 40 50

0

1

2

3

4%

wei

ght o

f oil

Time(minutes)

4.6 Time optimization for the clinkered catalyzed reaction

73

4.9 Optimization of gauge of the wire for Iron coil used as antenna for the microwave

assisted catalytic pyrolysis of biomass using clinker as catalyst



having a gauge of1.6mm,2.7mm and 3.3 mm. Each of the coil was used for heating a mixture of

the fine powder of biomass and clinker catalyst in 91 ratio (B C) for 15 minutes. For each of the

experiment the mixture was loaded to the Iron coil inside the baked clay reactor and placed on a

baked clay disc. The height of each of the coil was 1.4 cm, its internal diameter was 4.3 mm and

external diameter was 4.8 mm.

GC-MS analysis of bio-oil obtained after pyrolysis of Biomass.

4.10 Chemical composition of the bio oil obtained by microwave metal interaction

pyrolysiss of biomass in an iron coil antenna

The oil obtained by microwave metal interaction pyrolysis of biomass contains 27 compounds.

This contains 19 compounds of oxygenated nature, 13 of which have low oxygen contents and

six are highly oxygenated. However the total oxygen contents of the oil was found only 15.14 %.

The oxygen content of preliminary bio-oil is in the range of 40%. While that of the upgraded oil

is 20-30%. This results relatively good quality oil. This oil also contain four hydrocarbons and

four nitrogenous compounds. It contains 7.87 % hydrocarbons in addition to 8.83 % of the

nitrogen containing compounds. Unlike the bio oil obtained by conventional pyrolysis it contains

a very small fraction of the furan and its derivatives [138]. The only one of furans is furan

methanol in the highest concentration of 2.29 %. It does not contain any anhydro sugar however

contains carbonyl compounds [139]. Most of the compounds are aromatic in nature which

indicates that this pyrolysis follow different mechanism than the conventional pyrolysis. This can

be supported by the presence of acetylene gas in the gaseous mixture. Where addition reaction of

acetylene in the presence of iron results the formation of benzene [140].This reaction is believed

as giving oil of different type and upgraded nature due to the faster and volumetric heating

through microwaves. Here the selectivity of products is kinetic as well as catalytic in nature.

74

Figure 4.7 GC –MS spectra of bio –oil obtained after pyrolysis of Biomass using Iron coil antenna.

, 16-Nov-2016 + 13:15:55

4.11 6.11 8.11 10.11 12.11 14.11 16.11 18.11 20.11 22.11 24.11 26.11 28.11 30.11 32.11 34.11 36.11

Time0

100

%

biomass h -1 Scan EI+

TIC

1.96e9

11.31

7.37

6.79

4.86 6.45

10.818.91

7.68

9.86

14.46

13.76

12.85

11.90

35.41

22.0018.27

14.90

17.44

16.8815.86

19.12

21.72

21.1419.93

32.93

29.8126.1824.27

22.18

23.3425.25

27.02 29.3028.00

32.59

30.95

35.28

34.62

33.76

35.85

75

Table 4.1 GC-MS analysis of the pyrolysate obtained in Iron coil without catalyst.

(Oxygen Contents = 15.14 %) (Hydrocarbons=7.87)

S.No

Retention

time

Name Molecular

Weight

Relative %

Concentration

1 6.45 2,4-Hexadienenitrile , 93 0.562012

2 7.37 C5H6O22-Furanmethanol ,

(O = 0.74)%

98 2.291968

3 8.91 C6H8O , 2-Cyclopenten-1-

one, 2-

methyl- ,

(O = 0.3)%

96

1.805478

4 10.81 C6H8O , 2-Butenal, 2-

ethenyl- ,

(O = 0.30)%

96

1.814418

5 11.31 C7H7NO2 , Carbamic acid,

phenyl ester ,

(O =4.1 )%

137

17.64911

6

11.90

C17H20O3 , 3-

Oxaspiro[5.5]undecane-1,5-

dione, 4-methyl-3-phenyl- ,

(O = 0.2)%

272

1.252134

7 12.85 C8H16 , 3-Octene, (Z)- ,

112 0.327457

8 13.76 C7H8O , Phenol, 3-methyl- ,

(O = 3.2)%

108 15.707

9

14.90 C8H12O . Ethanone, 1-(1-

cyclohexen-1-yl)- ,

(O =0.4 )%

124

3.430634

76

10 16.88 C8H10O , Phenol, 2,3-

dimethyl- ,

(O = 1.3)%

122

1.55863

11 17.44 C8H10O , Phenol, 3-ethyl-

(O = 0.3)%

122

2.971787

12 18.27 C10H8 , Azulene

128

4.969995

13 19.12 C10H10O2 , Phenol, 4-

ethenyl-, acetate

(O = 0.5)%

162

2.896274

14 21.72 C11H10 ,

Benzocycloheptatriene

142

1.34685

15 22.00 C8H10N2O , Urea, 1-

methyl-1-phenyl- ,

(O = 0.6)%

150 5.702975

16 22.18 C11H10 , Benz\

ocycloheptatriene ,

142

1.224279

17 24.27 C7H13NO4 , dl-2-

Aminopimelic acid , 1

(O = 0.2)%

175

0.571572

18 26.18 C22H31NO5 ,Acrylic acid,

3-(3,4,5-trimethoxyphenyl)-,

(octahydroquinolizin-1-

yl)methyl ester ,

(O = 0.3)%

389 1.55169

19 29.81 C14H17NO9 , Tetraacetyl-

d-xylonic nitrile ,

(O = 0.05)%

343

0.145906

77

20 32.93 C17H31F3O2 , 3-

Trifluoroacetoxypentadecane

,

(O = 0.2)%

324

2.564134

21 34.62 C20H18O2 ,9,10-

Ethanoanthracene, 9,10-

dihydro-11,12-diacetyl- ,

(O = 0.1)%

290

1.46353

22 35.28 C17H31F3O2 , 3-

Trifluoroacetoxypentadecane

,

(O = 0.2)%

324

2.564134

23 35.41 C20H36O2 , Z,Z-4,16-

Octadecadien-1-ol acetate ,

(O = 0.9)%

308

8.974637

24 35.85 C24H38O4, Diisooctyl

phthalate

(O =2.1 )%

390

13.29198

25 36.12 C10H10Cl2O2, 1,1-

Dichloro-2-methyl-3-(4,4-

diformyl-1,3-butadien-1-

yl)cyclopropane

(O = 0.1)%

232

0.694352

26 4.85 C5H5N , 2,4-

Pentadienenitrile ,

79

0.857843

78

4.11 Effect of cement catalyst on product distribution of the pyrolystae obtained by the


Cement catalyzed microwave metal interaction pyrolysis of the biomass is intended for

upgrading the bio oil. Unlike the preliminary bio oil produced by the conventional pyrolysis of

biomass, this bio oil was found almost immiscible with water [46]. While the preliminary bio oil

of the conventional pyrolysis contains 33% water. This brownish thick material was soluble in

the organic solvent both of polar and non-polar nature. Both the catalyzed and un-catalyzed

microwave metal interaction of biomass is upgrading the bio oil as compared to the conventional

pyrolysis. Here bio oil is up graded by reducing the amount of water and lowering the oxygen

contents or increasing the amount of hydrocarbons. In case of catalyst like cement these are the

active pores, molecular holes and the solid acid base behavior which is responsible for stabilizing

the active moieties, holding oxygen and facilitating the hydrogenation, cyclization and

aromatization of the products formed. This can be observed in table 4.3 from the GC-Ms analysis

of the bio oil produced by this cement catalyzed microwave metal interaction pyrolysis of

biomass in iron coil. This oil is composed of 16 compounds unlike 26 compounds produced by

the un catalyzed reaction. The concentration of hydrocarbons is relatively less than the un-

catalyzed reaction. This might be due to the easy exchange of oxygen and aromatization capacity

of the cement Figure 4.6 - 4.1 table. That is why it contains 52.09 % aromatic compounds, the

greatest fraction in which is that for phenolic compounds. This oil also contains fluorinated

compounds the source of which is Teflon tap around the reactor and glass lid of the reactor. This

may give fluorine or compounds of fluorine which react with the active moieties produced by

decomposition of biomass. Unlike the bio oil produced by conventional pyrolysis of biomass this

contains very small quantity of furans i.e. 3.03 % of Furan methanol. This oil also contains some

nitrogenous compounds the source of which is mainly plant based nitrogen or the nitrogen of air

present in small quantities in the initial stages. The oxygen content for this oil is 15.58 which is

far less than those observed for conventional pyrolysis. However a little bit greater than those for

un-catalyzed reaction. The reason is presence of adsorbed oxygen on the active sites and its

desorption at high temperature and reaction with active moieties stabilized there

79

Figure 4.8 GC-MS spectra of bio –oil obtained after cement catalyzed pyrolysis of Biomass using Iron coil antenna.

a

, 16-Nov-2016 + 11:00:47

4.11 6.11 8.11 10.11 12.11 14.11 16.11 18.11 20.11 22.11 24.11 26.11 28.11 30.11 32.11 34.11 36.11

Time0

100

%

biomass e -2 Scan EI+

TIC

4.28e8

11.25

5.30

3.92

7.33

6.80

5.65

6.07

8.907.51

8.54

10.82

14.42

13.73

12.8111.90

35.4514.44

35.43

27.1221.9718.24

17.4216.84

14.8921.94

19.08

26.90

22.01

24.17

32.94

31.7729.7328.60

30.23

35.24

32.97

34.62

35.46

35.48

35.97

36.19

80

Table 4.2 GC-MS analysis of the oil obtained after cement catalyzed pyrolysis of Biomass (Total

oxygen contents = 15.58)

S.N

o

Retention

time

Name and Formula M.Wt Peak area

1 5.30 C7H8 , Toluene , 92 2.471137

2 7.33 C5H6O2 , 2-Furanmethanol , (O =

0.98 )%

98 3.036746

3 11.25 C6H6O, Phenol , 94 (O = 3.45 ) % 94 20.30851

4 13.19 C34H38N4O6 ,Hematoporphyrin ,

(O = 0.69)%

598 4.366075

5 13.73 C7H8O , Phenol, 3-methyl- , 108 (O

=1 )%

108 19.21

6 17.42 C16H14Cl6O4 , 1,45,8-

Dimethanonaphthalene-2,3-diol,

5,6,7,8,9,9-hexachloro-

1,2,3,4,4a,5,8,8a-octahydro-, , (O =

1.54 )%

480 1.936864

7 18.24 C7H6F2 ,2,4-Difluorotoluene ,

128

7.755235

8 21.97 C11H19N3O , Bicyclo[2.2.1]heptan-

2-one, 4,7,7-trimethyl-,

semicarbazone , (O = 3.64)%

209 6.619576

9 24.23 C30H61NO5Si3 , Prost-13-en-1-oic

acid, 9-(methoxyimino)-11,15-

bis[(trimethylsilyl)oxy]-,

599 2.283593

81

trimethylsilyl ester, (O = 0.30 )%

10 27.12 C7H13NOS2 , Dithiocarbamate, S-

methyl-,N-(2-methyl-3-oxobutyl)- ,

(O = 0.35 )%

191 4.226434

11 32.94 C17H31F3O2 , 3-

Trifluoroacetoxypentadecane , (O =

0.38)%

324 3.908219

12 35.13 C14H15O4P , Phosphinic acid,

di(phenoxymethyl)- , (O = 0.25)%

278 1.110205

13 35.24 C17H30O2 , 9,12-Hexadecadienoic

acid, methyl ester , (O =0.57)%

266 4.815228

14

35.45

C11H18O2 , Cyclohexanone, 2,2-

dimethyl-5-(3-methyloxiranyl)-,

[2α(R*),3α]-(.+-.)-

(O =1.76)%

182 10.03465

15 35.57 C19H24N2O2 , Curan-19,20-diol,

16,17-didehydro-, (19S)- , 312 (O

=0.44)%

312 4.381399

16 36.11 C33H49NO2 , 6-Azacholest-4-en-7-

one, 6-benzyl-3α-hydroxy- (O

=0.23)%

491 3.535434

82


microwave assisted pyrolysis in iron coil

Oil from Kaolin catalyzed reaction was analyzed for its components using GC-Ms. The result of

this study are presented in table 4.4. It can be seen from the table that this oil contains 29

compounds. This number is almost equal to the number of compounds formed by the un

catalyzed reaction. It contains 10.83 % hydrocarbons. This is greater than the uncatalysed

reaction. The uncatalyzed reaction produce 7.87% hydrocarbons. This is because that the

complex silicate aluminosilicate kaolin is catalyzing the hydrogenation of carbon moieties and

discourage the oxygenation through acceptance of active oxygen moieties. That is why the

oxygen contents of this oil is 13.49% which is less than those for uncatalyzed reaction. The

difference is due to the active hydrated sites. Unlike the conventional pyrolysis of biomass this

oil does not contain greater quantities of furans. Here is only 3.21 % of furan methanol. In this

bio oil produced by kaolin catalyzed reaction phenols are found in greater abundance. This is the

due to the combine action of metal catalysis, silicate catalysis and the unique mode of heating

through microwave metal interaction.

83

Figure4.9 GC –MS-spectra of bio –oil obtained after kaolin catalzed pyrolysis of Biomass using Iron coil antenna.

, 16-Nov-2016 + 12:31:20

4.17 6.17 8.17 10.17 12.17 14.17 16.17 18.17 20.17 22.17 24.17 26.17 28.17 30.17 32.17 34.17 36.17

Time0

100

%

biomass g -1 Scan EI+

TIC

1.30e9

11.28

7.356.80

5.31

4.01

4.656.47

10.808.92

8.579.84

14.42

13.74

12.82

11.90

21.98

18.26

14.88

17.42

16.8515.85

19.08

21.47

20.8719.75

35.43

32.92

31.80

29.81

24.2322.59

23.48

26.18

25.22

27.23 29.24

31.40

35.28

33.92

35.54

84

Table 4.3 GC-MS analysis of the pyrolysate obtained in Iron coil using kaolin as catalyst

(19 compounds)[Oxygen =13.49%

S.No

Retention

Time

Name and Formula M.Wt.in

gram

Relative %

Concentration

1 5.31 C7H8 , Toluene 92 2.297575

2

7.35 C5H6O2 , 2-

Furanmethanol

(O = 1.08)%

98

3.321989

3 8.57 C8H,Bicyclo[4.2.0]octa- 1,3,5-triene 104 1.630069

4 8.92 C6H8O , 2-Butenal, 2- ethenyl-

(O = 0.43)%

96

2.590251

5 10.80 C6H8O ,2-Butenal, 2- ethenyl-

(O = 0.39)%

96

2.367033

6 11.28 C6H6O , Phenol

(O = 3.71)%

94

21.80394

7 12.82 C6H12N2 , Cyclohexanone,

hydrazine

112

3.032467

7 13.74 C7H8O , Phenol, 3- methyl-

(O = 2.44)%

108 16.5807

8 14.88 C7H8O2 , Phenol, 2- methoxy-

(O = 1.022.440.343.710.43)%

124 3.961191

85

9 16.85 C8H10O ,Phenol, 2,6- dimethyl-

(O = 0.19)%

122

1.471461

10 17.42 C7H10Si , Silane, 1,3-

butadiynyltrimethyl-

122

3.201906

11 18.26 C10H8 , Azulene 128 6.918488

12 19.08 C10H10O2 ,Phenol,4- ethenyl-, acetate

(O = 0.68)%

162

3.454911

13 21.47 C7H10Si , Silane, 1,3-

butadiynyltrimethyl-

122

1.53317

14 21.98 C9H10O2,2-Methoxy-4- vinylphenol ,

(O = 1.81)%

150 8.510862

15 22.59 C19H21NO4 Tricyclo[4.3.1.1(2,5)]und

e c -3-ene, 10-

methyl-10-(p- nitrobenzoyl)oxy-

(O = 0.1)%

327 0.606986

16 24.23 C11H14N2 , 5-IT ,

174

1.358615

17 27.23 C25H44N2O5S , 2- Myristynoyl

pantetheine ,

(O = 0.17)%

484

1.153

86

18 29.81 C18H34O3 , Ricinoleic acid

(O = 0.10.170.11.81

0.680.191.022.440.343.710. 4

3 ) %

298

0.881378

19 31.80 C17H31F3O23- ne

Trifluoroacetoxypentadeca

(O = 0.2)%

324

2.199177

20 32.92 C17H31F3O2,3Trifluoroacetoxypentadecane

(O = 0.2)%

324 2.974218

21 35.43 C10H16O , 1-Ethynyl-1- cyclooctanol

(O = 0.47)%

152 4.556598

22 35.54 C17H32O2 , 7-Methyl-Z- tetradecen-1-ol

acetate

(O = 0.1)%

268

1.023627

23 36.15 C19H13BrClNO3,3-[3-Bromophenyl]-7-

chloro-3,4- dihydro-10-hydroxy-

1,9(2H,10H)-acridinedione

(O = 0.06)%

417

0.603927

87

Effect of clinkered catalyst on pyrolysis of Biomass in Iron –coil antenna.

4.13 Effect of clinkered brick catalyst on product distribution of the pyrolystae obtained

by the microwave assisted pyrolysis in iron coil

Results of GC-Ms analysis of the bio oil obtained by clinker catalyzed reaction of microwave

metal interaction pyrolysis of water hyacinth in iron coil reactor are presented in table 4.4. This

reaction gives 29 compounds major fraction of which is composed of the substituted aromatic

compounds mainly phenols. The reason for the formation of this large number of compounds is

the very high temperature almost near the melting point of iron and the highest activities of the

clinker at this high temperature. It is also expected that the clinker catalyst becomes active

absorbing material at the high temperature due to enhancement of its dielectric properties at high

temperature. One of the reason for the greater quantity of aromatics in bio oil is the

aromatization favoured at very high temperature [141]. The reason for large number of

oxygenated compounds is also very high temperature which is the cause of rapid desorption of

oxygen moieties entrapped by the catalyst in molecular holes and pores [142]. Despite of large

number of oxygenated compounds the oxygen contents of the oil is less than those for un-

catalyzed reaction. These are 11.4 % of oxygen contents for this catalytic reaction and 15.15%

for the un-catalyzed reaction. The reason is stabilization of oxygen moieties by the active

catalyst. However the hydrocarbons are less than those for un-catalyzed reaction. This is because

of the interaction of catalyst sites bearing adsorbed oxygen with the hydrocarbon moieties

produced by the polymerization of excited acetylene and other unsaturated hydrocarbon moieties

[65]. A significant number of nitrogenous compounds are observed in the table. The source of

which are two; plant based nitrogen and small quantities of the nitrogen of air present in the

reactor at the start and entrapped in the pores of catalyst [143].

88

Figure 4.10 GC –MS spectra of bio –oil obtained after clinkered catalyzed pyrolysis of Biomass using Iron coil antenna.

, 16-Nov-2016 + 11:47:05

4.17 6.17 8.17 10.17 12.17 14.17 16.17 18.17 20.17 22.17 24.17 26.17 28.17 30.17 32.17 34.17 36.17

Time0

100

%

biomass f -1 Scan EI+

TIC

9.87e8

11.29

5.30

4.84

4.64

7.366.78

6.46

8.90

8.55 10.819.04

9.89

35.43

35.41

14.44

13.74

12.82

11.90

32.92

32.1021.9818.27

14.88

17.43

16.8615.30

19.09

21.49

20.87

29.82

27.03

24.26

22.1824.12

22.27

26.1724.76

29.4527.24

28.71

31.93

30.47

34.45

34.29

34.21

35.54

35.58

35.61

36.18

36.38

89

Table 4.4 GC-MS analysis of the pyrolysate obtained in iron coil using clinker as catalyst

(%O=11.4)

S.

No

Retention

Time

Name and Formula M.Wt

in

grams

Relative %

Concentration

1 4.84 C5H4N2O2 , Pyridine, 2-nitro- , 124 (O

=0.25)%

124

1.006022

2 5.30 C7H8 , Toluene , 92 92 2.185517

3 7.36 C5H6O2 , 2-Furanmethanol , 98 (O

=0.75)%

98

2.32365

4 8.90 C6H8O , 2-Butenal, 2-ethenyl- , 96 (O

=0.45)%

96

2.734026

5 10.81 C7H12 , Cyclopentane, ethylidene- 96 2.111382


(O =3.10)%

18.23091

7 11.90 C7H10O , 2,4-Heptadienal, (E,E)-

(O = 0.008)%

110

2.031718

8 12.82 C6H8O2,3-Methylcyclopentane-1,2-

dione

(O = 0.57)%

112

2.01167

9 13.74 C7H8O , p-Cresol

(O = 0.67)%

108

4.563655

90

10 14.44 C7H8O , Phenol, 3-methyl- , (O = 1.43)% 108 9.671263

11 14.88 C8H12O , 5-Hexen-2-one, 5-methyl-3-

methylene- , 124

(O = 0.45)%

124

3.514829

12 16.86 C8H10O , Phenol, 2,6-dimethyl-

(O = 0.06)%

122

1.539282

13 17.43 C7H9N , 6-Amino-6-methylfulvene 107 2.950488

14 18.27 C10H8 , 4-Phenylbut-3-ene-1-yne , 128 5.779719

15 19.09 C8H8O , 6- Methylenebicyclo[3.2.0]hept-

3-en-2- one

(O = 0.29)%

120

2.226832

16 21.49 C8H7N , Indolizine 117 1.223169

17 21.98 C9H10O2 , 2-Methoxy-4-vinylphenol

(O = 1.20)%

150

5.679391

18 24.26 C18H22N2O , Cyclohex-2-enone, 3-[2-(1H-

indol-3-yl)ethylamino]-5,5-

dimethyl-

(O = 0.14)%

282

2.592589

19

27.03

C17H31F3O2,3Trifluoroacetoxypentadecane

(O = 0.16)%

324

1.651171

20 27.24 C7H15Cl , Heptane, 4-chloro- 134 1.216544

91

21 29.82 C17H31F3O3-Trifluoroacetoxypentadecane

(O =0.24)%

324

2.501148

22 31.93 C14H24O2 , 2-Propenoic acid, undec-10-enyl

ester (O = 0.07)%

224

0.503654

23 32.10 C40H82OHexadecane,1,1-bis(dodecyloxy)-

(O =0.19 )%

594

3.679223

24 32.92 C16H34O , 2-Hexadecanol (O = 0.25)% 242 3.852118

25 34.29 C17H31Cl , 7-Heptadecyne, 1- chloro- 270 0.886162

26 34.45 C17H33Cl , 7-Heptadecene, 1-chloro- 272 1.102273

27 35.43 C18H32O2 , 17-Octadecynoic acid

(O = 0.87)%

280 7.624713

28 35.95 C13H17NO4 , 1- Oxaspiro[4.5]decan-3-

carboxylic acid, 2-oxo-4-cyano-, ethyl ester

(O = 0.20)%

251 0.820864

29 36.18 C25H34O7 , Acetic acid, 13- acetoxymethyl-

17-acetyl-9-hydroxy- 10-methyl-3-oxo-

2,3,6,7,8,9,10,11,12 ,

(O =0.13)%

446

0.548826

92

Results for Copper coil antenna

4.14Cement weight optimization using copper antenna

Catalyst was employed for two purposes; increasing the yield of the process in terms of the bio

oil or decreasing the amount of residue and improving the quality of bio oil. In this regard the

weight of catalyst was optimized for ensuring both or any of the above mentioned in addition to

the catalyst economy. The relative amount of catalyst was optimized by varying the relative

weight of catalyst with respect to biomass in the range of 11 to 101. Each of the experiment was

carried out in triplicate and the average is reported in figure 4.10. Significant difference in the

relative mass of the fractions as well as efficiency can be seen with variation in the relative mass

of catalyst. Where the efficiency of the process was determined using the following formula.

Variation in the amount of oil can be corelated to the availability of catalytic sites which are

initially offered by a static system and then due to the rapid formation of the gaseous product and

vapours thoroughly mixed catalyst comes to a suspended form resulting a fluidized system.

Where the produced gases and vapours acts as medium. It can be seen from the figure that the

amount of oil varies in a regular way until the maximum amount of oil. It can further be

observed that the amount of oil is lower at high concentration of catalyst relative to the amount

of biomass. This is because that at high concentration of catalyst the chance of rapid settling and

aglomeration of the catalyst is greater resulting greater quatities of the catalyst in the bed which

lead to the extensive cracking and formation of energetic moities as well as char. At the bed

greater quantities of active species are produced which does not get quenched and stabilized due

to the to aglomerated and greater quatntities of catalyst in the bed rather than suspended catalyst.

There is more charing and gassification that is why the amount of both gases and residue inreases

while that of bio oil decreases. With decreasing amount of catalyst until 15 ratio of the biomass

and catalyst the amount of oil increased to a maximum and then decrease is observed. This

decrease is due to the non availability of sufficient sites for stabilization reaction [65 ]. In case of

the lower concentrations of catalyst these are the insufficient sites which are responsible for the

lower concentration of oil however sufficient for the gasification of the biomass at the operating

high temperature of the system [144 ]. The gases obtained were found combustible and are

93

believed as composed of producer gas, methane and acetylene in addition to the water vapours [

145]. Unlike simple thermocatalytic conversion of biomass [146], this catalytic and microwave

metal interaction pyrolysis of biomass have different mechanisim here the oxides of metals may

act as microwave absorber which enhances the heat contents of the system and ensures smoother

pyrolytic degradation. The structural features of the catalyst are responsible for stabilisation of

some of the reactive species and determining the chemical nature of the resulting oil and gaseous

products of pyrolysis of biomass.

94

1:1 2:1 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

17.0

17.5

18.0

18.5

19.0

19.5

20.0%

wei

ght o

f oil

Biomass:catalyst ratio

Figure 4.11 Biomass to catalyst weight optimization for the cement catalyzed reaction in

copper coil.

95

4.15 Time optimization for cement catalyzed and copper antenna (microwave metal


The yield of reaction may depend upon the time of exposure to the microwave flux in a copper

antenna [147]. This is because that the amount of heat and temperature of copper coil is

dependent on the time of exposure to microwaves [148 ]. Where both the temperature and heat

are responsible for the net quantity of fractions of products of pyrolysis and the nature of

products [149]. Time optimization reactions were carried out for this cement catalyzed

microwaves assisted reaction in order to save energy and obtain maximum yield. This study was

conducted in the range of 5-50 minute. Each of these time optimization experiments were carried

out in triplicate and average results are reported in figure 410. Decrease in the amount of residue

and increase in efficiency can be observed with variation in reaction time. This was also

associated with increase in the amount of liquid and gaseous product. It can be seen from the

table that the process give maximum yield of oil when the time of reaction is 25 minutes. Beyond

this there is no change in the amount of oil and this was selected as the optimum time for

reaction.

96

0 10 20 30 40 50

0

5

10

15

20%

wei

ght o

f oil

Time (minutes)

Figure 4.12 Time optimization for the cement catalyzed reaction.

97

4.16 Optimization of the gauge of wire for copper coil antenna

This process of the pyrolytic conversion of biomass into bio oil uses the interaction of

microwaves with copper coil which produce large quantity of heat. This heat is utilized for the

thermal degradation of biomass. This heat is produced due to changes in the energy and speed of

electrons on the surface of copper. These depend upon the skin depth which is the fraction of

surface through which the microwaves penetrates [149] Where skins depth of each and every

metal is characteristic. Increase in the number of skins may increase the amount of generated

heat and the number of reflections of microwaves . Number of skins may depend upon the shape

of the metal in which it is employed for example strip, wire and cylinder. It has been reported by

our group that tightly coiled wires can produce larger quantities of heat for effective pyrolysis as

compared to strips and cylinders . Here the amount of heat depends upon the number of turns of

coil and even the diameter of the coil which ensures repeated reflections and skin penetrations. It

is also expected that variation in gauge of the wire may also changes the amount of heat [150].

Variation in the gauge affect the amount of heat in two ways; variation in the number of turns,

which varies the number of skins and even interactions and it may also play role in transfer and

storage of heat. In this pyrolytic conversion of biomass it is the generated heat which is

responsible for the yield and nature of bio oil. The effect of gauge of antenna wire on the amount

of bio oil was investigated in four set of experiments. The gauge of wire for these experiments

was based on the size of available copper wires in the local market of electrical industry. The

antenna coils for each set of experiments were made of 2.5, 1.7, 1.5 and 0.9 mm wires. Each of

this experiment was conducted using 51 ratio of the biomass to catalyst. The results of this study

are presented in table 3.14. It can be seen from the results that variation in the gauge results

changes in the amount of oil as well as gases. This is due to the variation in the amount of heat as

well as the catalytic activity of copper surface. Variation in surface changes the amount of oil

and gas accordingly.

98



Kaolin was used as the catalyst for upgrading preliminary bio oil produced by the microwave

metal interaction pyrolysis of water hyacinth in copper coil reactor. This silicate based catalyst

may affect the yield of the fraction of product oil, gas and char by variation in its ratio with

respect biomass due to the number and availability of sites for catalysis [151]. In order to have

maximum yield of oil as well as efficiency of pyrolysis the relative weight of this catalyst was

optimized in the range of 11-110 weight ratio (Catalyst Biomass). Each of the experiment was

conducted by heating that mixture for 25 minutes in the copper coil antenna through

microwaves. Results are given in table 3.13and Figure 4.15.











99

1:1 2:1 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

11

12

13

14

15

16

% w

eigh

t of o

il

Biomass :catalyst ratio

Figure 4.13 Biomass to catalyst weight optimization for the kaolin catalyzed pyrolysis of

Biomass in copper coil antenna.

100

4.18 Time optimization for kaolin catalyzed and copper antenna (microwave metal



antenna. This is because that the amount of heat and temperature of copper coil is dependent on

the time of exposure to microwaves [147]. Where both the temperature and heat are responsible

for the net quantity of fractions of products of pyrolysis and the nature of products [148]. Time

optimization reactions were carried out for this kaolin catalyzed microwaves assisted reaction in

order to save energy and obtain maximum yield. This study was conducted in the range of 5-50

minute. Each of these time optimization experiments were carried out in triplicate and average of

the three is reported in figure 414. Decrease in the amount of residue and increase in efficiency

can be observed with variation in reaction time. This was also associated with increase in the

amount of liquid and gaseous product. It can be seen from the table that the process give

maximum yield of oil when the time of reaction is 25 minutes. Beyond this there is no change in

the amount of oil and this was selected as the optimum time for reaction.

101

0 10 20 30 40 50

0

2

4

6

8

10

% we

ight o

f oil

Time (minutes)

Figure 4.14 Time optimization for the kaolin catalyzed reaction

102


pyrolysis of biomass using copper coil as antenna

Burnt bricks are composite materials mainly composed of silicates and oxides of metals [152]. In

addition this s a porous material having active sites [153]. This material was used as catalyst for

improving the yield of bio oil produced in this microwave metal interaction pyrolysis of water

hyacinth. Its use as catalyst in the present work is also intended for upgrading the bio oil.

Variation in the relative weight of this porous composite material may help to find out the ratio

responsible for improving the yield of oil or efficiency of the process. It may also enable the

selectivity of product fraction. In addition to the yield up-gradation of the bio is also correlated to

the active sites where the optimum quantity of active sites depends upon the quantity, particle

size and mode of applying the catalyst. In the present work fine powder of this catalyst was

thoroughly mixed with fine powder of the biomass in weight ratios ranging from 11-110. Each of

the experiment was conducted in triplicate. The mixture was exposed to the microwaves in

copper coil reactor for 30 minutes and the products obtained were condensed using cold traps

and condenser system. Results are presented in figure 4.15. It can be seen from the table3.18 that

clinker powder have significantly different activity than kaolin and cement catalyst. Unlike the

two it forms less quantity of water. This might be due to the highly anhydrous nature of catalyst

which avoids interactions between water forming moieties. The amount of oil was also found to

vary with variation in the amount of catalyst. Just like kaolin and cement catalyst both the yield

of oil and % efficiency of the process was found greater at lower concentration of the catalyst.

This might be due to the possible agglomeration and settling down of catalyst at high

concentration and the suspended form of catalyst by the vapours and gases of medium in the

lower concentration. It was based on high efficiency of the process and high concentration of oil

10:1 ratio was selected as the optimum for further work.

103

1:1 2:1 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

2

4

6

8

10%

wei

ght o

f oil

Biomass:catalyst ratio

Figure 4.15 Biomass to catalyst weight optimization for the clinker catalyzed reaction.

104

4.20 Time optimization for clinker catalyzed and copper antenna (microwave metal



antenna [121]. This is because that the amount of heat and temperature of copper coil is

dependent on the time of exposure to microwaves [147]. Where both the temperature and heat

are responsible for the net quantity of fractions of products of pyrolysis and the nature of

products [148]. Time optimization reactions were carried out for this cement catalyzed

microwaves assisted reaction in order to save energy and obtain maximum yield. This study was

conducted in the range of 5-50 minute. Each of these time optimization experiments were carried

out in triplicate and average of the three was reported in figure 416. Decrease in the amount of

residue and increase in efficiency can be observed with variation in reaction time. This was also




reaction.

105

0 10 20 30 40 50

0

2

4

6

8

10

% w

eight

of o

il

Time (minutes)

Figure 4.16 Time optimization for the clinker catalyzed reaction.

106

4.21Optimization of gauge of the wire for copper coil used as antenna and clinker as





the fine powder of biomass and clinker catalyst in 91 ratio (B C) for 35 minutes.

4.22 Characterization of oil obtained after pyrolysis of Biomass using copper coil antenna

The effect of catalyst on the chemical composition of pyrolysate was investigated using four set

of experiments. In each set of experiment copper coil of the optimum dimensions was used as

antenna and heat generating device (Copper wire 2.5 mm, coil external diameter 4.8 cm . In the

first set of three experiments biomass was pyrolysed in a copper coil and microwaves as source

of energy. This was used as reference. The chemical composition of this was determined using

GC-MS and presented in table 4.7. It can be seen from the table that the pyrolysate was resolved

into 21 compounds. The distribution of these is described as 2 types of the compounds are

nitrogenous in nature and forming a total of 26.217%, 5 hydrocarbons which contributes to

13.189 % of the waxy oil, 5 compounds were found rich in oxygen and 6 compounds of less

oxygenated nature were found in this pyrolysate. Each of them contributes a total of 11.696%

and 39.868 % respectively. Despite of having this large number of oxygenated compounds the

total oxygen contents of the oil is 16.66 % which is far less than for conventional thermal and

catalytic Three of the 21 compounds were found halogenated in nature. It can be seen from the

chemical composition of the oil in table 4.7 that this pyrolysate contains significant quantities of

the nitrogenous compounds. The source of which is plant based nitrogen which it absorbs from

water in the pond. Part of that is inorganic nitrogen and part of that is in the form of complex

organic molecules including protein [154 ]. Another source of nitrogenous compounds is the

small quantities of air in the reactor before the reaction which form nitrogenous compounds with

the reactive moieties produced during the reaction. The chance for this relatively less due to the

flushing out of air by the products of pyrolysis, inert nature of nitrogen and the relatively small

quantity of the air present in the reactor. Unlike the previous investigations this pyrolysate

contains significant quantities of the hydrocarbons [155]. This also contains less quantity of

furans and it derivative [156]. Unlike the previous investigations this product does contain

107

anhydrosugar despite of having a large quantity of the oxygenated compounds. The presence of

halogenated compounds can be attributed to two sources; it has been described in the

experimental section that the reactor is fastened with Teflon tape for quick fit closure of the

reactor and strength of reactor. This may decompose into halogens and result the formation of

halogenated compounds. Another source is plant based halides [157].

108

Figure 4.17 GC- MS spectra of oil obtained after pyrolysis of Biomass using copper coil antenna.

, 10-Nov-2016 + 13:35:15

4.19 6.19 8.19 10.19 12.19 14.19 16.19 18.19 20.19 22.19 24.19 26.19 28.19 30.19 32.19 34.19 36.19

Time0

100

%

biomass d -1 Scan EI+

TIC

3.58e8

11.26

7.33

6.795.313.91

10.77

8.897.65 10.74

14.45

13.72

12.80

11.32 12.82

14.46

22.02

17.42

14.89

17.40

14.9316.86

18.26

19.10

21.5220.88

35.80

33.14

31.32

29.4824.25

32.39

35.7534.75

35.94

36.11

36.52

109

(Oxygen Contents = 1.27 + 0.528 +5 .727 + 1.24 + 0.94 + 2.31 + 1.00 + 0.11 + 0.63 + 0.1 +

1.72 + 0.1 + 0.2 + 0.13 + 0.16 + 0.5 = 16.66%)

Table 4.5 GC-MS analysis of the pyrolysate obtained using copper coil antenna without

catalyst.

S.NO

Retention

Time

Name and Formula M.Wt

in

grams

Relative %

Concentration

1 5.31 1,5-Hexadien-3-yne, 2-methyl- ,

92

2.001

2 6.79 N-Methyl-7-azabicyclo(2,2,1)hept-2-ene

,

109 1.693

3 7.33 2-Furanmethanol ,

(1.27%)

98

3.883

4 8.89 Cyclopentene, 3-ethyl-

96

1.873

5 10.77 2,4-Hexadienal, (E,E)-

(0.528%)

96

3.168

6 11.26 Carbamic acid, phenyl ester

(5.727%)

137

24.524

7 12.80 1,2-Cyclopentanedione, 3-methyl-

(1.24%)

112

4.334

8 13.72 Benzyl alcohol ,

(0.94%)

108

6.369

9 14.45 Phenol, 3-methyl-

(2.31%)

108

15.608

10 14.89 Mequinol ,

(1.00%)

124

3.91

11 16.86 1-Bromo-2-(4-hydroxyphenyl)ethane ,

(0.11%)

200 1.413

110

12 17.42 Silane,1,3-butadiynyltrimethyl-

122

4.464

13 18.26 4-Phenylbut-3-ene-1-yne ,

128

5.535

14 19.12 Phenol, 4-ethenyl-, acetate

(0.63%)

162

2.122

15 19.12 Phenol, 4-ethenyl-, acetate

(0.63%)

162

2.122

16 21.52 Naphthalen-1,4-imine-9-carboxylic acid,

1,2,3,4-tetrahydro-, ethyl ester

(0.1%)

217 0.658

17 22.02 2-Methoxy-4-vinylphenol

(1.72%)

150

8.076

18 22.09 Cholestan-3-one, dimethylhydrazone,

(5α)- ,

428 0.582

19 29.48 Decane, 1-(ethenyloxy)- ,

(0.1%)

184

0.612

20 31.27 3-Pyrazolin-5-one, 2,3-dimethyl-1-

phenyl-4-(3,4,5-

trimethoxyphenylcarbonylmethylamino)-

(0.2%)

411 0.775

21 33.14

3,3,3-Trifluoro-N-(2-fluorophenyl)-2-

(trifluoromethyl)propionamide

(0.13%)

289 2.485

22 34.75 2-(Di-acetyl methyl) cyclo octanone

oxime

(0.16%)

239 0.774

23 35.80 2-Decen-1-ol, (E)-

(0.53%)

156

5.131

111



Cement is a clinkered material obtained by extensive dehydration and decarbonation reaction at

very high temperature. It is mainly composed of silicates. These silicates are characterized for

their unique structural and chemical features [158]. It has a porous structure and also have

molecular cages [159]. It may also have electrostatic forces in the molecular holes and pores

[160]. It was reported in our previous work that this material may stabilize the free radicals and

retard water and highly oxygenated compound formation [161]. It is also expected that this

catalyst may also help in the formation of aromatic compounds. This catalyst is composed of

compounds like oxides of metals which have dielectric properties [162] and making it active

toward the microwaves. The use of cement in this microwave heated and assisted pyrolysis

system is partially due to the capacity of upgrading the bio oil and partly because of microwave

activity which is expected to further enhance the yield and quality of bio oil. It can be seen from

table 4.8for reaction without catalyst and only in copper coil; the yield of oil is only 10% while

in table 4.7 for the cement catalyzed reaction, it is 20%

Catalyst is also expected to change the nature of products. It can be seen from table 3.7 and 3.8

that both the number and nature of products of bio oil is different for catalyzed and un-catalyzed

products. Bio oil formed by un-catalyzed reaction of the microwave assisted reaction in copper

coil give 21 compounds and those of cement catalyzed oil contains 9 and a small fraction of an

unidentified compound. This indicates that catalyst has role in determining both the nature and

number of pyrolysis products through stabilizing highly reactive free radicals. Further it can also

be observed that the oxygen contents of the un-catalyzed product is 16.66% and those for cement

catalyzed oil are 14.73%. In case of the oil produced by un-catalyzed reaction most of the

oxygenated compounds rich in oxygen and in this case most of them are either phenolic or have

relatively smaller proportion of oxygen. This oil also contains hydrocarbons greater than the un-

catalyzed reaction. This give a total of 11.6% hydrocarbons and the un-catalyzed reaction

produce only 3.88 % of hydrocarbons. As compared to the oil produced by conventional thermal

and catalytic pyrolysis of biomass, this microwave assisted catalytic and non-catalytic pyrolysis

give oil of highly improved nature. This bio-oil is almost immiscible with water, containing low

112

oxygen contents and also contain some fraction of hydrocarbons or hydrocarbon like compounds

e.g. phenols and other aromatics.

113

Figure 4.18 GC – MS spectra of bio –oil obtained after cement catalyzed pyrolysis of Biomass using copper coil antenna.

, 08-Nov-2016 + 14:19:18

3.96 5.96 7.96 9.96 11.96 13.96 15.96 17.96 19.96 21.96 23.96 25.96 27.96 29.96 31.96 33.96 35.96

Time0

100

%

biomass 8 11 16-3 Scan EI+

TIC

6.02e9

11.27

7.36

14.45

13.74 22.0517.44

14.9218.31 19.07 35.4832.98

114

Table 4.6 GC-MS analysis of the pyrolysate obtained in copper coil using cement as

catalyst (Total oxygen contents = 14.73)

S.NO

Retention

Time

Name and formula M.Wt Relative %

Concentration


(O = 1.37%)

98

4.20

2 11.27 Phenol ,

(O = 5.68%)

94

33.40

3 13.74 Phenol, 3-methyl- ,

(O = 4.16%)

108

28.07

4 14.92 5-Hexen-2-one, 5-methyl-3-

methylene- ,

(O = 0.79%)

124 5.36

5 17.44 Phenol, 2,3-dimethyl- ,

O = 0.77%) 122

5.89

6 18.31 Azulene 128

7.68

7 22.05 Ethanone, 1-(2-hydroxy-5-

methylphenyl)- ,

(O = 1.66%)

150 7.80

8 32.98 4-Undecene, 2-methyl-, (E)- 168 3.92

9 35.48 11-Tridecyn-1-ol ,

(O = 0.30%)

196

3.65

115



Kaolin or China clay is aluminosilicate and belongs to the kaolinite family of clays [163]. It is

associated with extensive number of water molecules [164]. Unlike the clinkered brick powder

and cement this hydrated material is composed of calcium alumino silicates with oxides of heavy

metals [165]. Its catalytic properties are here expected due to the silicate network. This material

is associated with molecular holes which expectedly have the power to stabilize the reactive and

unstable moieties produced by the cracking of biomass molecules [166]. In order to investigate

the catalytic properties of this material it was mixed with biomass powder in optimized quantity

and pyrolysed in copper coil reactor in the microwave oven. The GC-Ms analysis of the oily

product is given in table 4.10. It can be seen from the table that it is composed of 19 compounds

unlike 21 compounds of the un-catalyzed reaction. The total quantity of hydrocarbons is 7.07%

unlike 3.88 % of the un-catalyzed process. The total oxygen contents of this oil is 15.66% while

those for the un-catalyzed is 16.66%. As compared to the un-catalyzed process it contains less

quantity of the nitrogenous compounds. It contains no halogenated compounds. The reason may

be the acidic character of the kaolin which inhibit the formation of these compounds [167].

116

Figure 4.19 GC-MS spectra of bio – oil obtained after kaolin catalyzed pyrolysis of Biomass using copper coil antenna.

, 10-Nov-2016 + 12:44:32

4.02 6.02 8.02 10.02 12.02 14.02 16.02 18.02 20.02 22.02 24.02 26.02 28.02 30.02 32.02 34.02 36.02

Time0

100

%

biomass c -1 Scan EI+

TIC

9.41e8

11.26

7.35

6.785.314.83

6.41

10.778.907.66

9.80

14.45

13.73

12.81

11.90

22.01

18.2717.41

14.89

16.86

15.84

19.08

21.4920.90

35.7533.1131.6531.09

24.2422.19 26.2124.92 27.30 29.8328.7434.82

33.64

36.08

117

Table 4.7 GC-MS analysis of the pyrolysate obtained in copper coil using kaolin as

catalyst (19 compounds) (Hydrocarbons = 7.07) [15.66%]

S.NO Retention

time

Name and Formula M.Wt % Conc

1 5.31 1,3,5-Cycloheptatriene

92

1.36

2 6.78 Furan, 3-methyl-

(% O = 0.27)

82

2.15

3

7.35 2-Furanmethanol ,

(% O = 0.70)

98

4.85

4 8.90 2-Cyclopenten-1-one, 2-

methyl- ,

(% O = 0.21)

96

1.24

5

10.77

1,4-Butanediol, 2,3-

bis(methylene)- ,

(% O = 0.65)

114

2.33

6 11.26 Carbamic acid, phenyl

ester , (% O = 5.33)

137 22.82

7 12.81 1,2-Cyclopentanedione,

3-methyl-

(% O = 1.32)

112 4.63

8 13.73 Phenol, 3-methyl- (% O

= 0.95)

108 6.39

118

9 14.45 Phenol, 3-methyl-

(% O = 2.50)

108

16.92

10 14.89 5-Hexen-2-one, 5-

methyl-3-methylene-

(%O = 0.68)

124 5.29

11 16.86 1H-1,2,3,4-Tetrazole-

1,5-diamine, N(1)-[(2-

methoxyphenyl)methyl]-

(% O = 0.10)

220 1.39

12 17.41 Silane, 1,3-

butadiynyltrimethyl- ,

122 5.62

13 18.27 4-Phenylbut-3-ene-1-yne 128 5.71

14 19.08 6-Methylenebicyclo

[3.2.0]hept-3-en-2-one

(% O = 0.41)

120 3.89

15 21.49 Indolizine

(% O = 1.53)

117

1.47

119

16 22.01 4-Hydroxy-2-

methylacetophenone ,

(% O = 0.70)

150 7.17

17 24.24 2-H-Inden-2-one, 1,3-

dihydro-, oxime ,

(% O = 0.11)

147 1.01

18 33.11 1-Hexadecanol, 2-

methyl- , (% O = 0.18)

256 2.68

19 35.75 13-Heptadecyn-1-ol ,

(% O = 0.20)

252

3.08

120


by the microwave assisted pyrolysis

Clinkered or burnt brick is hard material obtained by excessive heating of the clay bricks. This

may pass through extensive dehydration, decarbonation, and clinkerization by excessive heating

and burning [168]. It is mainly composed of the silicate skeleton of diverse chemical and

structural features [169]. In the present work clinkered brick powder was used as catalyst for

upgrading the bio-oil produced by the microwave metal interaction pyrolysis of biomass in a

copper coil at as high temperature as the melting point of copper [170]. Usually this high

temperature is favourable for the gasification of biomass [171]. However in this case it is the

unique way of heating, presence of microwaves and catalytic effect of metal coil as well as

clinker, oil of highly upgraded nature is produced [177]. It is also expected that metal oxides

present in the clinkered brick powder offer unique environment of electrical forces due to their

dielectric nature [172]. The effective catalytic activity of the clinkered brick powder can be seen

from table 3.18. Unlike the uncatalyzed process it forms greater number of the compounds. This

may be attributed to a number of factors including the flux of microwaves which is different for

the catalytic process. In the presence of catalyst it is the presence of dielectric material which is

responsible for the greater flux and change in the electrostatic properties of catalyst and overall

electric charge environment [173]. That is why greater number of compounds can be observed in

bio-oil of this clinker catalyzed process. It has been mentioned in our previous work that cement

and clinkered material may act as Lux- Flood acid and bases and have properties of stabilizing

and retaining active oxygen moieties [174]. Therefore responsible avoiding the formation of

excessive quantities of water and oxygenated compounds. It can be seen from table 3.18 that as

compared to the oil produced by un-catalyzed process the oil of clinker catalyzed reaction

contain greater quantities and number of hydrocarbons.It contains five hydrocarbons while the

oil obtained by un-catalyzed process contain only two hydrocarbons. The total concentration of

hydrocarbons is 19.43% in bio oil of this clinker catalyzed reaction while that for un-catalyzed

reaction is 3.88%. It can be seen from table 4.9 that most of the oxygenated compounds are

aromatic in nature the most abundant of which is phenol having a concentration of 20.09%. It

also contains nitrogenous compounds, the source of which is described in discussion on bio oil

produced from reaction using no catalyst. Despite of having greater number of compounds its

oxygen contents is less than the bio oil produced from microwave metal interaction pyrolysis

121

using no catalyst. The oxygen contents for clinkered catalyzed bio oil are 13.67% and those for

the un-catalyzed reaction are 16.66%.

122

Figure 4.20 GC –MS spectra of bio –oil obtained after clinkered catalyzed pyrolysis of Biomass using copper coil antenna.

, 10-Nov-2016 + 12:00:19

4.02 6.02 8.02 10.02 12.02 14.02 16.02 18.02 20.02 22.02 24.02 26.02 28.02 30.02 32.02 34.02 36.02

Time0

100

%

biomass b -1 Scan EI+

TIC

1.72e9

11.30

7.36

5.29

4.84

6.77

6.45

8.90

8.54

10.80

9.89

11.34

14.49

13.77

12.87

11.91

22.03

18.2714.90

17.48

16.8815.90

19.17

21.53

20.9019.79

35.7633.12

28.1024.27

22.21

22.92

25.74 27.11 32.6331.2129.85

29.21

34.82

35.89

123

Table 4.8 GC-MS analysis of the pyrolysate obtained in copper coil using clinker as

catalyst (O=13.67 %)

S.NO

Retention

time

Name of compound M.Wt Relative %

Concentration

1 4.84 Pyridine ,

79

1.03

2 5.29 Cyclobutene, 2-

propenylidene- ,

92 1.98


(O= 1.53%)

98

4.69

4

8.9

Cyclopentane,

ethylidene-

96 2.69

5 10.80 4,5-Nonadiene

96

3.14

6 11.30 Phenol,

(O= 3.42%)

94

20.09

7 11.91 1,4-Diphenyl-1-

pentanone

(O=0.13%)

238 1.93

8 12.87 Cycloheptanone, 2-

ethyl- ,

(O=0.69%)

140 6.00

9 13.77 Phenol, 3- methyl-,

(O=0.82%)

108

5.51

10 14.49 p-Cresol ,

108 (O= 1.8%)

108

12.15

11 14.90 Phenol, 2- methoxy-

,

124

4.43

124

(O= 1.14%)

12 15.90 Cyclohexane

carboxaldehyde,

3,3-dimethyl-5-

oxo-

(O=0.59%)

154 4.11

13 17.48 Phenol, 2,3-

dimethyl-

(O=0.47%)

122

2.04

14 18.27 Naphthalene

128

9.48

15 19.17 Benzaldehyde, 2-

methyl-

(O=0.66%)

120

0.83

16 21.53 Indolizine ,

117

0.60

17 22.03 2-Methoxy-4-

vinylphenol

(O=2.02%)

150

3.41

18 24.27 1H-Indene, 3- methyl-

130

2.14

19 25.78 2- Trimethylsiloxy-

6-hexadecenoic

acid, methyl

ester ,

(O=0.1%)

356

0.28

20 28.10 2-Oxazolamine,

4,5-dihydro-5-

(phenoxymethyl

)-N-

311

1.39

125

[phenylamino)carbonyl]

(O=0.23%)

21 33.12 1-Dodecanol,

3,7,11-trimethyl-

, (O=0.15%)

228 1.38

22 35.76 9-Octadecynoic

acid

O=0.03%)

280 1.03

23 35.89 1-Hexadecanol, 2-

methyl-

(O = 0.1%)

256

1.98

126

Optimization studies for different catalyst using Aluminium coil Antenna.

4.26Relative weight of catalyst (cement) and Biomass optimization.

Aluminium belongs to III A group of the periodic table and is associated with a number of

catalytic properties due to vacant orbitals in the valence shell. This metal may react with air and

can generate as high temperature as 3000 oC. It melts at 660 oC and spark in the microwave

oven generating greater quantity of heat. It may heat up to its melting point on exposure to the

microwaves [175]. Earlier workers worked with it in microwaves for metallurgy and metal

recovery. In the present work aluminum coil was used as heat generating and microwave

receiving antenna for the microwave metal interaction pyrolysis of water hyacinth as biomass.

This process was further catalyzed by cement which is a clinkered material having molecular

holes and pores. It is intended to increase the oil yield and over efficiency of the pyrolysis. It is

also used for up gradation of the bio oil produced during this pyrolytic reaction. The relative

weight of catalyst is important in optimizing the catalytic activity of any catalyst. In order to

have an effective and economical amount of catalyst, the weight of catalyst was optimized in the

range of 11to110 ratio of catalyst to biomass. The progress of reaction and effectiveness of the

catalyst was monitored in terms of the relative % weight of product fractions. Results of this

study are presented in figure 4.17. In the start this system offers a static catalytic system however

the later on catalyst carry over/entrainment due to the vapours and gaseous products converts it

into a turbulent system which may behave like fluidized bed. Violent reaction was observed in

the aluminium coil. This might be due to two reasons; microwave activity of the aluminium and

the reaction of cement with aluminium or oxygen from the biomass with aluminum. The reaction

of aluminium with oxygen may generate excessive quantities of heat which results violence in

reaction. This can be confirmed from the corroded coil after reaction. It can be seen from the

table that this reaction generate excessive quantities of gases and relatively smaller quantities of

oil. Further the efficiency of reaction is also greater. Variation in the amount of catalyst changed

the amount of oil. It can be observed that the amount of oil is far greater in case of greater

concentration of catalyst. The reason for this is aglomeration and settling of the bulk of catalyst.

It is also because of the extensive cracking which results the formation of greater quantites of

gaseous product. At relatively lower concentration it was the availabilty of catalyst in suspended

form which offer active sites for the stabilization, condensation and quenching of active moities

127

resulting in greater quantities of oil. At still lower concentration of catalyst the number of active

sites decreases resulting decrease in the quantity of oil.

It can be seen from the figure that this process give highest oil yield when the catalyst and

biomass are in 1:4 and 1:5 ratio. Therefore 1:5 ratio was selected as the optimum ratio for

onward reactions.

128

1:1 2:1 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

6

7

8

9

10%

wei

ght o

f oil

Biomass :catalyst ratio

Figure 4.21optimization of catalyst(cement) weight using aluminium coil antenna.

129

4.27 Time optimization for cement catalyzed and aluminium coil antenna for microwave

metal interaction Pyrolysis

Optimum time for the microwave assisted and cement catalyzed reaction in aluminium coil was

investigated by varying reaction duration in the range of 5-50 minutes. Each of these time

optimization experiments were carried out in triplicate and average of the three is reported in

figure 4.22. The yield of reaction was investigated in terms of the amount of oil and %

efficiency. It can be observed from figure 4.22 that increase in reaction duration is associated

with increased efficiency and yield of the oil. Where both the temperature and heat are

responsible for the net quantity of fractions of products of pyrolysis and the nature of products

[176]. This study was carried out to take measure for saving energy and obtaining maximum

yield. Decrease in the amount of residue and increase in efficiency can be observed with

variation in reaction time. This was also associated with increase in the amount of liquid and

gaseous product. It can be seen from the table that the process give maximum yield of oil when

the time of reaction is 25 minutes. Beyond this there is no change in the amount of oil and this

was selected as the optimum time for reaction.

130

0 10 20 30 40 50

0

2

4

6

8

10

% we

ight o

f oil

Time (minute)

Figure 4.22Time optimization for the cement catalyzed reaction in aluminium coil.

131

4.28 Optimization of the gauge of wire for aluminium coil

Microwave metal interaction results sparking and heat generation. The amount of heat generated

may depend upon the nature of metal and the area interacting with microwaves [21]. It may also

depend upon the thermal conductivity and heat capacity of metals. Variation in the area and mass

of the aluminum was investigated as a function of the gauge of wire used for the preparation of

coil. This controlls both the amount of heat and the way of interaction of active species with the

aluminum resulting variation in the amount of product fractions and the nature of products as

well. In this pyrolytic conversion of biomass it is the generated heat which is responsible for the

yield and nature of bio oil. The effect of gauge of antenna wire on the amount of bio oil was

investigated in four set of experiments. The gauge of wire for these experiments was based on

the size of aluminum wires available in the local market. The antenna coils for each set of

experiments were made of 2.5, 1.7, 1.5 and 0.9 mm wires. Each of this experiment was

conducted using 51 ratio of the biomass to catalyst. The results of this study are presented in

table 3.24. It can be seen from the results that variation in the gauge results changes in the

amount of oil as well as gases. This is due to the variation in the amount of heat as well as the

catalytic activity of copper surface. Variation in surface changes the amount of oil and gas

accordingly.


metal interaction pyrolysis of biomass using aluminium coil as antenna

Variation in the amount of catalyst and mode of applying the catalyst is responsible for variation

in extent of reaction and even the nature of reaction [177]. The amount of kaolin catalyst with

respect to biomass was varied in the range of 11to110 mass ratio. The results of this study for

aluminium coil reactor are presented in figure 4.23. It can be seen from the results that the oil

fraction is less in case of greater proportion of catalyst. However a net increase was observed

with lowering the amount of catalyst until 15 ratio. After this there was constancy in the amount

of oil.




132








133

1:1 2:1 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

6

7

8

9

10

% w

eigh

t of o

il

Biomass : catalyst ratio

Figure4.23Biomass to catalyst weight optimization for the kaolin catalyzed reaction

134

4.30 Time optimization for kaolin catalyzed pyrolysis of Biomass aluminium coil antenna

for microwave metal interaction Pyrolysis

The yield of reaction may vary with variation in the amount of input energy required for

reaction. In case of this microwave assisted reaction the amount of this energy depends upon the

time of exposure to the microwaves. Longer exposure times results the generation of greater

quantities of heat which is responsible for the conversion of more and more biomass into the oil,

gas and char fractions. In this batch type reactor time optimization is necessary to avoid

excessive use of energy and ensure maximum yield. Optimum time of this kaolin catalyzed

reaction was investigated in the range of 5-50 minute. Each of these time optimization

experiments were carried out in triplicate reported in Figure 4.24. Decrease in the amount of

residue and increase in efficiency can be observed with variation in reaction time. This was also




reaction.

135

0 10 20 30 40 50

0

2

4

6

8

10

12

% we

ight o

f oil

Time (minutes)

Figure4.24 Time optimization for the kaolin catalyzed reaction in aluminium coil reactor

136

4.31 Optimization of the gauge of wire for aluminium coil




heating a mixture of the fine powder of biomass and kaolin catalyst in 5:1ratio (B C) for

25minutes.


pyrolysis of biomass using aluminium coil as antenna

The amount of clinkered brick powder was optimized in the range of 1:1 to1:10 catalyst to

biomass weight ratio for aluminium coil microwave assisted reaction. The idea behind was to

select that ratio of catalyst which gives maximum amount of oil. Each of this experiment was

conducted in triplicate. The results of this study are presented in Figure 4.25. It can be seen from

the results that the process give less oil at 11 ratio which increases with decrease in the relative

amount of catalyst at onward ratios. A corresponding increase in efficiency can also be observed

with increasing amount of biomass. This is because of the greater heat capacity of clinker and

relatively less temperature and heat in the system. Decreasing amount of catalyst increases the

net amount of heat available for reaction rather than absorbed by greater quantity of clinker. And

clinker is only stabilizing the active species. Based on greater quantity of heat 15 ratio was

selected for onward work.

137

1:1 2:1 3:1 4:1 5:1 6:1 7:1 8:1 9:1 10:1

5

6

7

8

9

10

11%

weigh

t of o

il

Ratio of biomass with respect to catalyst

Figure4.25 Biomass to catalyst weight optimization for the clinker catalyzed reaction.

138

4.33 Time optimization for clinker catalyzed microwave metal interaction Pyrolysis in

aluminium coil

Time optimization studies for the clinkered catalyzed reaction in aluminium coil was carried out

in the range of 5-50 minutes. The results of this study are presented in Figure 4.26. It can be

observed that the reaction starts even in the initial 2-3 minutes that is why the products of

reaction including small quantity of water, gases and residue were observed when the reaction

was carried out for 5 minutes. After words significant changes in the amount of products were

observed. It can be observed from the table 3.29 that the amount of oil is maximum when the

time for reaction was 25 minutes. Beyond this no significant change were observed in the

amount of oil or efficiency of the process therefore this was selected as the optimum time for

reaction.

139

0 10 20 30 40 50

0

2

4

6

8

10

12

% we

ight o

f oil

Time (minute)

Figure 4.26 Time optimization for the clinker catalyzed pyrolysis in aluminium coil .

140

4.34 Optimization of gauge of the wire for Aluminium coil used as antenna for the





heating a mixture of the fine powder of biomass and kaolin catalyst in 5:1ratio (B C) for

25minutes.

4.35 GC-Ms analysis of the bio oil obtained by microwave assisted pyrolysis of biomass using

Aluminium coil

Biomass was pyrolysed in an aluminium coil using microwaves as source of energy. The oil

obtained at the optimum conditions was analyzed using GC-MS. The results of this analysis are

presented in table 4.14. It can be seen from the table that the bio oil was resolved into 18

compounds. Most of these are of oxygenated nature. However the total oxygen contents are

relatively less than those obtained by conventional pyrolysis [180]. These are only 14.7 % unlike

30 % of the bio oil obtained by conventional fast pyrolysis. This oil also contains nitrogenous

compounds, the source of which is plant based nitrogen [181]. While the source of halogen is

most probably the Teflon tap used for leak proofing and mechanical strength of the reactor. The

only two hydrocarbons found in this oil are 3-Nonene and1, 3, 5-Cycloheptatriene. Where 1,3,5-

Cycloheptatriene is the most abundant among the two and is cyclic in nature. This microwave

assisted process involves cracking, cyclization and aromatization. The proof for which is the

greater concentration of phenolic compounds. The most abundant of these is phenol 25.18 %

while in 23.37% relative abundance is 3-methylphenol. This aromatization is believed as

catalyzed by the aluminium oxide and even aluminium during the interaction of active moieties

with the coil. This oil contains a very small fraction of the only one furan i.e. furan methanol.

Unlike the previous investigations this product does contain anhydrosugars despite of having a

large quantity of the oxygenated compounds. Another characteristic feature of the oil is the

absence of water in this pyrolysate [182].

141

Figure 4.27 GC-MS spectra of bio - oil obtained from the pyrolysis of Biomass without catalyst.

, 17-Nov-2016 + 13:43:12

4.17 6.17 8.17 10.17 12.17 14.17 16.17 18.17 20.17 22.17 24.17 26.17 28.17 30.17 32.17

Time0

100

%

biomass m -1 Scan EI+

TIC

4.97e8

8.86

6.43

4.98

4.61

4.27

6.07

5.36

7.48

7.27

8.66

8.05

8.87

10.67

10.30

9.81

9.28

14.78

10.98

12.30

12.01

12.90

14.3913.1922.01

20.55

16.02

15.40 17.4916.4220.0118.90 20.80

24.4522.09

24.06

25.0825.78

26.90 27.9328.78

29.20

142

Table 4.9 GC-MS analysis of the oil obtained in Aluminium coil without catalyst(O

=12.62%)

S.NO

Retention

Time

Name and Formula M.Wt in

grams

Relative %

Concentration

1 4.61 C7H8BrN , N-Vinylpyridinium

bromide , 185

185

0.706817

2 4.98 C7H8 , 1,3,5-Cycloheptatriene 92 3.309737

3 6.07 C5H7N3O2 , 3,4-Dimethyl-4-nitroso-

2-pyrazolin-5-one (O = 0.6)%

141 2.956659

4 6.43 C5H6O2,2-Furanmethanol (O =

2.02)%

98 6.247701

5 7.48 C5H7NO , 2-Pentenenitrile, 5-

hydroxy-, (E)-

(O = 0.5)%

97 3.30794


(O = 4.2)%

94

25.18093

7 10.30 C7H8O , Phenol, 3-methyl- (O =

1.2)%

108 23.371

8

10.98 C7H8O2 , Mequinol (O =1.5

)%

124 6.00416

9 12.01 C8H10O,Phenol, 2,5-dimethyl-

(O = 0.3)%

122

3.069225

10 12.30 C8H10O , Phenol, 3-ethyl- 5.774818

143

(O = 0.7)% 122

11

14.39 C10H11NO2,Ethyl3pyridyl)propenoate

(O = 0.2)%

177 1.540101

12 14.78 C10H14O,3,5-Heptadienal,ethylidene-

6-methyl-

(O = 0.8)%

150 8.076207

13

16.02 C9H9N , 2-Propyn-1-amine, N,N-di-

2-propynyl-

131 1.298694

14 20.01 C11H18N2O2,Acetamide, N- methyl-N-

[4-(3- hydroxypyrrolidinyl)-2butynyl]-

(O =0.1)%

210 0.717573

15

20.55 C9H18 , 3-Nonene, (E)-

126

2.798443

16

22.01 C14H28O , E-7-Tetradecenol

(O =0.2 )%

212 3.767613

17

22.09 C6H7N5O2,4-Hydrazonhydroxyimino-

4,5,6,7-tetrahydrobenzofurazan

(O = 0.2)%

1.263155

18

24.45 C7H12O2 Z-3-Methyl-2-hexenoic acid

(O =0.1)%

128

0.60872

144



Bio oil obtained by cement catalyzed microwave assisted reaction in aluminium coil was found

to contain 8.30 % hydrocarbons and 14.07 % oxygen contents. Furan methanol is the only furan

of this oil unlike those of the bio oil obtained by conventional pyrolysis which contains a large

number and concentration of furans [183]. It is because of the catalysis of cement, aluminium

and microwave flux this oil is highly upgraded and contains no water in miscible form [184].

This oil also contain nitrogenous compounds the source of which is plant based nitrogen where

this biomass contains 25 % of proteins in addition to the inorganic nitrogenous compounds. Two

major phenols contribute 39.72 % to the total. Each of the phenol and 3-methyl phenol occurs in

20.96 and 18.76% respectively. Unlike the previous investigation here in this cement catalyzed

reaction sulphur containing compounds can be observed in addition to the nitrogenous

compounds. This plant based sulphur is fixed in compounds due to the joint catalytic action of

cement, aluminum and aluminum oxide.

145

Figure 4.28 GC –MS spectra of bio-oil obtained after cement catalyzed pyrolysis of Biomass using Aluminium coil antenna.

, 16-Nov-2016 + 13:59:26

4.17 6.17 8.17 10.17 12.17 14.17 16.17 18.17 20.17 22.17 24.17 26.17 28.17 30.17 32.17 34.17 36.17

Time0

100

%

biomass i -1 Scan EI+

TIC

1.67e9

11.32

7.38

5.31

4.04

6.80

6.62

10.808.93

8.58

9.84

14.47

13.76

12.84

11.92

35.44

22.00

14.90

18.27

17.45

15.87 16.86 19.14

20.88

19.76

32.93

29.83

24.27

22.19

23.03

27.0426.18

25.25

29.6527.61

32.2830.09 31.01

35.29

34.6033.18

35.85

146

Table 3.10 GC-MS analysis of the pyrolysate obtained in Aluminium coil using cement as

catalyst (Total oxygen contents) = (15.68) %

S.NO

Retention

time

Name and Formula M.Wt in grams Relative %

Concentration

1 4.04 C3H7NO , Propanamide (O = 0.1)% 73 0.862228

2 5.3

1

C7H8 , 1,6-Heptadien-3-yne 92

0.213838

3 7.38 C5H6O2 , 2-Furanmethanol (O =

1.2)%

98

3.91025

4

8.93 C7H7NO3 , 1-Carboxymethyl-2(1H)-

pyridone

(O =0.81)%

153

1.946105

5 10.80 C6H10O2,1,4Butanediol,2,3bis(meth-

(O = 0.6)%

114 2.248237

6 11.32 C6H6O , Phenol (O =3.5%) 94 20.96237

7 12.84 C6H8O2 ,1,2-Cyclopentanedione, 3-

methyl- (O = 1.19)%

112

4.196985

8 13.76 C7H8O , Phenol, 3-methyl- (O =

0.86)%

108

18.76

9 14.90 C7H8O2, Phenol, 2-methoxy- (O

=1.13 )%

124

4.401386

10 15.87 C8H14O,2,4-Pentadien-1-ol,propyl-,

(2Z)- , 126

(O = 0.3)%

126

2.800029

147

11 17.45 C8H10O , Phenol, 3-ethyl- (O =0.4

)%

122 3.500275

12 18.27 C10H8 , Naphthalene 128 4.714476

13 19.76 C11H7F4NS,3-Benzylsulfanyl-3-

fluoro-2-trifluoromethyl-acrylonitrile

261 0.88574

14 20.88 C9H12O2,Phenol, 4-ethyl-2-methoxy-

(O = 0.1)%

152 0.800778

15 22.00 C9H10O22-Methoxy-4-vinylphenol

(O =1.5 )%

150 7.288831

16 22.19 C11H10 , 1,4-Methanonaphthalene,

1,4-dihydro-

142 0.069639

17 24.27 C17H22N2O4,2-(4-Hydroxy-4-

methyl-tetrahydro-pyran-3-ylamino)-

3-(1H-indol-2-yl)-propionic acid (O =

0.4)%

318

1.992433

18 26.18 C19H30N2O3 , N-(5-Nitro-O-tolyl)

lauramide

(O = 0.1)%

334

0.877519

19 27.04 C21H34S2,5α-Androstan-16-

one,cyclic ethylene mercaptole ,

350 1.283579

20 29.83 C25H44N2O5S,2Myristynoylpanteine

,

(O = 0.09)%

484

1.227142

21 32.83 C25H44N2O5S,2Myristynoylpantetne

,

(O = 0.1)%

484 1.075941

22 32.93 C12H24 , 4-Undecene, 5-methyl-,

(E)-

168

3.377694

148

23 34.45 C26H27N5O6 , Morphinan-4,5-

epoxy-3,6-di-ol, 6-[7-

nitrobenzofurazan-4-yl]amino- , (O =

0.1)%

505

0.661556

24 35.29 C15H16ClN3S,N-[4-(4-

Chlorophenyl)isothiazol-5-yl)-1-

methylpiperidin-2-imine ,

305

0.471745

25 35.44 C20H36O2 , Z,Z-4,16-Octadecadien-

1-ol acetate ,

(O = 0.8)%

308

8.396805

26 19.14 C10H10O2 , Phenol, 4-ethenyl-,

acetate ,

(O = 0.6)%

162

3.072431


by the microwave assisted pyrolysis

Clinkered or burnt brick reactions in aluminum coil produce an upgraded oil. This oil was

analyzed by GC-Ms. The results of this study are presented in table 4.16. It can be seen from the

results that this oil contains less number of compounds as compared to the uncatalysed reaction.

This contains only 8 compounds. This limited number of compounds is due to the effective

stabilization of the active moieties by the active sites of catalyst. This catalyst have pores of

various size and complex silicate composition. This reaction is also catalyzed by the material of

the coil which is aluminium and small fraction of aluminium oxide deposited on the coil in the

initial stages of reaction. The oxygen contents of the oil are 16.5% which is slightly greater than

the oil obtained by un-catalyzed reaction. The reason might be activity of oxygen and oxygen

containing moieties at the coil. It can be seen from the analytical results that the oil contain

significant quantities of nitrogenous compounds. The most abundant of which is Carbamic acid,

phenyl ester having a relative concentration of 24.65% while next in concentration is 3',8,8'-

149

Trimethoxy-3-piperidyl-2,2'-binaphthalene-1,1',4,4'-tetrone. Its relative concentration is 7.84%.

It also contain p-cresol as one of the abundant compound instead of phenol present in the oil

obtained by un-catalyzed reaction. This oil contains 5.28% of the 1H-Indene, 1-methylene- as the

only hydrocarbon. It can also be seen that most of the compounds are high molecular weight.

This is because of the joint activity of catalyst and aluminium coil which facilitates the

condensation of active moieties into bigger molecules.

150

4.29 GC-MS spectra of bio –oil obtained after clinker catalyzed pyrolysis of Biomass using Aluminium coil antenna.

, 16-Nov-2016 + 14:49:31

4.11 6.11 8.11 10.11 12.11 14.11 16.11 18.11 20.11 22.11 24.11 26.11 28.11 30.11 32.11 34.11 36.11

Time0

100

%

biomass j -1 Scan EI+

TIC

2.51e9

35.91

11.31

7.40

6.855.36

4.06 10.828.95

35.42

14.48

13.75

12.84

11.91

35.32

22.01

14.9118.30

17.4416.8715.87 19.12

34.98

32.94

29.81

27.0524.27

32.28

36.00

36.05

151

Table 4.11 GC-MS analysis of the pyrolysate obtained in Aluminium coil using clinker as

catalyst. (Total oxygen contents) = (16.5%)

S.NO Retention time Name and Formula M.Wt Relative %

Concentration

1 7.41 C5H6O2 ,2-Furanmethanol ,

(O = 1.4)%

98

4.482543

2 11.31 C7H7NO2 , Carbamic acid,

phenyl ester , (O = 5.7)%

137 24.64755

3 13.75 C7H8O , p-Cresol (O = 3.2)% 108

22.0006

4 14.91 C8H12O , 3,5-Heptadien-2-one,

6-methyl-, (E)-

(O = 0.6)%

124

4.932819

5 18.30 C10H8 , 1H-Indene, 1-

methylene-

128 5.282215

6 22.01 C9H10O2 , 4-Hydroxy-3-

methylacetophenone

(O = 1.6)%

150

7.837113

7 35.32 C28H25NO7 , 3',8,8'-

Trimethoxy-3-piperidyl-2,2'-

binaphthalene-1,1',4,4'-tetrone

(O =1.8 )%

487

7.83967

8 32.42 C21H38O2Cyclopropanenonanoic

acid, 2-[(2-

butylcyclopropyl)methyl]-, methyl

ester

(O = 2.2)%

322

22.97748

152


microwave assisted pyrolysis in Aluminium coil

Kaolin catalyzed reaction in Aluminium coil is giving boi-oil of upgraded nature. It is

immiscible with water. And composed of 14 compounds as determined by the GC-Ms analysis.

The oxygen contents of this oil are 16.67% which is slightly greater than those of oil obtained by

the reaction of un-catalyzed process. This oil also contain greater proportion of the furan

methanol which is either due to the rapid escape of this compound during cracking or

stabilization by the joint action of kaolin, aluminium and aluminium oxide layer on the coil. The

three hydrocarbons contribute 7.95% to the total concentration of oil which is due to the capacity

of catalyst and coil to stabilize the active hydrocarbon moieties at this relatively lower

temperature as compared to that of iron coil and copper coil. Here the expected temperature is in

the range has slightly higher oxygen co 600-660 oC. This catalyst is also favouring cyclization

and aromatization which is clear from the greater concentration of phenolic compounds. The

most abundant of which is phenol in 28.83% relative concentration. Next in abundance is 3-

methyl phenol having a concentration 27.57 %. In addition to the nitrogenous compounds this

oil also contains fluorinated compounds. The source of fluorine is Teflon and that of nitrogen is

plant based nitrogen.

153

Figure 4.30 GC-MS spectra of bio-oil obtained after kaolin catalyzed pyrolysis of Biomass using Aluminium coil antenna.

, 17-Nov-2016 + 12:03:40

4.40 6.40 8.40 10.40 12.40 14.40 16.40 18.40 20.40 22.40 24.40 26.40 28.40 30.40 32.40 34.40 36.40

Time0

100

%

biomass k -1 Scan EI+

TIC

5.13e8

8.84

6.42

4.97

3.82

6.06

5.93

8.63

7.48

6.818.02

10.66

10.26

9.78

9.25

14.7712.2810.95

11.97

11.45

12.88

14.17

14.79

16.01 20.8416.83

18.94 19.58

22.63

22.0123.39 24.26

36.4025.13

28.4727.81 36.87

154

Table 4.12 GC-MS analysis of the pyrolysate obtained in Aluminium coil using kaolin as

catalyst (19 compounds) (oxygen contents 18.6)

S.NO Retention

time

Name and Formula M.Wt in

gram

Relative %

Concentration

1 4.97 C7H8 , 1,5-Hexadien-3-yne, 2-

methyl-

92 0.38433

2 6.42 C5H6O2 , 3-Furanmethanol

(O = 2.0)%

98

6.452728

3 7.48 C7H12O 3-Heptyn-1-ol

(O = 1.3)%

112

3.258262

4 8.63 C9H13NO2 , Ethinamate

(O = 0.6)%

167

3.306361

5 8.84 C6H6O , Phenol (O = 4.9)% 94

28.83176

6 10.26 C7H8O, Phenol, 3-methyl-

(O = 4.0)%

108

27.573

7 12.28 C8H8O2 , 2,7-Dioxa-

tricyclo[4.4.0.0(3,8)]deca-4,9-

diene (O = 1.8)%

136 7.886323

8 12.88 C10H8 , Azulene ,

128

5.300413

9

14.17 C12H18O2 , Acetate, 4-(1,1-

dimethylethyl)-1-methyl-4-

penten-2-ynyl ester , (O = 0.2)%

194 1.723399

10 14,77 C9H10O2 , 4-Ethylbenzoic acid

(O = 1.4)%

150 7.035491

11 16.01 C18H22N2O , Cyclohex-2-enone,

3-[2-(1H-indol-3-yl)ethylamino]-

5,5-dimethyl- , 282 (O = 0.07)%

282 1.249375

155

12 16.83 C16H12N4O4 ,

Furazandicarboxamide, N,N'-

diphenyl-, 2-oxide , (O = 0.1)%

324 0.706969

13

20.84

C16H25F7O2 , 3-

Heptafluorobutyroxydodecane

(O = 0.9)%

382

4.023147

14 22.63 C10H18 , Bicyclo[3.1.1]heptane,

2,6,6-trimethyl-, [1R-(1α,2α,5α

138 2.268446

156

CHAPTER-V

5.1 CONCLUSIONS AND OUTLOOK

Microwave metal interaction pyrolysis was found effective for the conversion of biomass (water

hyacinth) into highly upgraded oil. The method was faster and product effective. Three different

types of metals Iron, Copper and Aluminium were used as antenna which generated heat and as

high temperature as the melting point of metal. The reactions were carried out both in the

absence and presence of cement, clay and clinker catalyst. In each case bio oil of highly

upgraded nature was prepared. These water immiscible bio oils were found having improved

quantities of oxygen contents. Among the investigated metals and catalyst the best results were

observed for iron coil and clinker catalyst for oxygen contents i.e. 11.4% as compared 30-40%

oxygen contents of conventional pyrolysis. This oil also contains various quantities of

hydrocarbons. Among the investigated metals and catalyst the best results were observed for

copper metal and cement catalyst i.e. 13.1% hydrocarbons. These oils were found to contain

phenolic compounds the best among them is aluminium coil and kaolin catalyst i.e. 64%.These

catalyst were found to affect the yield of bio oil as well. Among the catalyst-clinkered was

found the best in enhancing the yield while among the antenna the highest yield was observed for

copper coil experiments. This process is economical in terms of the use of low cost biomass and

catalyst, low power and shorter reaction time, upgraded oil and better yield.

5.2 Future Directions

One of the most important things of this microwave interaction pyrolysis is the preparation of

microwave device which can be used as microwave pyrolyzer. One of our future plan is to

fabricate a microwave device (pyrolyzer) which can be continuously for the fast pyrolysis of

biomass. Another plan is to utilize the same device for the disposal of a Varity of waste and

conversion of coal into oil and gas. This technique will also be extended to gasification of

biomass, waste plastic and coal.

157

5.3 COMPARISON

The effect of catalyst on chemical composition of the bio oil was investigated by comparing the

GC-Ms profile of the oils obtained by the microwave metal interaction pyrolysis using different

metals as antenna and each of the kaolin, cement and clinker (burnt brick) as catalyst in separate

experiments. In case of the copper coil the oil obtained by catalysis of clinker was found the best

in hydrocarbon and oxygen contents. It contains 13.1% hydrocarbons and 13.67% oxygen

contents. In comparison to clinker, cement catalyzed reaction give oil containing 13.1 %

Hydrocarbons and 14.37 % oxygen contents. While these for kaolin catalyzed reactions are 7%

hydrocarbons and 15.66 % oxygen contents respectively.

Among the reactions carried out in aluminium coil, cement catalyzed reactions give oil of better

quality in terms of oxygen contents and hydrocarbons. The oxygen content of this oil was found

15.68% while the total hydrocarbon contents were 8.34%. In case of clinker the amount of

hydrocarbon were found to be 5.28% while the oxygen contents are 16.5 %. The amount of

hydrocarbons in the oil obtained by kaolin catalyzed reactions in aluminium coil is 7.8% and the

% of oxygen contents are 18.6.

The oil obtained by clinker catalyzed reactions in iron coil contains 9.9% hydrocarbons and 11.4

% oxygen contents. This oil for kaolin catalyzed reaction was found to contain10.7%

hydrocarbons and 13.49% oxygen. Oil obtained by cement catalyzed reactions contain 2.4%

hydrocarbons and 15.58% oxygen content.

158

CHAPTER -VI

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